JP3187484B2 - Colorant having branched poly (oxyalkylene) component and intermediates thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to novel permanent or temporary colorants, their intermediates and processes for their preparation, in particular branched poly (oxyalkylenes) having substantially poly (ethyleneoxy) moieties. A) a polychain compound having one or more polyglycidol residue segments in the side chain.

[0002]

2. Description of the Related Art In one aspect, a colorant is desired to have good water-washing properties and low stain as properties required for temporary coloring of a polymer. A colorant useful in a color code during a process or manufacturing process is provided. Furthermore, in another embodiment, the colorant is required to be non-elutable from a thermoplastic resin, particularly from a polyolefin, and in this case, the colorant is physically blended for permanent coloring.

[0003] The novel poly (oxyalkylene) of the present invention
The intermediate containing the component has a reactive site such as a reactive hydrogen atom, one or more aldehydes, amino, nitroso, nitro and the like, and is useful for producing a colorant by a conventionally known reaction.

Regarding the temporary coloring of the present invention, US Pat.
o. The poly (ethyleneoxy) substituted colorants described in US Pat. No. 3,157,633 are widely accepted in the industry. These coloring substances are usually applied to yarns such as nylon yarns before being heat set. The colorant comprises a combination of a coloring radical such as azo and one or two poly (ethyleneoxy) groups, preferably wherein the poly (ethyleneoxy) group is bonded to the coloring radical via an amino nitrogen. .

[0005] Temporary coloring of nylon is a problem.
The colored yarn, or woven woven fabric, tufted carpet is heat-set to fix the yarn more or less permanently, and the colorant is easily removed in subsequent finishing polishing operations That is not possible. Therefore, it is necessary to perform a special troublesome reduction or oxidation treatment to remove coloring.

[0006] Kuster Continuous D
With the advent of carpet dyeing techniques such as Yer, it is no longer necessary to polish nylon carpets or the like with a large amount of water before dyeing, and this polishing with water is not preferable except for the removal of temporary coloring. This water polishing process further complicates the problem environmentally, because of the large amount of water used.

Conventionally, this temporary coloring was about 0.5% based on the weight of the yarn, but recently, during the tufting operation, a higher concentration of coloring is needed to correctly identify the end of the yarn. Has been requested. When conventional colorants are used at high levels, above 0.5%, it is very difficult or even impossible to remove all the colorants after processing.

[0008] In the handling of yarns, a particularly troublesome problem arises when monitoring and detecting the end of the yarn that has broken during graphic tufting. If, for example, different yarns of different dyeability are tufted together and dyed, this different dyeability results in a color pattern or pattern. In such tufting methods using uncolored yarns, it is often difficult to distinguish different yarn types. For example, the distinction between polyamide and polyester, the distinction between lightly dyed polyamide and deeply dyed polyamide, or yarn or woven fabric,
Alternatively, it is often difficult to distinguish by physical differences in thickness.

[0009] During tufting, monitor for damage,
In order to rejoin inline and return to the original correct thread,
It is known to use coloring or dyeing substances. For example, U.S. Pat. No. 4,877,411 describes that the coloring substance is chemically affected by the yarn and the color disappears after a relatively short time.

[0010] However, it is very difficult to control the loss of color and there is a risk that the color will be inadequate at the point where it is most necessary to monitor, detect and identify the yarn. . Therefore, if a temporary colorant of a different color that can be removed by subsequent washing can be used, it is easier to repair and restore the broken yarn end.

However, conventional temporary colorants are not sufficiently washable and are not suitable for use at high enough levels to identify and manipulate individual yarn ends.

In another embodiment of the present invention, ie, where a thermoplastic resin is permanently colored, the chromophore bound to the poly (oxyalkylene) is described, for example, in US Pat.
o. No. 4,812,141. While the colorants of this patent are useful for their intended use, prolonged or intense contact with solvents often elutes significantly.

[0013]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. (1) Easily removed from yarns, particularly nylon yarns, without requiring significant washing and polishing. It is an object of the present invention to provide a temporary coloring substance that can be used.

(2) An object of the present invention is to provide a temporary coloring substance which can be used at a higher concentration than before.

(3) It is an object of the present invention to provide a temporary coloring substance having visibility suitable for identifying a yarn end.

(4) It is an object of the present invention to provide a colorant having excellent solvent non-extractability from a thermoplastic resin.

[0017]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a compound having the following structural formula and excellent detergency and non-staining properties.

C- (Z) _1-8 wherein C is a residue of a reactant having 1 to 8 nucleophilic site residues to which the Z component is bonded, wherein the Z component is at least 60% by weight of poly (oxyalkylene), said poly (oxyalkylene) having (a) at least one glycidol residue segment of 2-6 glycidol residues attached to the nucleophilic site of C. And (b) the poly (oxyalkylene) further comprises ethylene oxide (EO);
Containing one or more residues of epoxide reactants of propylene oxide (PO) or other epoxide reactants or mixtures of butylene oxide (BO), and EO, PO, BO
(C) comprising a total of 10-600 residues, or a mixture thereof, wherein at least about 75 mol% of the EO residues are present;
The ratio of the sum of -O-PO- and -O-BO- bonds to the sum of all functional oxy bonds of the glycidol residue is less than 1 and the molar ratio of EO residues to glycidol residues is 4 to 75.

The preferred embodiment in this case is as follows.

(A) The total number of the other epoxide-reactive substance residues is 150 to 400. (B) EO residue is 90% of the other epoxide reactant residue
Consisting of -100 mol%. (C) the poly (oxyalkylene) component contains at least one glycidol residue segment containing 2 to 6 glycidol residues.

(D) The poly (oxyalkylene) component contains at least one glycidol residue segment having three separate poly (oxyalkylene) branches.

(E) Each of the poly (oxyalkylene) components is independently terminated at its terminal by a hydrogen atom, acyl or a group selected from substituted, unsubstituted alkyl, cycloalkyl and aryl. (F) Poly (oxyalkylene) branches terminated by hydrogen atoms. (G) The number of Z components is 1 to 4.

Preferred colorants of the present invention have the following structural formula:

QN = N-Ar (azo) Q ₁ (N = N-Ar) _2,3 (polyazo) M = CH-Ar (methine) M = N-Ar (azamethine)

[0025]

Embedded image Ar ₃ C ⁺ (triarylmethane) DN = N-Ar (quaternary azo) wherein Q is a carbocyclic or heterocyclic aromatic group or a diazotizable amine, and may be substituted or unsubstituted. : Phenyl; naphthyl; thiazol-2-yl; benzothiazol-2
-Yl; 1,3,4-thiadiazol-2-yl; 1,
2,4-thiadiazol-5-yl; isothiazol-
5-yl; isoxazol-5-yl; 2,1-benzisothiazol-3-yl; 2-thienyl; 3- and 4-pyridyl; pyrazol-5-yl; 3- and 4-
Phthalimidyl; 1,2,4-triazol-3-yl; or 4,5 (3,3-dimethyl-1-oxotetramethylene) thiazol-2-yl; Q ₁ is M is an active methylene residue; Ar is substituted or unsubstituted: aniline; naphthylamine;
2,3,4-tetrahydroquinoline; 3,4-dihydro-2H-1,4-benzoxazine; 2-aminothiazole; 2,3-dihydroindole; carbazole; phenoxazine; phenothiazine; 2-aminothiophene; D is an aromatic heterocyclic radical containing a quaternary nitrogen atom and is unsubstituted or substituted: thiazol-2-yl;
Benzothiazol-2-yl; 1,3,4-thiadiazol-2-yl; 1,2,4-thiadiazol-5-yl; isothiazol-5-yl; 2,1-benzisothiazo- R-3-yl; pyrazol-5-yl; 1,3
4-triazol-2-yl; 3- or 4-pyridyl; or 4,5 (3,3-dimethyl-1-oxotetramethylene) thiazol-2-yl;
Wherein at least one -Z is Q, Q ₁ or -Ar
What exists in any of the.

More preferred groups of the colorant of the present invention are those having the following structural formulas for the Q-, Q ₁ , -Ar, M- and D- components.

Preferred colorants are those having an aromatic residue Q- selected from the following structural formula:

[0028]

Embedded image Wherein R ₂ is a hydrogen atom, or lower alkyl, lower alkoxy, halogen, cyano, formyl, alkanoyl,
Aroyl, thiocyano, lower alkylthio, arylthio, lower alkylsulfonyl, arylsulfonyl,-
R ₃ is a hydrogen atom; or lower alkyl, aryl, arylazo, halogen, SO ₃ aryl, carbalkoxy, unsubstituted or substituted sulfamoyl, unsubstituted or substituted carbamoyl, nitro, trifluoromethyl or arylazo. R ₄ is a hydrogen atom; cyano, formyl, carboxy, nitro, thiocyano, lower alkylsulfonyl, arylsulfonyl, trifluoromethyl, alkanoyl, aroyl, unsubstituted or substituted sulfamoyl or unsubstituted or substituted carbamoyl; Or lower alkyl, lower alkoxy, halogen, cyano, carboxy, alkanoyl, aroyl, arylazo, -SO
R ₅ is a 1-3-substituted member selected from ₃ aryl, alkylsulfonyl, arylsulfonyl, unsubstituted or substituted carbamoyl, unsubstituted or substituted sulfamoyl, alkylthio, thiocyano, 2-cyanoethylthio, 2-cyanoethylsulfonyl, or alkanoylamino; Hydrogen atom, or lower alkyl, cycloalkyl, aryl, alkylthio, arylthio, cyanomethylthio,
Halogen, alkylsulfonyl, arylsulfonyl,
A group selected from lower alkoxy, benzylthio, allylthio, unsubstituted or substituted sulfamoyl, thiocyano, or alkanolamino; R ₆ is a hydrogen atom, or alkyl, aryl, alkylthio, alkylsulfonyl,
A group selected from halogen, cyano, 2-carbalkoxyethylthio, or benzylthio; R ₇ is a hydrogen atom; or lower alkyl, halogen, nitro, lower carbalkoxy, cyano, alkylthio, 2-hydroxyethylthio, arylthio, alkylsulfonyl R ₈ is a hydrogen atom, or a group selected from lower alkyl, lower alkoxy, halogen, nitro, or unsubstituted or substituted sulfamoyl; R ₉ is lower alkyl, aryl, Cyano, lower carbalkoxy, cyclohexylcarbonyl,
R ₁₀ is a hydrogen atom; or a 1-3-substituted member selected from alkanoyl, aroyl, halogen, formyl, unsubstituted or substituted carbamoyl, thiocyano, alkylsulfonyl, arylsulfonyl, unsubstituted or substituted sulfamoyl, nitro, arylazo, or cinnamoyl; R ₁₁ is a hydrogen atom, a 1-3-substituted member selected from lower alkyl, halogen, lower alkoxy, lower alkylsulfonyl, arylsulfonyl, carbalkoxy, aryl, unsubstituted or substituted carbamoyl, unsubstituted or substituted sulfamoyl, formyl, or thiocyano; cycloalkyl, lower alkyl, aryl, alkylsulfonyl or those selected from arylsulfonyl,; R ₁₂ is a hydrogen atom; or lower alkyl, aryl, cyano, nitro, lower Karubarukoki , Carbamoyl, 1-2 substituents selected from lower alkylthio, or cyanomethyl;
R ₁₃ is selected from a hydrogen atom, lower alkyl, lower alkylthio, arylthio, carbalkoxy, halogen, lower alkylsulfonyl, or arylsulfonyl; R ₁₄ is selected from a hydrogen atom, unsubstituted or substituted alkyl, aryl, cycloalkyl, or allyl R ₁₅ is a hydrogen atom; or lower alkyl, lower alkoxy, halogen, nitro, cyano, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl,
Or a 1-2 substituent selected from aryloxy; Ar is an aromatic residue selected from the following structural formula:

[0029]

Embedded image However, in the formula, R ₁₆ is a hydrogen atom or lower alkyl, trifluoromethyl, lower alkoxy, arylthio, aryloxy, halogen, —CH ₂ —O—Z or —O—
R ₁₇ and R ₁₈ are each independently substituted with -z, linear or branched lower alkenyl; cycloalkyl; hydroxy, alkoxy, alkyl, halogen, or alkanoyloxy. A group selected from lower alkoxy, cyano, alkanoyloxy, or -LZ,
Or phenyl substituted by 2 or more;
2 straight or branched chain alkyl, and of the following structural formula:

[0030]

Embedded image Cyano, halogen, 2-pyrrolidino, phthalimidino,
Vinylsulfonyl, acrylamide, o-benzoic acid sulfonimide, a group of the following structural formula,

[0031]

Embedded image Alkyl substituted with one or more phenyl; lower alkyl, lower alkoxy, phenyl substituted with halogen, carboxy, cyano, carboxy, or acyloxy; R ₁₉ is a hydrogen atom, lower alkyl, lower alkanoylamino, lower alkoxy, R ₂₀ is a hydrogen atom; lower alkyl; lower alkyl substituted with hydroxy, acyloxy, phenyl, cycloalkyl, halogen or alkoxy; cycloalkyl; phenyl; lower alkyl, lower alkoxy, halogen, hydroxy, alkanoyl W is selected from phenyl substituted with amino, carboxy, carboxy, cyano, or alkanoyloxy; W is lower alkylene having 1-3 carbon atoms; hydroxy, halogen,
Alkylene substituted with alkoxy or acyloxy;
Vinyl; 1,2-phenylene; 1,2-phenylene substituted with lower alkyl, lower alkoxy, halogen, carboxy, or carboxy; 1,2-cyclohexylene; —O—CH ₂ —; —CH ₂ OCH ₂ — ; -SC
H ₂ —; —N (R ₂₁ ) CH ₂ —; —N (R ₂₁ ) CH ₂ C
H ₂ —; —CH ₂ N (R ₂₁ ) CH ₂ —; wherein the alkyl groups represented by R ₁₇ and R ₁₈ may be further substituted with a group selected from the following group: O-
_{R 21; -SO 2 -R 22;} -CON (R 21) R 23; -SO
_{2 N (R 21) R 23} ; -N (R 21) SO 2 -R 22; -OC
_{O-R 23; -OCO 2 R} 23; -OCON (R 21) R 23;
—SR ₂₄ or —SO ₂ CH ₂ CH ₂ SR ₂₄ ;
₂₁ and R ₂₃ are a hydrogen atom; lower alkyl; hydroxy,
Lower alkyl substituted with aryloxy, halogen, cycloalkyl, or phenyl; cycloalkyl; phenyl; phenyl substituted with lower alkyl, lower alkoxy, halogen, hydroxy, alkanoylamino, carboxy, carboxy, cyano, or alkanoyloxy R ₂₂ represents the same substituent as that of R ₂₁ and R ₂₃ except for a hydrogen atom; R ₂₄ represents R ₂₁
And in addition to those described for R _23, benzothiazole - 2-yl, benzimidazolyl - 2-yl, pyridyl, pyrimidinyl, 1,3,4-thiadiazolyl,
R ₂₅ , R ₂₆ , and R ₂₇ are each independently selected from a hydrogen atom and lower alkyl; R ₂₈ is a hydrogen atom; 1,3,4-oxadiazolyl, naphthyl, or triazolyl;
Cycloalkyl, alkyl, 2-thienyl, phenyl,
R ₂₉ is a hydrogen atom; or a 1-2 substituent selected from lower alkyl, lower alkoxy and halogen; R ₃₀ is cyano, carbalkoxy, alkylsulfonyl R, arylsulfonyl, or unsubstituted or substituted carbamoyl;
₃₁ is selected from a hydrogen atom, lower alkyl, and aryl; _R32 and _R33 are each independently selected from a hydrogen atom, lower alkyl, lower alkoxy, halogen, or -Z; wherein X is a covalent bond , Oxygen, or sulfur; L is X or —SO ₂ —, —SO ₂ N (R ₂₁ ) —,
_{-COO -, - N (SO 2} -R 22) - or -N (R
₂₁ )-wherein the compound contains at least one -Z component; wherein Q ₁ is
A monovalent or trivalent aromatic residue: -Ar ₁ -L ₂ -Ar _2- , or -Ar ₁ -L ₄ (Ar ₃ ) -Ar ₂ -where Ar ₁ , Ar ₂ and Ar ₃ are each Unsubstituted or substituted phenylene, naphthalenediyl, quinolinediyl, benzothiazoldiyl and 1,3,4-
Wherein the common substituents for Ar ₁ , Ar ₂ , and Ar ₃ are lower alkyl, lower alkoxy, and halogen; wherein L ₂ is a covalent bond ; -O-;-S
-; -SO _2- ; -SS-; -C (= O)-; -O-
C (= O) -O-; -CON (Y)-; -N (Y)-;
_{-N (SO 2 Y 1) -} ; - SO 2 N (Y) -; - NHC
(＝ O) NH—; —NHC (＝ O) —O—; arylene;
- alkylene -L ₃ - alkene -; - L ₃ - alkylene -L ₃ -; - alkylene -L ₃ - arylene -L ₃ - alkylene -; - L ₃ - arylene -L ₃ -; - alkylene -
L _3- ; -L ₃ -alkylene-arylene-alkylene-
L ₃ -; - L ₃ - alkylene -L ₃ - alkylene -L ₃
Y is a hydrogen atom or is selected from unsubstituted or substituted alkyl, cycloalkyl and phenyl; Y ₁ is selected from unsubstituted or substituted alkyl, cycloalkyl and phenyl; L ₃ is -O
-; -S-; -SO _2- ; -CO _2- ; -CON (Y)
_{-; - SO 2 N (Y} ) -; - N (SO 2 Y 1) - from those selected; L ₄ is -C (-) ₂ -Y or -N (-)
Those selected from _2; wherein, M represents one selected from active methylene residues of the following structural formulas;

[0032]

Embedded image Here, R ₃₅ is cyano, —CON (R ₃₆ ) R ₃₇ , —CO
Selected R ₃₆ and R ₃₇ are a hydrogen atom, a cycloalkyl, unsubstituted or substituted alkyl, phenyl, phenyl substituted by lower alkyl, lower alkoxy, halogen; ₂ R _36, -COR ₃₈ or -SO ₂ R _38, Stuff; R ₃₈
Is a substituent similar to R ₃₆ and R ₃₇ except for a hydrogen atom;
₃₉ is selected from lower alkyl, cycloalkyl or aryl; R ₄₀ is selected from hydrogen atom, alkyl or aryl; R ₄₁ is selected from hydrogen atom, lower alkyl, aryl or carbalkoxy;
R ₄₂ is a hydrogen atom; or a 1-2 substituted group selected from lower alkyl, lower alkoxy and halogen; R ₄₃ is lower alkenyl, lower alkyl, optionally substituted benzyl,
Hydroxyalkyl, carbamoyl alkyl, - alkylene -CO ₂ ^- M ⁺ or - alkylene -SO
₃ ^- M ⁺ ; M ⁺ is H ⁺ , Na ⁺ , K ⁺ , Li ⁺ or N
Those selected from H ₄ ^+; X ^- is Cl ^-, Br ^-, CH
A counter anion selected from ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , ZnCl ₄ ⁻² / 2; R ₄₄ is aryl or optionally substituted aryl; provided that the compound has at least one —Z component; Including.

Wherein D is selected from the following structural formulas:

[0034]

Embedded image Wherein R ₃ is a hydrogen atom; or lower alkyl, aryl, arylazo, halogen, cyano, formyl,
Carbalkoxy, nitro, thiocyano, lower alkylsulfonyl, arylsulfonyl, trifluoromethyl,
Alkanoyl, aroyl, unsubstituted or substituted sulfamoyl or unsubstituted or 1-2 substituents selected from substituted carbamoyl; R ₄ is a hydrogen atom; or lower alkyl,
Lower alkoxy, halogen, cyano, carbalkoxy,
1 selected from alkanoyl, aroyl, arylazo, —SO ₃ aryl, alkylsulfonyl, arylsulfonyl, unsubstituted or substituted carbamoyl, unsubstituted or substituted sulfamoyl, alkylthio, thiocyano, 2-cyanoethylthio, 2-cyanoethylsulfonyl, and alkanoylamino R ₃ is a hydrogen atom;
Or a lower alkyl, cycloalkyl, aryl, alkylthio, arylthio, cyano methyl thio, halogen, alkylsulfonyl, arylsulfonyl, lower alkoxy, benzylthio, arylthio, unsubstituted or substituted sulfamoyl, thiocyano or a group selected from alkanoyloxy nor amino,; R ₆ Is a hydrogen atom; or alkyl,
A group selected from aryl, alkylthio, alkylsulfonyl, halogen, cyano, 2-carbalkoxyethylthio or benzylthio; R ₇ is a hydrogen atom; or lower alkyl, halogen, nitro, lower carbalkoxy,
A 1-2 substituent selected from cyano, alkylthio, 2-hydroxyethylthio, arylthio, alkylsulfonyl, and arylsulfonyl; R ₈ is a hydrogen atom;
Or a group selected from lower alkyl, lower alkoxy, halogen, nitro, or unsubstituted or substituted sulfamoyl; R ₁₀ is a hydrogen atom; or lower alkyl, halogen, lower alkoxy, lower alkylsulfonyl, arylsulfonyl, carbalkoxy, aryl, unsubstituted or substituted carbamoyl, unsubstituted or substituted sulfamoyl, formyl or 1-3 substituents selected from the thiocyano,; R ₁₁ is a hydrogen atom, cycloalkyl, lower alkyl, aryl, alkylsulfonyl or those selected from arylsulfonyl,; R ₁₂ Is a hydrogen atom; or a 1-2 substituent selected from lower alkyl, aryl, cyano, nitro, lower carbalkoxy, carbamoyl, lower alkylthio, or cyanomethyl; R ₁₃ is a hydrogen atom;
Those selected from lower alkyl, lower alkylthio, arylthio, carbalkoxy, halogen, lower alkylsulfonyl, or arylsulfonyl; R ₃₄ is lower alkyl, lower alkenyl, or optionally substituted benzyl,
Hydroalkylation, carbamoyl alkyl, - alkylene -CO ₂ ^- M ^+, or - alkylene -SO ₃ ^- M
⁺ (Where, ^- M ⁺ is ^{H +, Na +, K +} , Li + or NH ₄ ⁺⁾ from those selected; X ^- are Cl ^-, Br ^-,
CH ₃ SO ₄ ⁻ , C ₂ H ₅ SO ₄ ⁻ , ZnCl ₄ ⁻² / 2
Wherein at least one poly (oxyalkylene) component Z is present.

Preferred intermediates are those wherein C is a nucleophilic residue obtained from a primary or secondary amine, a hydroxyl compound, a mercapto compound, a sulfinic acid, a sulfonamide, an imide or a sulfonimide.

More preferably, C is obtained from an organic nucleophile selected from those of the following structural formula:

[0037]

Embedded image Wherein R ₁ is independently substituted or unsubstituted alkyl having ₁ to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 5 to 7 carbon atoms; 'Is selected from a hydrogen atom or R ₁ ; E is a divalent cyclic moiety.

Further preferred intermediates are aniline wherein C is substituted or unsubstituted; naphthylamine; 1,2,3,4
-Tetrahydroquinoline; 3,4-dihydro-2H-
1,4-benzoxazine; 2-aminothiazole; indole; 2,3-dihydroindole; carbazole; naphthylamine; phenoxazine; phenothiazine; diphenylamine; 2-aminothiophene; aminopyridine or julolidine.

Particularly preferred intermediates of the present invention are compounds wherein C is selected from the structural formula:

[0040]

Embedded image Here, P is a hydrogen _{atom; -N = O; -NH 2;} -NH
—NH ₂ ; NO ₂ ; COR ₄₈ (where R ₄₈ is selected from a hydrogen atom, unsubstituted or substituted alkyl, cycloalkyl or aryl); N ₂ ⁺ X ⁻ (where X
^-Is a counter ion); -N = CH- _R49 or -CH = N-
R ₄₉ (where R ₄₉ is selected from alkyl, cycloalkyl and aryl); R ₁₆ is a hydrogen atom or lower alkyl, trifluoromethyl, lower alkoxy, arylthio, aryloxy, halogen, —CH ₂ —O
1- selected from -Z or -O-alkylene-O-Z
R ₁₇ and R ₁₈ are -z, linear or branched lower alkenyl; cycloalkyl; cycloalkyl substituted with hydroxy, alkoxy, alkyl, halogen or alkanoyloxy; phenyl; lower alkoxy, cyano, Alkanoyloxy, or phenyl substituted with one or more of the groups selected from -LZ; linear or branched alkyl having 1 to 12 carbon atoms;

[0041]

Embedded image Cyano, halogen, 2-pyrrolidino, phthalimidino,
Vinylsulfonyl, acrylamide, o-benzoic acid sulfonimide, a group of the following structural formula,

[0042]

Embedded image R ₁₉ is a hydrogen atom, lower alkyl, lower alkanoylamino, lower alkoxy, lower alkyl, lower alkoxy, phenyl substituted with halogen, carboxy, cyano, carboxy, or acyloxy; R ₂₀ is a hydrogen atom; lower alkyl; hydroxy,
Lower alkyl substituted with acyloxy, phenyl, cycloalkyl, halogen or alkoxy; cycloalkyl; phenyl; lower alkyl, lower alkoxy, halogen, hydroxy, alkanoylamino, carbalkoxy, carboxy, cyano, or phenyl substituted with alkanoyloxy W is lower alkylene having 1 to 3 carbon atoms; alkylene substituted with hydroxy, halogen, alkoxy or acyloxy; vinyl; 1,2-phenylene; lower alkyl, lower alkoxy, halogen, carboxy, or carbalkoxy 1,2-phenylene; 1,2-cyclohexylene; —O—CH ₂ —; —CH ₂ OCH ₂ —;
_2- ; -N (R ₂₁ ) CH _2- ; -N (R ₂₁ ) CH ₂ CH
₂ -—— CH ₂ N (R ₂₁ ) CH ₂ —; wherein the alkyl group represented by R ₁₇ and R ₁₈ may be further substituted with a group selected from the following group: —O -R ₂₁ ;
—SO ₂ —R ₂₂ ; —CON (R ₂₁ ) R ₂₃ ; —SO ₂ N
(R ₂₁ ) R ₂₃ ; -N (R ₂₁ ) SO ₂ -R ₂₂ ; -OCO-
_{R 23; -OCO 2 R 23;} -OCON (R 21) R 23; -S
R ₂₄ or —SO ₂ CH ₂ CH ₂ SR ₂₄ ; provided that R ₂₁ and R ₂₃ are a hydrogen atom; lower alkyl; lower alkyl substituted by hydroxy, aryloxy, halogen, cycloalkyl, or phenyl; cycloalkyl; Phenyl; lower alkyl, lower alkoxy, halogen, hydroxy, alkanoylamino, carboxy, carboxy, cyano, or phenyl substituted with alkanoyloxy; R ₂₂ is R ₂₁ except for a hydrogen atom
And R ₂₃ represent the same substituents as those for R ₂₃ ; R ₂₄ represents, in addition to those described for R ₂₁ and R ₂₃ , benzothiazol-2-yl, benzimidazol-2-yl, pyridyl, pyrimidinyl, 1,3 , 4-thiadiazolyl, 1,
3,4-oxadiazolyl, naphthyl, or triazolyl; R ₂₅ , R ₂₆ and R ₂₇ are each independently selected from halogen and lower alkyl; R ₂₈ is a hydrogen atom;
Cycloalkyl, alkyl, 2-thienyl, phenyl,
R ₂₉ is a hydrogen atom; or a 1-2 substituent selected from lower alkyl, lower alkoxy and halogen; R ₃₀ is cyano, carbalkoxy, alkylsulfonyl R, arylsulfonyl, or unsubstituted or substituted carbamoyl;
₃₁ is selected from a hydrogen atom, lower alkyl, and aryl; _R32 and _R33 are each independently selected from a hydrogen atom, lower alkyl, lower alkoxy, halogen, or -Z; wherein X is a covalent bond , Oxygen, or sulfur; L is X or —SO ₂ —, —SO ₂ N (R ₂₁ ) —,
_{-COO -, - N (SO 2} -R 22) -, - N (R 21) -
Alternatively, those selected from -CON (R ₂₁ )-; provided that
The compound contains at least one -Z component.

Preferred intermediates of the present invention are those selected from the following structural formulas:

[0044]

Embedded image Wherein R ₁₆ and R ₁₇ are the same as above; P ₁ , P ₂ ,
P ₃ and P ₄ represent a hydrogen atom, nitro, amino, hydrazino,
HET is benzothiazole; thiazole; 1,3,4-thiadiazole;
1,2,4-thiadiazole; pyridine, thiophene,
L ₁ is an aromatic heterocyclic radical obtained from 2,1-benzisothiazole; L ₁ is —O—, —S—, —SO
_{2 -, - N (R 3} ) -, - SO 2 N (R 3) -, or _{-N (SO 2 -R 4) -} , one selected from; wherein
R ₃ is a hydrogen atom, -Z, or an alkyl, aryl, unsubstituted or substituted groups selected from cycloalkyl,; R ₄ is alkyl, aryl, unsubstituted or substituted group selected from cycloalkyl; X ₁ is -C (= _{O) -, - SO 2 -} ,
-S-.

In all of the above alkyl or alkylene, alkoxy, etc. radicals or components which are or contain aliphatic hydrocarbon components, these radicals or components are, unless otherwise stated, 1 to 12 Contains unsubstituted or substituted carbon atoms.

Further, cycloalkyl includes a 5- to 7-membered alicyclic group, and aryl means an unsubstituted or substituted carbocyclic and heterocyclic aromatic group containing 2 to 14 carbon atoms.

In one embodiment, the colorant of the present invention is a polymerizable, liquid-reactive colorant, which is not added to a solvent or a dispersion medium as a solution or dispersion, but in a solvent-free form. It can be added to the reaction mixture or it can be added to one component of the reaction mixture.

This is extremely advantageous in terms of method compared to solvent systems, since it does not require a foreign, non-reactive or reactive solvent or dispersion medium and does not require removal of the solvent or dispersion medium from the product. .

As the thermoplastic resin applicable in the present invention, any known resin can be used as long as it is basically a thermoplastic resin. Here, “thermoplastic” has the same meaning as the usual concept, and means a resin that softens or melts when heated. This thermoplastic resin is clearly distinguished from a thermosetting resin in basic physical properties and chemical properties. Here, the term “thermosetting resin” is the same as the usual concept, and means a resin which becomes permanently hard when heated and cured.

The thermoplastic resins used in the present invention include polyolefin polymers such as polyethylene, linear low density polyethylene, polypropylene, polybutylene, or copolymers with ethylene, propylene or butylene. Examples of other thermoplastic polymers include polyvinyl chloride, polyvinylidene chloride, cellulose acetate, cellulose acetate butyrate, cellulose resins such as cellulose acetate propionate, poly (methyl methacrylate), styrene allylonitrile copolymer, polystyrene , Polycarbonate and allylonitrile-
Examples include butadiene-styrene terpolymer (ABS), polyamides such as nylon-6, nylon-6,6, poly (ethylene terephthalate), especially glycol-modified poly (ethylene terephthalate) and poly (butylene terephthalate).

As described above, the coloring agent is used in a small amount required for the desired coloring with respect to the thermoplastic resin. The actual amount depends on the color tone desired, the coloring power of the chromophore, the overall molecular weight of the colorant, ie chromophore + poly (oxyalkylene) chain length, and the like.

Generally, it is about 0.001 to 10%, preferably about 0.01 to 3%, more preferably about 0.01 to 1.0%, based on the total weight of the resin composition.

Other conventional additives such as plasticizers, antioxidants, stabilizers, lubricants, flame retardants, nucleating agents and the like can be appropriately used.

It has been found that the coloring agent of the present invention does not have any adverse effect on conventional additives.

When the coloring agent of the present invention is used correctly, it does not impair the transparency of the resin. Furthermore, it can be used in combination with a conventional clarifying agent together with a coloring agent, thereby providing a colored product having excellent transparency. Examples of clarifying agents in this case include benzylidene sorbitol, including substituted benzylidene sorbitol, for example, as described in US Pat. U.S. Patent No. 4,016,118; 4,3
71,645; JP-B-53-117044.

The hue of the colorant depends mainly on the substituents present on the basic chromophore. A wide variety of colors or hues can be obtained by mixing two or more colorants. Mixing in this case can be easily performed based on the same melting properties governed by the nature of the polymer chains, since the colorant is a polymeric substance. Thus, the colorants are generally meltable,
The mutual compatibility is also very good.

The coloring agent of the present invention can be added to a thermoplastic resin by a conventional method. For example, the resin may be simply added to the resin in a plasticized or molten state, that is, before being formed into a final shape by extrusion, blow molding, or the like.

For example, when coloring a polyolefin,
A colorant consisting of a poly (oxyalkylene) -substituted chromophore is directly added to the molten polymer or mixed into pellets, or a colorant is mixed with the resin powder before extrusion, and then as in the case of a non-colored polyolefin resin. Coloring can be carried out by molding or extrusion by ordinary means.

In addition, a resin or vehicle containing a coloring agent at a high concentration is first prepared, and this concentrate is made into a liquid or solid, such as powder or pellets, and this is mixed with a thermoplastic resin. It can also be used.

The liquid form is advantageous in some respects as compared with the solid form, and can be added directly to the molten polymer if desired, and does not need to contain a foreign solvent or dispersion medium. This method will have a very positive effect on the properties of the final thermoplastic product.

In addition, the colorant may be mixed in advance with a small amount of a solvent or a dispersion medium having good compatibility with the resin to make the method advantageous.

The aromatic amine intermediate is one of the present invention and is produced through several steps. In a first step, the aromatic amine is hydroxyalkylated by reaction with glycidol at 80-150 ° C. to give an aromatic amine intermediate having both primary and secondary hydroxyl groups. The glycidol is added in the presence of an inert gas such as nitrogen until the desired amount of glycidol has reacted. This reaction is performed in the presence or absence of a solvent.
When a solvent is required, toluene, xylene, nitrobenzene, and dioxane are typical solvents. Examples of useful basic catalysts are potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide. The amount of basic catalyst is chosen appropriately but is usually about 0.05 to 2% by weight (based on the amine used). In addition, tertiary organic amines such as dimethylaminocyclohexane, triethylamine, benzyldimethylamine are also useful catalysts.

In the next step, the aromatic amine intermediate from the first step is the final aromatic amine intermediate by hydroxyalkylation with ethylene oxide or propylene oxide at about 80-150 ° C. The alkylene oxide is added in the presence of an inert gas such as nitrogen until the desired amount of alkylene oxide has been absorbed.

When propylene oxide was initially used as the alkylene oxide, an additional amount of ethylene oxide was added later,
The desired detergency is imparted to the polymer compound.

The colorants of the present invention can be prepared in various ways depending on the chromophore to be added to the polymer. Hereinafter, the method will be described in the following (I) to (IX). These paths are illustrative and do not limit the scope of the invention.

[0066] path I H-X H-Ar Q -NH 2 ---> Q-N 2 + X - -----> Q-N = N-Ar [I] nitrite [II] Coupler [IV [III] In this route I, the azo colorant of the present invention diazotizes a carbocyclic or heterocyclic amine (I) to obtain a diazonium salt, which is coupled with an aromatic coupling component intermediate (III). To obtain an azo colorant (IV). Where Q
-And -Ar are as defined above, and one of Q- and -Ar contains at least one -Z component.
The diazotization of the aromatic amine can be performed by various known methods. Coupling is usually carried out in dilute mineral or organic acids such as acetic acid, propionic acid and is facilitated by increasing the pH to 3-4 by the addition of certain bases.

The additional polymeric amines (I) of the present invention are prepared by the following routes IA, IB, IC.

[0068] Route IA involves converting the nitro compound (IA) to an amine intermediate (IIA) by catalytic hydrogenation. Any reduction catalyst can be used. For example, fine particles of Raney nickel, nickel oxide, and fine metal such as iron, cobalt, platinum, ruthenium, osmium, and rhodium can be used.

[0069] Pumice, asbestos, diatomaceous earth, alumina, silica gel, and activated carbon loaded with a metal catalyst are also effective. The amount of catalyst can be used in the range of about 0.025 to 15% by weight (based on the nitro intermediate used).

The reduction temperature is suitably in the range of about 20-90 ° C, but more preferably in the range of about 40-90 ° C. This is because the reaction time and the yield can be improved. 500-1800 psi (hydrogen) is used as the pressure during the reduction of the nitro intermediate.

The reduction reaction is usually performed in the presence of a suitable solvent. Examples of the solvent include lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ethers such as dioxane; hydrocarbons such as benzene, toluene, xylene, cyclohexane, petroleum ether, and an equal weight mixture of water and a lower alcohol. The amount of solvent is usually used in the range of 30-80% by weight (based on the total amount of solvent + nitro compound).

Route IB H ₃ C (C ＝ O) NH—Q′—SO ₂ Cl + H ₂ N—Q [IB] [IIB] —— H ₃ C (C ＝ O) NH—Q ′ —SO ₂ NH—Q base [IIIB] H ₃ C (C ＝ O) NH—Q′—SO ₂ NH—Q [IIIB] ————> H ₂ N—Q′—SO ₂ NH—Q Base [IVB] Route IB is carried out at a temperature of 0-100 ° C in the presence of an inorganic base,
Condensing the acetamidobenzenesulfonyl chloride intermediate (IB) with at least a stoichiometric amount of the directional group amine (IIB) to obtain an acetamido intermediate. Here, Q ′ is phenylene or substituted phenylene, and Q is the same as described above, and includes at least one —Z component. Further heating under basic conditions at a temperature of 80-100 ° C. hydrolyzes the acetamido intermediate to give the polyaromatic amine intermediate (IVB).

Route IC Base O ₂ N—Q′—SO ₂ Cl + H ₂ N—Q—> O ₂ N—Q′—SO ₂ NH—Q [IC] [IIB] [IIC] Hydrogen O ₂ N—Q _{'-SO 2 NH-Q ---->} H 2 N-Q' -SO 2 NH-Q [IIC] catalyst [IIIC] pathway IC a temperature 0-100 ° C., in the presence of an inorganic base,
Condensing the nitroarylenesulfonyl chloride intermediate (IC) with at least a stoichiometric amount of the directional group amine (IIB) to obtain a nitropolyaromatic intermediate (IIC). Here, Q ′ is the same as in the case of the path IB.

The corresponding polyaromatic amine intermediate (III
C) is prepared by catalytically reducing and converting a nitropolyaromatic intermediate (IIC) analogously to Route IA.

The methine coloring agent of the present invention is produced by the following routes II to IV. Note that the route II includes three steps.

In the first step, the primary hydroxyl-enriched aromatic amine intermediate H-Ar is reacted with an organic anhydride to form an ester intermediate. Generally, the aromatic amine intermediate H-Ar is reacted with acetic anhydride at a temperature in the range of 60-130 ° C. In this case, tertiary organic amines such as dimethylaminocyclohexane, triethylamine, benzyldimethylamine are used as useful catalysts.

In the second step, the aromatic ester intermediate from the first step is reacted with the Vilsmeier reagent, usually using N, N-dimethylformamide (DMF) and oxychloride to give the corresponding aldehyde. (Bull. SocietyChim. De Fran
ce, No. 10: 1898-89, October, 196
2; Angewandte Chemie 72, N
o. 22, 834-845, November, 1960). After base hydrolysis, the corresponding aromatic aldehyde intermediate, A
r-COH is separated.

Route II Step 3

[0079]

Embedded image Finally, in a third step, an aromatic aldehyde intermediate,
Ar-COH is reacted with an active methylene compound (VI) under Knoevenagel conditions to obtain a methine compound (VII).

The azamethine colorants of the present invention are made in two steps according to Route III.

[0081] In step 1, the aromatic amine intermediate (III) is nitrosated using nitrous acid to obtain a nitroso aromatic amine intermediate (VIII).

[0082] In the second step, the nitroso aromatic amine intermediate (VI
II) is reacted with an active methylene compound (VI) to give an azamethine compound (IX).

The cationic azo or methine colorant of the present invention can be produced by various methods. Some of them are described in the following routes (IV) to (VI). These paths are illustrative and do not limit the scope of the invention.

Route IV

[0085]

Embedded image Azo colorant (X) (where A is the remainder of the heterocyclic aromatic ring)
Is converted to the corresponding cationic colorant (XI) by reaction with an alkylating agent at elevated temperatures in the presence or absence of an inert solvent. A suitable example of an alkylating agent is
Dialkyl sulfate, alkyl halide, aralkyl halide, alkyl ester of sulfonic acid, activated vinyl compound, haloacetic acid and the like. Specific examples thereof include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, ethyl bromide, butyl bromide, methyl iodide, ethyl iodide, benzyl chloride, benzyl bromide, and methyl-p.
-Toluenesulfonate, butyl-p-toluenesulfonate, ethylbenzenesulfonate, acrylamide and bromoacetic acid.

The cationic methine colorants of the present invention
And VI.

Route V

[0088]

Embedded image In route V, the cationic methine colorant of the present invention (X
III) is obtained by condensing a substituted 2-methylene-1,3,3-trimethylindoline (Fisher base) (XII) with the aromatic aldehyde (V) at an elevated temperature in the presence or absence of an inert solvent. Can be

The base (XII) and the condensation method are known. These three bases are commercially available.

Route VI

[0091]

Embedded imageIn addition, cationic methine colorant (XV) is inert
High temperature displacement in the presence or absence of a solvent, in the presence of a catalyst
The quaternary basic salt (XIV) is converted to the above aromatic aldehyde
It is produced by condensation with (V). 4th
Grade bases (XIV) and condensation methods are known. helpful
Examples of quaternary bases are quaternized quinolines, benzothiazoles,
Benzoxazole, indolenine, benzimidazo
It is. The above anion, X^-Examples of Cl^-, B
r^-, I^-, CH_ThreeSO_Four ^-, C_TwoH _FiveSO_Four ^-In
You. The type of anion used depends on the separation method used and
And the particular quaternizing agent.

The following examples and tables illustrate certain compounds of the present invention and methods for their preparation. Here, all parts and percentages are based on weight.

The abbreviations for EO, PO, and BO are -C
_{H 2 CH 2 -, - CH} (CH 3) CH 2 -, - CH (C
₂ H ₅₎ CH ₂ - meaning. GL ₁ and GL mean glycidol units. In the structural formula, GL ₁ means a reactive residue of a glycidol unit, and GL means a glycidol unit terminated by another alkylene oxide. The number preceding the GL ₁ and GL represent the average number of glycidol units per reactive site of the nucleophile. For example, if this number is 2 in Example 1, one reactive site actually has one GL ₁ unit and the other reactive site has two G
It would be to have the L ₁ unit.

In Example 1A, “2GL / 100E
"OH" means that each hydroxyl of _one unit of GL is at least 1
Reacting with one ethylene oxide component EO (EO is present in a stoichiometric excess in the reaction system), and each terminal GL ₁ is reacting with ethylene oxide component EO (EO in the reaction system). Is present in excess of the stoichiometric amount). E of Example 1A
The numbers attached to O, PO, BO represent the average number of glycidol units per reactive site of the nucleophile.

[0095]

【Example】

 Example 1

[0096]

Embedded image 125 grams (1.34 mol) of aniline in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel,
And 0.6 grams of potassium hydroxide. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

397 grams (5.36 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 1A

[0100]

Embedded image The aniline 4 of Example 1 was placed in a 2 gallon autoclave.
Charge 389 grams (1 mole) of the glycidol intermediate and 2 grams of potassium hydroxide catalyst. Reactor with nitrogen 3
Purge to 60 psi, then heat to 250 ° F. under 5 psi nitrogen pressure. Next, 8000 grams (200 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours. At this time, the hydroxyl value of the reaction mixture was 38.2 (theoretical value was 35.2).
6).

After vacuum stripping at 200 ° F. for 15 minutes, the aniline 4GL / 200EO-H intermediate was converted to 8
It has an average gram molecular weight of 812 and is ready to use.

Example 1B

[0104]

Embedded image 145 grams of 85% phosphoric acid, 25 grams of 98% sulfuric acid, and 3 drops of 2-ethylhexanol defoamer are added to a 500 ml three-necked flask equipped with a thermometer, cooling bath, and mechanical stirrer. The mixture is cooled and 10.3 grams (0.1 mole) of 2-aminothiazole are added to the flask.
The mixture was further cooled to below 0 ° C. and then
35 grams of nitrosylsulfuric acid are added while maintaining the temperature below 5 ° C. After 3 hours, the mixture shows a positive nitrate test, slowly adding 1 gram of sulfamic acid and keeping the temperature below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker, aniline 4GL /
969 grams (0.11 mole) of the 200EO-H intermediate,
Charge 969 grams of water, 969 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The above diazo solution was dropped into a beaker over about 30 minutes, and the temperature was reduced to 10 ° C.
Keep less than. The resulting mixture was stirred for several hours and left overnight, after which the excess acid was neutralized to pH about 7 by adding 260 grams of 50% sodium hydroxide, maintaining the temperature below 20 ° C, and keeping the temperature below 493 nm. To give an orange oil with maximum absorption.

Embodiment 2

[0107]

Embedded image A dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel is charged with 125 grams (1.34 moles) of aniline and 0.6 grams of potassium hydroxide. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

397 grams (5.37 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 2A

[0111]

Embedded image The aniline 4 of Example 2 was placed in a 2 gallon autoclave.
Charge 389 grams (1 mole) of the glycidol intermediate and 4 grams of potassium hydroxide catalyst. Reactor with nitrogen 3
Purge to 60 psi, then heat to 250 ° F. under 5 psi nitrogen pressure. Next, 4400 grams (100 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours. At this time, when the hydroxyl value of the reaction mixture was measured, it was 75.5 (theoretical value was 70.
2).

After vacuum stripping at 200 ° F. for 15 minutes, the aniline 4GL / 100EO-H intermediate
It has an average gram molecular weight of 458 and is ready to use.

Example 2B

[0115]

Embedded image In a 2000 ml beaker, add m-toluidine 4GL / 100
490 grams (0.11 mole) of the EO-H intermediate, 49
Charge 0 grams, 490 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. Diazo solution from 14.3 grams of 3,4-dicyanoaniline (Example 1)
(Prepared in B) is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 50% sodium hydroxide 2
Add 60 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed to give a red liquid with a maximum absorption at 500 nm.

Embodiment 3

[0117]

Embedded image 172 grams (1.3 grams) of m-chloroaniline in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel.
4 moles), and 0.6 grams of potassium hydroxide. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

398 grams (5.37 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this time, the hydroxyl value of the m-chloroaniline 4-glycidol intermediate was 793 (theoretical value was 799).

Example 3A

[0121]

Embedded image In a 1 gallon autoclave are charged 417 grams (1 mole) of the m-chloroaniline 4-glycidol intermediate of Example 3 and 4 grams of potassium hydroxide catalyst. The reactor was purged three times with nitrogen to 60 psi, then
Heat to 250 ° F. under 5 psi nitrogen pressure. Next, 2640 grams (60 moles) of ethylene oxide were
Add at a rate to maintain a reading vapor pressure of less than si.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, the m-chloroaniline 4GL / 60EO-H intermediate has an average gram molecular weight of 3057 and is ready for use.

Example 3B

[0125]

Embedded image In a 4000 ml beaker, 336 grams of the m-chloroaniline 4GL / 60EO-H intermediate from Example 3A (0.
11 mol), 400 grams of water, 400 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. 4-phenylazoaniline 19.7 (0.1 mol)
The diazo solution from (prepared in Example 1B) was added dropwise to the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours, left overnight and then
The excess acid is neutralized to a pH of about 7 by adding 260 grams of 50% sodium hydroxide to maintain the temperature below 20 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. This methylene chloride solution was washed four times with water,
It is then dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give an orange liquid.

Embodiment 4

[0127]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 153 grams (1.0 mole) of 2,5-dimethoxyaniline and 0.8 mol of potassium hydroxide Charge gram. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

296 g (4.0 mol) of glycidol
Is slowly added dropwise via an addition funnel. The first two,
The temperature drops slightly due to the dropping of 3 ml, and heat is generated. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 4A

[0131]

Embedded image In a 2-gallon autoclave are charged 449 grams (1.0 mole) of the 2,5-dimethoxyaniline 4-glycidol intermediate of Example 4 and 4 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure. Next, 8800 grams (200 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, 2,5-dimethoxyaniline 4GL / 200E
The hydroxyl number of the OH intermediate was determined to be 3
It is 9.6 (theoretical 36.4), has an average gram molecular weight of 8500 and is ready to use.

Example 4B

[0135]

Embedded image In a 4000 ml beaker, add 4GL / 14 from Example 4A
723 grams of the 0EO-Hm-anisidine intermediate (0.1
1 mole), 730 grams of water, 730 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C.
2-amino-4-chloro-5-formylthiazole 1
A diazo solution (prepared in Example 1B) from 6.2 grams (0.1 mole) is added dropwise to the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 50% sodium hydroxide 2
Add 60 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed to give a bluish purple liquid.

Embodiment 5

[0137]

Embedded image In a 2000 ml beaker, 254 g (0.11 mol) of 6GL / 40EO-Hm-toluidine intermediate, 300 ml of water
Grams, 300 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. 4,5- (3,3-
A diazo solution (prepared in Example 1B) from 19.6 grams (0.1 mol) of dimethyloxytetramethylene) -2-aminothiazole was dropped into the beaker over about 30 minutes,
Maintain the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 260 grams of 50% sodium hydroxide was added to neutralize excess acid and bring the pH to about 7.
And maintain the temperature below 20 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate. The methylene chloride solvent is then filtered and stripped to give a red liquid.

Embodiment 6

[0139]

Embedded image 549 grams of 85% phosphoric acid, 150 grams of 98% sulfuric acid,
And 9 drops of 2-ethylhexanol defoamer with a thermometer,
Add to a 1000 ml three-necked flask equipped with a cooling bath and a mechanical stirrer. The mixture is cooled and 2-amino-6
-54 g (0.3 mol) of methoxybenzothiazole
To the flask. The mixture was further cooled to below 0 ° C., after which 105 grams of 40% nitrosylsulfuric acid was added.
Add while maintaining the temperature below 5 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker, add m-toluidine 4
525 grams (0.33 mole) of the GL / 27EO-H intermediate, 600 grams of water, 600 grams of ice, and urea 12
Charge gram. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours, allowed to stand overnight, and then 50% sodium hydroxide 7
Add 80 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. Remove the bottom salt layer,
The product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate. Then, the methylene chloride solvent was filtered,
Stripping gives a red liquid with a maximum absorption at 526 nm.

Comparative Example 6A

[0142]

Embedded image 549 grams of 85% phosphoric acid, 150 grams of 98% sulfuric acid,
And 9 drops of 2-ethylhexanol defoamer with a thermometer,
Add to a 1000 ml three-necked flask equipped with a cooling bath and a mechanical stirrer. The mixture is cooled and 2-amino-6
-54 g (0.3 mol) of methoxybenzothiazole
To the flask. The mixture was further cooled to below 0 ° C., after which 105 grams of 40% nitrosylsulfuric acid was added.
Add while maintaining the temperature below 5 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker, m-toluidine 2 was added.
427 grams (0.33 mole) of 7EO-H intermediate,
Charge 00 grams, 500 grams of ice, and 12 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 780 grams of 50% sodium hydroxide was added to neutralize excess acid to a pH of about 7 and to a temperature of 2
Keep below 0 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate.
The methylene chloride solvent is then filtered and stripped to give a red liquid with a maximum absorption at 526 nm.

Embodiment 7

[0145]

Embedded image In a 4000ml beaker, add aniline 4GL / 200EO-
Charge 969 grams (0.11 mole) of H intermediate, 1000 grams of water, 1000 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. A diazo solution (prepared in Example 6) from 18.4 grams (0.1 mole) of 2-amino-4-chlorobenzothiazole is added dropwise to the beaker over about 30 minutes, maintaining the temperature below 10C. The resulting mixture was stirred for several hours, left overnight, and then
The excess acid is neutralized by adding 260 grams of sodium hydroxide to a pH of about 7 and maintaining the temperature below 20 ° C.
The bottom salt layer is removed to give a red liquid with a maximum absorption at 524 nm.

Embodiment 8

[0147]

Embedded image 320 grams of acetic acid, 80 grams of propionic acid, and 2
-9 drops of ethyl hexanol defoamer, thermometer, cooling bath,
And add to a 1000 ml three-necked flask equipped with a mechanical stirrer. The mixture is cooled and 32.2 grams (0.2 mole) of 2-amino-5-ethylthio-1,3,4-thiadiazole are added to the flask. 5 ° C
Further cool to less than 40% nitrosyl sulfate
0 grams are added while maintaining the temperature below 10 ° C.
After 3 hours, the mixture showed a positive nitrate test, 2 grams of sulfamic acid was added slowly and the temperature was raised to 5
Keep below ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 2000 ml beaker, add m-toluidine 4
Charge 669 grams (0.22 mole) of GL / 60EO-H intermediate, 700 grams of water, 700 grams of ice, and 8 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours, allowed to stand overnight, and then 50% sodium hydroxide 5
Add 03 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. Remove the bottom salt layer to obtain a red liquid.

Embodiment 9

[0150]

Embedded image 180 grams of acetic acid, 41 grams of propionic acid, and 2
-4 drops of ethylhexanol defoamer, thermometer, cooling bath,
And a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture is cooled and 9.7 grams (0.1 mole) of 5-amino-3-methylpyrazole is added to the flask. The mixture was further cooled to less than 5 ° C.
35 grams of 0% nitrosylsulfuric acid are added while maintaining the temperature below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 2000 ml beaker, add m-toluidine 4
Charge 238 grams (0.11 mole) of the GL / 40EO-H intermediate, 250 grams of water, 250 grams of ice, and 8 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 50% sodium hydroxide 2
Add 68 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. Remove the bottom salt layer,
The product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give a yellow liquid with a maximum absorption at 418 nm.

Embodiment 10

[0153]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 215.5 grams (1.34 mol) of m-trifluoroaniline and 0.3 ml of potassium hydroxide. Charge 6 grams. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

298 grams (4.03 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this time, when the hydroxyl value of the m-trifluoroaniline 3-glycidol intermediate was measured, it was found to be 730 (theoretical value: 713).

Example 10A

[0157]

Embedded image In a 1 gallon autoclave are charged 383 grams (1.0 mole) of the m-trifluoroaniline 3-glycidol intermediate of Example 10 and 4 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure. Next, 4400 grams (100 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, m-trifluoroaniline 3GL / 100EO
The -H intermediate has an average gram molecular weight of 4783 and is ready for use.

Example 10B

[0161]

Embedded image In a 2000 ml beaker, 526 grams of m-trifluoromethylaniline 3GL / 50EO-H intermediate (0.11
Mol), 550 grams of water, 550 grams of ice, and 4 ureas
Charge gram. The mixture is cooled below 0 ° C. 3
A diazo solution (prepared in Example 9) from 9.5 grams (0.1 mole) of aminopyridine is added dropwise to the beaker over about 30 minutes, keeping the temperature below 10 ° C. The resulting mixture is stirred for several hours and left overnight, after which 268 grams of 50% sodium hydroxide are added to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed to give a yellowish orange liquid.

Embodiment 11

[0163]

Embedded image N-ethyl-1-naphthylamine 171 was added to a dry 1000 ml three-necked flask equipped with a nitrogen purge device, a heating mantle, a mechanical stirrer, a temperature controller, and an addition funnel.
Grams (1 mole) and 0.6 grams of potassium hydroxide. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

222 grams (3 moles) of glycidol are slowly added dropwise via the addition funnel. With the first few milliliters the temperature drops slightly and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 11A

[0167]

Embedded image In a 2 liter autoclave, N-ethyl-1-naphthylamine 3 glycidol intermediate 393 of Example 11
Grams (1 mole) and 4 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure. Next, 1430 grams (30 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, N-ethyl-1-naphthylamine 3GL / 30
The EO-H intermediate has an average gram molecular weight of 1713 and is ready to use.

Example 11B

[0171]

Embedded image In a 2000 ml beaker, 188 grams of N-ethyl-1-naphthylamine 3GL / 30EO-H intermediate (0.11
Mol), 200 grams of water, 200 grams of ice, and urea 4
Charge gram. The mixture is cooled below 0 ° C. 2
The diazo solution (prepared in Example 1B) from -amino-4-methylthiazole 11.3 (0.1 mol) is added dropwise to the beaker over about 30 minutes, keeping the temperature below 10 ° C. The resulting mixture is stirred for several hours and left overnight, after which 260 grams of 50% sodium hydroxide is added to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give a red liquid.

Embodiment 12

[0173]

Embedded image 180 grams of acetic acid, 41 grams of propionic acid, and 2
-4 drops of ethylhexanol defoamer, thermometer, cooling bath,
And a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture was cooled and 15 grams (0.1 mole) of 5-amino-3-methylisothiazole hydrochloride
To the flask. The mixture is further cooled to below 5 ° C, after which 35 grams of 40% nitrosylsulfuric acid are added, maintaining the temperature below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker, aniline 4GL /
529 grams (0.11 mole) of the 100EO-H intermediate,
Charge 550 grams of water, 550 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The above diazo solution was dropped into a beaker over about 30 minutes, and the temperature was reduced to 10 ° C.
Keep less than. The resulting mixture is stirred for several hours and left overnight, after which 260 grams of 50% sodium hydroxide is added to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer was removed and 493n
An orange liquid having a maximum absorption at m is obtained.

Embodiment 13

[0176]

Embedded image 180 grams of acetic acid, 40 grams of propionic acid, and 2
-6 drops of ethylhexanol defoamer, thermometer, cooling bath,
And a 500 ml three-necked flask equipped with a mechanical stirrer. The mixture is cooled and 15 grams (0.1 mole) of 3-amino-1,2-benzisothiazole are added to the flask. The mixture was further cooled to below 5 ° C., after which 37.5 grams of 40% nitrosylsulfuric acid was added at a temperature of 1
Add while maintaining below 0 ° C. After 3 hours, the mixture
A positive nitrate test is indicated, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. One more
After hours, a negative nitrate test becomes apparent.

In a 2000 ml beaker, aniline 4GL /
Charge 333 grams (0.11 mole) of the 60EO-H intermediate, 350 grams of water, 350 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 260 grams of 50% sodium hydroxide was added to neutralize excess acid to a pH of about 7 and to a temperature of 2
Keep below 0 ° C. The bottom salt layer is removed to give a magenta liquid.

Embodiment 14

[0179]

Embedded image 300 grams of acetic acid, 60 grams of propionic acid, and 2
-4 drops of ethylhexanol defoamer, thermometer, cooling bath,
And add to a 1000 ml three-necked flask equipped with a mechanical stirrer. The mixture is cooled and 4-aminopyridine 2
Add 8.2 grams (0.3 mole) to the flask. The mixture is further cooled to below 5 ° C., after which 135 grams of 40% nitrosylsulfuric acid are added while maintaining the temperature below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker, add m-toluidine 4
569 grams (0.33 mole) of GL / 30EO-H intermediate, 600 grams of water, 600 grams of ice, and 12 ureas
Charge gram. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours, allowed to stand overnight, and then 50% sodium hydroxide 8
The excess acid is neutralized to a pH of about 7 by adding 04 grams and maintaining the temperature below 20 ° C. Remove the bottom salt layer,
The product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give a yellowish orange liquid.

Embodiment 15

[0182]

Embedded image 183 grams of 85% phosphoric acid, 25 grams of 98% sulfuric acid, and 3 drops of 2-ethylhexanol defoamer are added to a 1000 ml three-neck flask equipped with a thermometer, cooling bath, and mechanical stirrer. The mixture was cooled and 2-amino-3,
16.3 grams (0.1 mole) of 5-dicyano-4-methylthiophene is added to the flask. This mixture is brought to 0 ° C
Further cooling to less than 40% nitrosyl sulfate
Add 5 grams while maintaining the temperature below 5 ° C. 3
After an hour, the mixture shows a positive nitrate test,
Add 2.5 grams of sulfamic acid slowly and bring the temperature to 5
Keep below ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 2000 ml beaker, aniline 4GL /
Charge 188 grams (0.11 mole) of the 30EO-H intermediate, 200 grams of water, 200 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 260 grams of 50% sodium hydroxide was added to neutralize excess acid to a pH of about 7 and to a temperature of 2
Keep below 0 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate.
Filter and strip the methylene chloride solvent,
A purple liquid having a maximum absorption at 556 nm is obtained.

Embodiment 16

[0185]

Embedded image In a 2000 ml beaker, m-toluidine 4GL / 40E
238 grams (0.11 mole) of OH intermediate, 250 parts of water
Grams, 250 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. A diazo solution (prepared in Example 13) from 17.8 grams (0.1 mole) of 2-amino-3-cyano-4,5-tetramethylene-thiophene was added dropwise to the beaker over about 30 minutes, and the temperature was increased. 10 ℃
Keep less than. The resulting mixture is stirred for several hours and left overnight, after which 260 grams of 50% sodium hydroxide is added to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed and the product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give a red liquid.

Embodiment 17

[0187]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 3,6-dimethylbenzomorpholine 21 was added.
7 grams (1.34 moles) and potassium hydroxide 0.
Charge 6 grams. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

298 grams (4.03 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this time, when the hydroxyl value of the benzomorpholine 3-glycidol intermediate was measured, it was found to be 536 (theoretical value: 584).

Example 17A

[0191]

Embedded image In a 2 gallon autoclave are charged 379 grams (1 mole) of the benzomorpholine 3 glycidol intermediate of Example 17 and 4 grams of potassium hydroxide catalyst. The reactor was purged three times with nitrogen to 60 psi, then
Heat to 250 ° F. under 5 psi nitrogen pressure. Next, 4400 grams (100 moles) of ethylene oxide was added to 80
Add at a rate to maintain a reading vapor pressure below psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, the benzomorpholine 3GL / 100EO-H intermediate has an average gram molecular weight of 4775 and is ready for use.

Example 17B

[0195]

Embedded image In a 2000 ml beaker, 525 grams of 3,6-dimethylbenzomorpholine 3GL / 100EO-H intermediate (0.
11 mol), 600 grams of water, 600 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. A diazo solution (prepared in Example 15) from 16.3 grams (0.1 mole) of 2-amino-3,5-dicyano-4-methylthiophene was added dropwise to the beaker over about 30 minutes and the temperature was raised to 10 ° C. Keep less than. The resulting mixture is stirred for several hours and left overnight, after which 260 grams of 50% sodium hydroxide is added to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. The bottom salt layer is removed to give a violet liquid with a maximum absorption at 578 nm.

Embodiment 18

[0197]

Embedded image 183 grams of 85% phosphoric acid, 25 grams of 98% sulfuric acid, and 3 drops of 2-ethylhexanol defoamer are added to a 500 ml three-neck flask equipped with a thermometer, cooling bath, and mechanical stirrer. The mixture is cooled and 17.6 grams (0.1 mole) of 4-amino-N-methylphthalimide are added to the flask. Further cooling the mixture below 0 ° C.
Thereafter, 35 grams of 40% nitrosylsulfuric acid was added at a temperature of 5%.
Add while maintaining below <0> C. After 3 hours, the mixture shows a positive nitrate test, slowly adding 1 gram of sulfamic acid and keeping the temperature below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 2000 ml beaker, add m-toluidine 4
Charge 190 grams (0.11 mole) of the GL / 30EO-H intermediate, 200 grams of water, 200 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over about 30 minutes, maintaining the temperature below 10 ° C. The resulting mixture was stirred for several hours and allowed to stand overnight, after which 50% sodium hydroxide 2
Add 60 grams to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. Remove the bottom salt layer,
The product is dissolved in methylene chloride. The methylene chloride solution is washed four times with water and then dried over sodium sulfate. The methylene chloride solvent is filtered and stripped to give an orange liquid.

Embodiment 19

[0200]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 138 g (1 mol) of p-nitroaniline, 400 g of xylene, and 0.6 g of potassium hydroxide Charge gram. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

296 grams (4 moles) of glycidol are slowly added dropwise via the addition funnel. With the first few milliliters the temperature drops slightly and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this time, when the hydroxyl value of the p-nitroaniline 4-glycidol intermediate was measured, it was found to be 777 (theoretical value: 776).

Example 19A

[0204]

Embedded image In a 2 liter autoclave, 217 grams of the p-nitroaniline 4 glycidol intermediate of Example 19 (0.
5 mol), and 4 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure.

Next, 4400 grams (100 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi. After the EO addition, the reaction mixture is post-heated at 120 ° C. for 2 hours.

After vacuum stripping at 200 ° F. for 15 minutes, the p-nitroaniline 4GL / 200-H intermediate has an average gram molecular weight of 9056 and is ready for use.

Example 19B

[0208]

Embedded image A 2000 ml autoclave is charged with 1326 grams (0.15 mole) of the nitroaniline 4GL / 200EO-H intermediate of Example 19A, 600 ml of ethyl alcohol, and 90 grams of wet Raney nickel catalyst. The autoclave is purged three times with hydrogen gas and heated to 85-90 C at a pressure of about 1300 psi. After about 2 hours, the hydrogen absorption ends. A sample is taken and the solvent is distilled off in vacuo. The IR spectrum of this sample showed no nitro band, indicating the presence of the amine, indicating that the reaction was complete. Cool and evacuate the autoclave. The reaction mixture is filtered and the product is isolated by distilling off the solvent under reduced pressure.

Example 19C

[0210]

Embedded image P-Aminoaniline 4GL / 200EO of Example 19B
A solution of 1128 grams (0.125 mol) of the -H intermediate, 45 ml of concentrated hydrochloric acid and 500 ml of water is added to a 5000 ml flask and cooled to 0-5C. Sodium nitrite 10
Add grams and maintain the temperature of the mixture below 10 ° C.
After 3 hours, the mixture showed a positive nitrate test, 2 grams of sulfamic acid was added slowly and the temperature was raised to 5
Keep below ° C. After an additional hour, a negative nitrate test becomes apparent.

A 4000 ml beaker equipped with a thermometer, cooling bath and mechanical stirrer is charged with 500 grams of water and 42 grams (0.13 mole) of chromotropic acid. The pH of this mixture was adjusted to 12 with 50% sodium hydroxide,
Cool to less than 5 ° C. The diazo solution is slowly dropped into the beaker, keeping the temperature below 5 ° C. and keeping the pH above 7 with versene (sodium salt of EDTA). When the addition is over, the resulting mixture is stirred for 3 hours for post-coupling. At the end of this, the pH is adjusted to 8.5 with dilute acetic acid, where the blue product has a maximum absorption at 623 nm.

Comparative Example 19D

[0213]

Embedded image 1113 grams (0.125 mole) of p-aminoaniline 200EO-H intermediate, 45 ml of concentrated hydrochloric acid, and 500 parts of water
Add the ml solution to the 5000 ml flask and cool to 0-5 ° C. Add 10 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

A 4000 ml beaker equipped with a thermometer, cooling bath and mechanical stirrer is charged with 500 grams of water and 42 grams (0.13 mole) of chromotropic acid. The pH of this mixture was adjusted to 12 with 50% sodium hydroxide,
Cool to less than 5 ° C. The diazo solution is slowly dropped into the beaker, keeping the temperature below 5 ° C. and keeping the pH above 7 with versen. When the addition is over, the resulting mixture is stirred for 3 hours for post-coupling. At the end of this, the pH is adjusted to 8.5 with dilute acetic acid, where the blue product has a maximum absorption at 623 nm.

Embodiment 20

[0216]

Embedded image 24.8 grams of 4,4'-methylenedianiline (0.1
25 mol), 90 ml of concentrated hydrochloric acid and 180 ml of water are added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and raise the temperature of the mixture to 10 ° C.
Keep less than. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Slowly add dropwise to the beaker over 0 minutes to maintain the temperature below 5 ° C. The resulting mixture was stirred for several hours and left overnight, after which the excess acid was neutralized to pH about 7 by the addition of 50% sodium hydroxide, maintaining the temperature below 20 ° C and maintaining the temperature at 453 nm. A yellow-orange product with maximum absorption is obtained.

Embodiment 21

[0219]

Embedded image 36 grams (0.125 mol) of 4,4'-methylenebis (3-nitroaniline), 90 ml of concentrated hydrochloric acid and 18 parts of water
Add 0 ml of the solution to a 500 ml flask and cool to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
An orange product having a maximum absorption at 80 nm is obtained.

Embodiment 22

[0222]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 153 grams (1.0 mole) of 2,5-dimethoxyaniline and 0.8 mol of potassium hydroxide Charge gram. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

296 g (4.0 mol) of glycidol
Is slowly added dropwise via an addition funnel. The first two,
The temperature drops slightly due to the dropping of 3 ml, and heat is generated. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 22A

[0226]

Embedded image In a 2 gallon autoclave, the 2,5-
Charge 449 grams (1.0 mole) of dimethoxyaniline 4 glycidol intermediate and 4 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure. Next, 8800 grams (200 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, 2,5-dimethoxyaniline 4GL / 200E
The hydroxyl number of the OH intermediate was determined to be 3
It turned out to be 9.6 (theoretical value is 36.4),
It has an average gram molecular weight of 500 and is ready to use.

Example 22B

[0230]

Embedded image 36 grams (0.125 mol) of 4,4'-methylenebis (3-nitroaniline), 90 ml of concentrated hydrochloric acid and 18 parts of water
Add 0 ml of the solution to a 500 ml flask and cool to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, 2,5-dimethoxyaniline 4
2210 grams of GL / 200EO-H intermediate (0.26
Mol), 500 grams of water, 500 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C.
The diazo solution is dropped into the beaker over 30 minutes, maintaining the temperature below 5 ° C. The resulting mixture was stirred for several hours and left overnight, after which 50% sodium hydroxide was added to neutralize excess acid to a pH of about 7 and to a temperature of 20.
Keeping below 0 ° C. gives a red product with a maximum absorption at 512 nm.

Embodiment 23

[0233]

Embedded image 30 grams (0.126 mol) of 4,4'-ethylene-di-m-toluidine, 90 ml of concentrated hydrochloric acid and 180 ml of water
Is added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
A yellowish orange product having a maximum absorption at 53 nm is obtained.

Embodiment 24

[0236]

Embedded image A solution of 36 grams (0.125 mol) of pararosaniline, 120 ml of concentrated hydrochloric acid and 270 ml of water is added to a 500 ml flask and cooled to 0-5 ° C. Sodium nitrite 3
Add 0 grams and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 5000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 100EO-
3446 grams (0.375 mole) of H intermediate, 500 water
Grams, 500 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over 30 minutes, maintaining the temperature below 5 ° C. The resulting mixture was stirred for several hours and left overnight, after which the excess acid was neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature was maintained below 20 ° C to 451 nm. A yellowish orange product having a maximum absorption is obtained.

Embodiment 25

[0239]

Embedded image 25 grams of 4,4'-diaminodiphenyl ether (0.126 mole), 90 ml of concentrated hydrochloric acid, and 180 ml of water
Is added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
An orange product having a maximum absorption at 90 nm is obtained.

Embodiment 26

[0242]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 138 grams (1.0 mol) of 4-methoxy-1,3-phenylenediamine and hydroxylated Charge 0.8 grams of potassium. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

592 g (8.0 mol) of glycidol
Is slowly added dropwise via an addition funnel. The first two,
The temperature drops slightly due to the dropping of 3 ml, and heat is generated. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 26A

[0246]

Embedded image In a 2 gallon autoclave are charged 434 grams (1.0 mole) of the 4-methoxy-1,3-phenylenediamine 4 glycidol intermediate of Example 26 and 4 grams of potassium hydroxide catalyst. Reactor with nitrogen 3 times, 60ps
i and then under 250 psi of nitrogen at 5 psi
Heat to ° F. Next, 8800 grams (200 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, 4-methoxy-1,3-phenylenediamine 4
The hydroxyl number was measured on the GL / 200EO-H intermediate and was found to be 70.9 (theoretical 72.9), with an average gram molecular weight of 9495 and ready to use.

Example 26B

[0250]

Embedded image 25 grams of 4,4'-diaminodiphenyl ether (0.125 mole), 90 ml of concentrated hydrochloric acid, and 180 ml of water
Is added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, cooling bath and mechanical stirrer, the 4-methoxy-
Charge 2469 grams (0.26 mole) of 1,3-phenylenediamine 4GL / 200EO-H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The above diazo solution was added to 30
Add dropwise to the beaker over a minute and maintain the temperature below 5 ° C. The resulting mixture was stirred for several hours and left overnight, after which time the excess acid was neutralized to pH about 7 by the addition of 50% sodium hydroxide, maintaining the temperature below 20 ° C.
A red product having a maximum absorption at 08 nm is obtained.

Embodiment 27

[0253]

Embedded image 31 grams (0.126 mole) of 4,4'-diaminodiphenyl sulfone, 90 ml of concentrated hydrochloric acid, and 180 ml of water
Is added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
An orange product having a maximum absorption at 85 nm is obtained.

Embodiment 28

[0256]

Embedded image 31 grams of 3,3'-diaminodiphenyl sulfone (0.126 mole), 90 ml of concentrated hydrochloric acid, and 180 ml of water
Is added to a 500 ml flask and cooled to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
An orange product having a maximum absorption at 64 nm is obtained.

Embodiment 29

[0259]

Embedded image 31 grams of 3,3'-dimethoxybenzidine (0.12
6 mol), 90 ml of concentrated hydrochloric acid and 180 ml of water.
Add to a 00 ml flask and cool to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture was stirred for several hours and left overnight, after which time the excess acid was neutralized to pH about 7 by the addition of 50% sodium hydroxide, maintaining the temperature below 20 ° C.
A red product having a maximum absorption at 30 nm is obtained.

Embodiment 30

[0262]

Embedded image A solution of 13.6 grams (0.126 mole) of m-phenylenediamine, 90 ml of concentrated hydrochloric acid, and 180 ml of water was added to 500
Add to the ml flask and cool to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture showed a positive nitrate test, 2 grams of sulfamic acid was added slowly,
Keep the temperature below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, cooling bath and mechanical stirrer, m-toluidine 4GL / 200
2392 grams (0.26 mol) of the EO-H intermediate, water 5
Charge 00 grams, 500 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is slowly dropped into the beaker over 30 minutes, keeping the temperature below 5 ° C. Stir the resulting mixture for several hours,
Leave overnight and then add 50% sodium hydroxide to neutralize excess acid to a pH of about 7 and maintain the temperature below 20 ° C. to obtain an orange product.

Embodiment 31

[0265]

Embedded image 4-amino- (4'-aminophenyl) benzamide 2
A solution of 8.6 grams (0.126 mole), 90 ml of concentrated hydrochloric acid, and 180 ml of water was added to a 500 ml flask,
Cool to 5 ° C. Add 20 grams of sodium nitrite,
Maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture shows a positive nitrate test, 2 grams of sulfamic acid are added slowly and the temperature is kept below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with thermometer, cooling bath and mechanical stirrer, m-toluidine 4GL / 200
2392 grams (0.26 mol) of the EO-H intermediate, water 5
Charge 00 grams, 500 grams of ice, and 4 grams of urea. The mixture is cooled below 0 ° C. The diazo solution is dropped into the beaker over 30 minutes, maintaining the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C to produce an orange color. Get things.

Embodiment 32

[0268]

Embedded image A solution of 20 grams (0.126 mole) of 1,8-diaminonaphthalene, 90 ml of concentrated hydrochloric acid, and 180 ml of water was added to 500
Add to the ml flask and cool to 0-5 ° C. Add 20 grams of sodium nitrite and maintain the temperature of the mixture below 10 ° C. After 3 hours, the mixture showed a positive nitrate test, 2 grams of sulfamic acid was added slowly,
Keep the temperature below 5 ° C. After an additional hour, a negative nitrate test becomes apparent.

In a 4000 ml beaker equipped with a thermometer, a cooling bath and a mechanical stirrer, aniline 4GL / 200EO-
Charge 2389 grams (0.26 mole) of H intermediate, 500 grams of water, 500 grams of ice, and 4 grams of urea.
The mixture is cooled below 0 ° C. Add the above diazo solution to 3
Add dropwise to the beaker over 0 minutes and maintain the temperature below 5 ° C. The resulting mixture is stirred for several hours and left overnight, after which the excess acid is neutralized to pH about 7 by the addition of 50% sodium hydroxide and the temperature is maintained below 20 ° C.
A yellow product having a maximum absorption at 43 nm is obtained.

Embodiment 33

[0271]

Embedded image A thiazole azoaniline intermediate (Example 1) was placed in a flask equipped with a heating mantle, stirrer, and nitrogen inlet / outlet.
75 g (0.047 mol) are added. After heating the flask to 40 ° C. and purging with nitrogen, 15.1 grams (0.12 mol) of dimethyl sulfate are introduced into the flask. The temperature is raised to 95 ° C. for 1 hour to complete the reaction. After cooling to 40 ° C., the pH is adjusted to 8.0 with a 10% solution of ammonium hydroxide to obtain a blue liquid having a maximum absorption at 601 nm.

Embodiment 34

[0273]

Embedded image To a flask equipped with a heating mantle, stirrer, and nitrogen inlet / outlet, add 175 grams (0.047 mol) of the benzothiazole azo intermediate (prepared in Example 6). After heating the flask to 40 ° C. and purging with nitrogen, 15.1 grams (0.12 mol) of dimethyl sulfate are introduced into the flask. The temperature is raised to 95 ° C. for 1 hour to complete the reaction. After cooling to 40 ° C., the pH is adjusted to 8.0 with a 10% solution of ammonium hydroxide to obtain a blue liquid having a maximum absorption at 620 nm.

Example 35

[0275]

Embedded image A mixture is prepared by adding 2937 grams (0.3 mole) of the aniline 4GL / 200EO-H intermediate (prepared in Example 1A) to 8 moles of acetic anhydride. The mixture is stirred mechanically and 5 drops of N-methylimidazole catalyst are added. After the initial exotherm, the reaction mixture is heated to 100-120 ° C and maintained at 110-110 ° C for an additional 2 hours to ensure reaction completion. The mixture is cooled and the product is isolated by removing the excess acetic acid and acetic anhydride at 90 ° C. under reduced pressure. The IR spectrum of the resulting liquid product shows no hydroxyl absorption and shows the characteristic carbonyl absorption of the corresponding acetate intermediate.

Example 35A

[0277]

Embedded image A dry 2000 ml three-necked flask is charged with 181 grams of N, N-dimethylformamide under nitrogen and cooled to 0 ° C. With mechanical stirring and cooling, 192 grams of phosphorus oxychloride are added over 1 hour. The resulting mixture is stirred at 0-5 <0> C for another 2 hours. Then, aniline 4
907 grams (0.3 mol) of the GL / 200EO-H acetate intermediate (from Example 35) are added dropwise. The reaction mixture is gradually heated to 90 ° C. and maintained at this temperature for a further 2 hours to ensure reaction completion. After cooling, the mixture is diluted with an equal volume of ice and 0.83 mol of sodium hydroxide (50% by weight). The resulting mixture is heated to 50-60 ° C. to hydrolyze the formylated acetate intermediate. The mixture is then neutralized with acetic acid and the product is extracted into methylene chloride. The methylene chloride layer is phase separated and dried over anhydrous magnesium sulfate. The methylene chloride solution is filtered and the solvent is removed at 90 ° C. under vacuum. The resulting liquid has a maximum absorption at 341 nm. The IR spectrum of the resulting liquid product shows the presence of hydroxyl absorption and the characteristic carbonyl absorption of the corresponding formyl intermediate.

Example 35B

[0279]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 442 grams (0.05 mole) of the aldehyde from Example 35A, 5.7 grams of ethyl cyanoacetate. (0.05 mol), 1 drop of piperidine catalyst and 300 ml of toluene. The mixture is heated under reflux until no more water condenses in the trap, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give a yellow liquid with a maximum absorption at 426 nm.

Embodiment 36

[0281]

Embedded image In a 500 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 445 grams (0.05 mole) of the aldehyde from Example 35A, 3.3 grams of malononitrile (0 grams). 0.05 mol), 1 drop of piperidine catalyst and 300 ml of toluene. The mixture is heated under reflux until no more water condenses in the trap, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give a yellow liquid with a maximum absorption at 426 nm.

Embodiment 37

[0283]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 442 grams (0.05 mole) of aldehyde from Example 35A, 1-phenylethylidenemalononitrile 8 0.4 g (0.05 mol), 1 drop of piperidine catalyst and 300 ml of toluene are added. The mixture is heated under reflux until no more water condenses in the trap, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution was dried over magnesium sulfate,
Filter into a 0 ml round bottom flask. The solution was stripped under reduced pressure to remove all volatiles and 500 nm
A red liquid with maximum absorption is obtained.

Embodiment 38

[0285]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 347 grams (0.05 mol) of aldehyde, 3-cyano-4-phenyl-2- (5H ) -Furanone 9.3 g (0.05 mol), piperidine catalyst 1
Add drops and 300 ml of toluene. This mixture is
Heat under reflux until water no longer agglomerates in the trap,
This takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution was dried over magnesium sulfate, and 1000 ml
In a round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give a red liquid with a maximum absorption at 530 nm.

Embodiment 39

[0287]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 457 grams (0.05 mol) of aldehyde, 3-ethoxycarbonyl-4-phenyl-2-phenyl.
9.3 grams (0.05 mole) of (5H) -furanone, one drop of piperidine catalyst and 300 ml of toluene are added.
The mixture is kept until no more water condenses in the trap.
Heat under reflux, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water.
The methylene chloride solution is dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. The solution was stripped under reduced pressure to remove all volatiles,
A red liquid having a maximum absorption at 504 nm is obtained.

Embodiment 40

[0289]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 442 grams (0.05 mol) of aldehyde, 3-methyl-1-phenyl-2-pyrazolone 8 were added. .
7 grams (0.05 mole), 1 drop of piperidine catalyst and 300 ml of toluene are added. The mixture is heated under reflux until no more water condenses in the trap, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give an orange liquid with a maximum absorption at 464 nm.

Embodiment 41

[0291]

Embedded image The benzomorpholine 3 of Example 17A was added to 6 mol of acetic anhydride.
A mixture is prepared by adding 2388 grams (0.5 mole) of the GL / 100EO-H intermediate. The mixture is stirred mechanically and 5 drops of N-methylimidazole catalyst are added. After the initial exotherm, the reaction mixture is heated to 100-120 ° C and maintained at 110-110 ° C for an additional 2 hours to ensure reaction completion. The mixture is cooled and the product is isolated by removing the excess acetic acid and acetic anhydride at 90 ° C. under reduced pressure. The IR spectrum of the resulting liquid product shows no hydroxyl absorption and shows the characteristic carbonyl absorption of the corresponding acetate intermediate.

Example 41A

[0293]

Embedded image A dry 2000 ml three-necked flask is charged with 45 grams of N, N-dimethylformamide under nitrogen and cooled to 0 ° C. Phosphorus oxychloride 4 with mechanical stirring and cooling
Add 8 grams over 1 hour. The resulting mixture is
Stir for a further 2 hours at 5 ° C. Then, 1246 grams (0.25 mol) of the benzomorpholine 3GL / 100EO acetate intermediate (prepared in Example 41) are added dropwise. The reaction mixture is gradually heated to 90 ° C. and maintained at this temperature for a further 2 hours to ensure reaction completion. After cooling, the mixture is diluted with an equal volume of ice and 0.65 mol of sodium hydroxide (50% by weight). Heating the resulting mixture to 50-60 ° C,
Hydrolyze the formylated acetate intermediate. Then
The mixture is neutralized with acetic acid and the product is extracted into methylene chloride. The methylene chloride layer is phase separated and dried over anhydrous magnesium sulfate. The methylene chloride solution is filtered and the solvent is removed at 90 ° C. under vacuum. The resulting liquid has a maximum absorption at 356 nm. The IR spectrum of the resulting liquid product shows the presence of hydroxyl absorption and the characteristic carbonyl absorption of the corresponding formyl intermediate.

Example 41B

[0295]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 242 grams (0.05 mole) of the aldehyde of Example 41, 3 (2H) -thianaphthalenone 9.
One gram (0.05 mole), one drop of piperidine catalyst and 300 ml of toluene are added. The mixture is heated under reflux until no more water condenses in the trap, which takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give a reddish orange liquid with a maximum absorption at 464 nm.

Example 42

[0297]

Embedded image In 7 mol of acetic anhydride, m-toluidine 4GL / 30EO-
A mixture is prepared by adding 1723 grams (1 mole) of the H intermediate. The mixture was mechanically stirred and N-
Add 5 drops of methylimidazole catalyst. After the initial exotherm, heat the reaction mixture to 100-120 ° C and 110-110 ° C.
And keep the reaction complete for 2 hours. The mixture is cooled and the product is isolated by removing the excess acetic acid and acetic anhydride at 90 ° C. under reduced pressure. The IR spectrum of the resulting liquid product shows no hydroxyl absorption and shows the characteristic carbonyl absorption of the corresponding acetate intermediate.

Example 42A

[0299]

Embedded image A dry 3000 ml three-necked flask is charged with 181 grams of N, N-dimethylformamide under nitrogen and cooled to 0 ° C. With mechanical stirring and cooling, 192 grams of phosphorus oxychloride are added over 1 hour. The resulting mixture is stirred at 0-5 <0> C for another 2 hours. Then, Example 42
M-toluidine 4GL / 30EO acetate intermediate 1
975 grams (1 mole) are added dropwise. The reaction mixture is gradually heated to 90 ° C. and maintained at this temperature for a further 2 hours to ensure reaction completion. After cooling, the mixture is diluted with an equal volume of ice and 2.5 mol of sodium hydroxide (50% by weight). The resulting mixture is heated to 50-60 ° C. to hydrolyze the formylated acetate intermediate. The mixture is then neutralized with acetic acid and the product is extracted into methylene chloride. The methylene chloride layer is phase separated and dried over anhydrous magnesium sulfate. The methylene chloride solution is filtered and the solvent is removed at 90 ° C. under vacuum. The liquid obtained is 342 nm
Has maximum absorption. The IR spectrum of the resulting liquid product shows the presence of hydroxyl absorption and the characteristic carbonyl absorption of the corresponding formyl intermediate.

Example 42B

[0301]

Embedded image In a 500 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 175 grams (0.1 mole) of the aldehyde of Example 42A, 3 (2H) -thianaphthalenone. 18.
2 grams (0.1 mole), 2 drops of piperidine catalyst and 300 ml of toluene are added. The mixture is heated at reflux until no more water condenses in the trap, including:
It takes about 4 hours. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 500 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give an orange liquid with a maximum absorption at 493 nm.

Embodiment 43

[0303]

Embedded image In a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean-Stark trap, mechanical stirrer, and heating mantle, 462 grams (0.05 mole) of aldehyde, 11.4 grams of substituted 3 (2H) -thianaphthalidene ( 0.05 mol), one drop of piperidine catalyst and 300 ml of toluene. The mixture is heated under reflux until no more water condenses in the trap, which comprises about 4
It takes time. The resulting mixture is dissolved in methylene chloride and washed three times with water. The methylene chloride solution is dried over magnesium sulfate and filtered into a 500 ml round bottom flask. The solution is stripped under reduced pressure to remove all volatiles to give a blue liquid with a maximum absorption at 600 nm.

Embodiment 44

[0305]

Embedded image 462 g (0.05 mol) of aldehyde, 7.3 g (0.05 mol) of 1,3-indandione, one drop of piperidine catalyst and 300 ml of toluene were charged with a thermometer, reflux condenser, Dean Stark trap, heating mantle and It was charged to a 1000 ml three-necked flask equipped with a mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in an orange liquid with a maximum absorbance of 501 nm.

Embodiment 45

[0307]

Embedded image 450 g (0.025 mol) of aldehyde, 5.6 g (0.025 mol) of thiazole intermediate, one drop of piperidine catalyst and 300 ml of toluene are charged with a thermometer, reflux condenser, Dean-Stark trap, heating mantle and mechanical stirrer Was charged into a 1000 ml three-necked flask equipped with. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in a blue-green liquid with a maximum absorbance of 658 nm.

Embodiment 46

[0309]

Embedded image 462 g (0.05 mol) of aldehyde, 5.6 g of dione
(0.05 mol), one drop of piperidine catalyst and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a purple liquid with a maximum absorbance of 557 nm.

Embodiment 47

[0311]

Embedded image Acetic acid 200 g, 2-methylene 1,3,3-trimethylindoline 8.8 g (0.05 mol), formylaniline, 3GL / 200EO-H intermediate 461 g (0.05 mol)
Mol) was charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, heating mantle and mechanical stirrer. The mixture was heated at 95 ° C., and then 95-1
It was kept at 00 ° C. for a further 6 hours. The reaction mixture was cooled and transferred to a 1000 ml round bottom flask to remove acetic acid. As a result of adjusting the pH of the obtained product to 7 with 25% sodium hydroxide, a blue-red liquid having a maximum absorbance of 546 nm was obtained.

Embodiment 48

[0313]

Embedded image 180 g (1.34 mol) of 1,2,3,4-tetrahydroquinoline in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, and potassium hydroxide 0.
Charge 6 grams. While stirring, the mixture is heated by a heating mantle and temperature controller.

298 grams (4.03 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. The aniline 12 was added to a dry 1000 ml three-necked flask equipped with an addition funnel.
5 grams (1.34 moles) and potassium hydroxide 0.
Charge 6 grams. While stirring, the mixture is heated by a heating mantle and temperature controller.

397 grams (5.36 moles) of glycidol are slowly added dropwise via the addition funnel. The temperature drops slightly with the first few milliliters,
Fever begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this point, the hydroxyl number of this tetrahydroquinoline 3 glycidol intermediate was determined to be 763 (theoretical, 63
2).

Example 48A

[0319]

Embedded image In a 1 gallon autoclave are charged 487 grams (1.37 moles) of the tetrahydroquinoline 3 glycidol intermediate of Example 48 and 2 grams of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure. Next, 1808 grams of ethylene oxide (41.1
Mol) at such a rate as to maintain a reading vapor pressure of 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours. At this time, the hydroxyl value of the reaction mixture was 38.2 (theoretical value is 35.6).

After vacuum stripping at 200 ° F. for 15 minutes, tetrahydroquinoline 3GL / 30EO-H
The intermediate has a gram molecular weight of 1675 and is ready for use.

Example 48B

[0323]

Embedded image Tetrahydroquinoline 3GL / 30E of Example 48A
838 g (0.5 mol) of the OH intermediate was dissolved in 6 mol of acetic anhydride to obtain a mixture. This mixture is stirred mechanically,
Five drops of N-methylimidazole catalyst were added. After the first exotherm, the reaction mixture is heated to 100-120 ° C.
The temperature was further maintained at 110-110 ° C for 2 hours to complete the reaction. The mixture was cooled and excess acetic acid and acetic anhydride were removed at 90 ° C. under reduced pressure to separate the product. The IR spectrum of this liquid product showed a lack of hydroxyl absorption and a characteristic carbonyl absorption of the corresponding acetate intermediate.

Example 48C

[0325]

Embedded image 45 g of N, N-dimethylformamide was charged to a dried 1000 ml three-necked flask under a nitrogen atmosphere, and cooled to 0 ° C. 48 g of phosphorus oxychloride was added dropwise over 1 hour under cooling and stirring. The resulting mixture was stirred at 0-5 <0> C for another 2 hours. Then, 838 g (0.5 mol) of the tetrahydroquinoline 3GL / 10PO / 10EO-acetate intermediate of Example 48B was added dropwise.

The reaction mixture was gradually heated to 90 ° C. and kept at this temperature for another 2 hours to complete the reaction. After cooling, the mixture was diluted with an equal volume of ice and 0.65 mol (50% by weight) of sodium hydroxide. The resulting mixture was heated at 50-60 ° C until the formylated acetate intermediate hydrolyzed. The resulting mixture was neutralized with acetic acid and the product was extracted into methylene chloride. The methylene chloride phase was separated and dried over anhydrous magnesium sulfate. The methylene chloride solution was filtered and the solvent was removed at 90 ° C. under reduced pressure. The IR spectrum of the liquid product showed the presence of hydroxyl absorption and the characteristic carbonyl absorption of the corresponding formyl intermediate.

Example 48D

[0328]

Embedded image Acetic acid 400 g, 2-methylene-1,3,3-trimethylindoline 17.3 g (0.1 mol), formyl-tetramethyltetrahydroquinoline 3GL / 100EO-
170.2 g of H intermediate (obtained in Example 48C)
(0.1 mol) was charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, heating mantle and mechanical stirrer. The mixture was heated to 95C with a heating mantle and kept at a temperature of 95-100C for an additional 6 hours. The reaction mixture was cooled and transferred to a 1000 ml round bottom flask to remove acetic acid. As a result of adjusting the pH of the obtained product to 7 with 25% sodium hydroxide, a blue-red liquid was obtained.

Example 49

[0330]

Embedded image 21 g of methylium methylbenzothiazole iodide (0.
07 mol), formylaniline 4GL / 100EO-H
337 g (0.07 mol) of the intermediate and 0.2 g of the morpholine catalyst were charged to a 1000 ml three-necked flask equipped with a thermometer, a reflux condenser, a heating mantle and a mechanical stirrer. The mixture was heated to 95 ° C. with a heating mantle,
The temperature was kept at 5 ° C. for another 3 hours. The reaction mixture was cooled and transferred to a 1000 ml round bottom flask to remove all volatiles and collect the red liquid.

[0331]

Embedded image 70 g (0.47 mol) of 2-methylbenzothiazole were rapidly added to the cased plastic bottle at 13C with 133.2 g (0.94 mol) of methyl iodide. The bottle was sealed with a stopper and copper wire and placed in a steam bath for about 2 hours. At the end of this reaction time, the bottle was opened and excess methyl iodide was vaporized and removed. The product was isolated as a crushed solid. Training example 50

[0332]

Embedded image The aniline 4GL / 200EO-H intermediate 2 of Example 1A
203 grams (0.25 mol) were charged into a 3000 ml three-necked flask with 100 ml of concentrated hydrochloric acid and 25 ml of water to form a mixture. The mixture was stirred and cooled to 0 ° C. Then, a solution of 19 g (0.28 mol) of sodium nitrate dissolved in 75 ml of water was added dropwise over 1.5 hours while maintaining the temperature at 0 ° C. The mixture was warmed to room temperature and stirred for another 2 hours. Excess nitrite was destroyed by pulling a vacuum for 30 minutes.

After cooling to 0 ° C., the mixture was neutralized with dilute sodium hydroxide solution and the product was extracted into methylene chloride. The methylene chloride phase was separated and dried over anhydrous magnesium sulfate. The methylene chloride solution was filtered and the solvent was removed at 90 ° C. under reduced pressure. This liquid product had a maximum absorbance of 400 nm, and a characteristic nitroso absorption was recognized by IR spectrum.

Example 50A

[0335]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of intermediate, 7.1 g (0.05 mol) of homophthalonitrile and 300 ml of toluene
1000 m with thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
1-necked three-necked flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and dried.
Filtered into a 000 ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in an orange liquid with a maximum absorbance of 489 nm.

Example 50B

[0337]

Embedded image 446 g of the nitrosoaniline 200EO-H intermediate (0.
05 mol), 7.1 g (0.05 mol) of homophthalonitrile and 300 ml of toluene were charged into a 1000 ml three-necked flask equipped with a thermometer, a reflux condenser, a Dean-Stark trap, a heating mantle and a mechanical stirrer. . The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in an orange product with a maximum absorbance of 489 nm.

Embodiment 51

[0339]

Embedded image Nitroso-m-oxyaniline 5GL / 200EO-H
476 g (0.05 mol) of intermediate, 7.1 g (0.05 mol) of homophthalonitrile and 300 ml of toluene
1000 m with thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
1-necked three-necked flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and dried.
Filtered into a 000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a red product with a maximum absorbance of 505.5 nm.

Example 51A

[0341]

Embedded image Nitroso-m-oxyaniline 200EO-H intermediate 4
47 g (0.05 mol), 7.1 g of homophthalonitrile
(0.05 mol) and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate, 1000
Filtered into a ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in a maximum absorbance of 50
A 5.5 nm red product was obtained.

Embodiment 52

[0343]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 8.3 g (0.05 mol) of benzoylnitromethane and 300 m of toluene
1 with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
It was charged in a three-necked ml flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. Drying the resulting methylene chloride solution over magnesium sulfate,
Filtered into a 1000 ml round bottom flask. Removal of all volatiles from this solution under reduced pressure gave a yellow product with a maximum absorbance of 427 nm.

Example 52A

[0345]

Embedded image 446 g of the nitrosoaniline 200EO-H intermediate (0.
Benzoylnitromethane (8.3 g, 0.0 mol)
5 mol) and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from this solution under reduced pressure gave a yellow product with a maximum absorbance of 427 nm.

Embodiment 53

[0347]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 3.3 g (0.05 mol) of malononitromethane and 300 ml of toluene
1000 m with thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
1-necked three-necked flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and dried.
Filtered into a 000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in an orange product with a maximum absorbance of 503 nm.

Example 53A

[0349]

Embedded image 440 g of the nitrosoaniline 200EO-H intermediate (0.
05 mol), 3.3 g (0.05 mol) of malononitromethane and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a red product with a maximum absorbance of 503 nm.

Embodiment 54

[0351]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 6.4 g (0.05 mol) of cyanoacetylurea and 300 ml of toluene
1000 m with thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
1-necked three-necked flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and dried.
Filtered into a 000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a yellow product with a maximum absorbance of 416 nm.

Example 54A

[0353]

Embedded image 446 g of the nitrosoaniline 200EO-H intermediate (0.
05 mol), 6.4 g (0.05 mol) of cyanoacetylurea and 300 ml of toluene were charged into a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. . The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a yellow product with a maximum absorbance of 416 nm.

Embodiment 55

[0355]

Embedded image Nitrosoaniline 4GL / 100EO-H intermediate 241
g (0.05 mol), 3-methyl-1-phenyl-2-
8.7 g (0.05 mol) of pyrazolone and toluene 3
1 ml with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
It was charged in a 000 ml three-necked flask. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. As a result of removing all volatiles from this solution under reduced pressure,
A red product with a maximum absorbance of 522 nm was obtained.

Embodiment 56

[0357]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 11.3 g (0.05 mol) of substituted 3 (2H) -thianaphthalidene and 300 ml of toluene were charged with a thermometer, reflux condenser, Dean-Stark trap, heating mantle and mechanical stirrer. Was charged into a 1000 ml three-necked flask equipped with. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a bluish-green product with a maximum absorbance of 650 nm.

Example 57

[0359]

Embedded image Nitrosoaniline 4GL / 100EO-H intermediate 241
g (0.05 mol), 11.3 g of a thiazole intermediate
(0.05 mol) and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate, 1000
Filtered into a ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in a maximum absorbance of 67.
A blue-green product of 2 nm was obtained.

Embodiment 58

[0361]

Embedded image Nitrosoaniline 4GL / 100EO-H intermediate 241
g (0.05 mol), 7.3 g of 1,3-indandione
(0.05 mol) and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate, 1000
Filtered into a ml round bottom flask. Removal of all volatiles from this solution under reduced pressure resulted in a maximum absorbance of 52
A red product of 0 nm was obtained.

Example 59

[0363]

Embedded image Nitrosoaniline 4GL / 100EO-H intermediate 241
g (0.05 mol), the dione intermediate 11.3 g (0.0
5 mol) and 300 ml of toluene were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water. The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a blue product with a maximum absorbance of 618 nm.

Example 61

[0365]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 9.3 g (0.05 mol) of 3-cyano-4-phenyl-2-furanone and 300 ml of toluene were charged with a thermometer, a reflux condenser, a Dean-Stark trap, and a heating mantle. And a 1000 ml three-necked flask equipped with a mechanical stirrer. The mixture was heated at reflux temperature and continued for about 4 hours until no more water was condensed in the trap. The resulting mixture was dissolved in methylene chloride and washed three times with water.
The resulting methylene chloride solution was dried over magnesium sulfate and filtered into a 1000 ml round bottom flask. Removal of all volatiles from the solution under reduced pressure resulted in a blue-violet product with a maximum absorbance of 565 nm.

Example 61

[0367]

Embedded image Nitrosoaniline 4GL / 100EO-H intermediate 241
g (0.05 mol), 1-naphthol 7.2 g (0.0
5 mol) and 50 ml of water were charged to a 500 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer.
The pH of this mixture was adjusted to 6.0 with sodium bicarbonate solution and 2 g of morpholine catalyst was added. The mixture was then heated at 75 C for about 7 hours. The resulting mixture was a blue-green product with a maximum absorbance of 613 nm.

Example 62

[0369]

Embedded image Nitrosoaniline 4GL / 200EO-H of Example 50
460 g (0.05 mol) of the intermediate, 50.8 g (0.05 mol) of 1,5-naphthalenediol and 50 ml of water
1000 m with thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer
1-necked three-necked flask. The pH of this mixture was adjusted to 6.0 with sodium bicarbonate solution and 2 g of morpholine catalyst was added. The mixture was then heated at 75 C for about 7 hours. The resulting mixture was a blue product with a maximum absorbance of 605 nm.

Example 62A

[0371]

Embedded image Nitrosoaniline 4GL / 200EO-H intermediate 446
g (0.05 mol), 8 g of 1,5-naphthalenediol
(0.05 mol) and 50 ml of water were charged to a 1000 ml three-necked flask equipped with a thermometer, reflux condenser, Dean Stark trap, heating mantle and mechanical stirrer. 5. The pH of the mixture is adjusted with sodium bicarbonate solution.
It was adjusted to 0 and 2 g of morpholine catalyst was added. The mixture was then heated at 75 C for about 7 hours. The resulting mixture was a blue product with a maximum absorbance of 605 nm.

Example 63

[0373]

Embedded image 13 g (0.05 mol) of 80% o-formylbenzenesulfonic acid sodium salt (80% purity), aniline 4G
L / 100EO-H479g (0.1mol), urea 1g
And 6 g of diluted mineral acid were charged into a 1000 ml flask. Then, after heating at 90 ° C. for 3 hours, 8 g of clonanyl was added, and the mixture was further heated for 2 hours. The fire was then removed and cooled to room temperature. The resulting mixture was stirred for several hours, allowed to stand for one day and night, and then sodium hydroxide was added to neutralize excess acid to a pH of about 7, and the temperature was adjusted to 20.
C. or less. The bottom salt layer was removed and the product was dissolved in methylene chloride. The methylene chloride solution was washed four times with water, dried over sodium sulfate, then filtered and stripped to give a bluish green product having a maximum absorbance of 635 nm.

Example 64

[0375]

Embedded image 26 g (0.1 mol) of 80% o-formylbenzenesulfonic acid sodium salt (80% purity), 254 g (0.2 mol) of m-toluidine 4GL / 20EO-H intermediate,
1.4 g urea and 6 g dilute mineral acid were charged to a 500 ml flask. Then, after heating at 90 ° C. for 3 hours, 16 g of clonanil was added, and the mixture was further heated for 2 hours. The fire was then removed and cooled to room temperature. The resulting mixture was stirred for several hours, allowed to stand for one day and night, and then sodium hydroxide was added to neutralize excess acid to a pH of about 7,
The temperature was kept below 20 ° C. The bottom salt layer was removed and the product was dissolved in methylene chloride. The methylene chloride solution was washed four times with water, dried over sodium sulfate, and then filtered and stripped from the methylene chloride solution.
A blue-green product with a maximum absorbance of 655 nm was obtained.

Example 65

[0377]

Embedded image 13 g (0.05 mol) of 80% o-formylbenzenesulfonic acid sodium salt (80% purity), 482 g (0.1 mol) of m-anisidine 4GL / 100EO-H intermediate, 1 g of urea and 6 g of dilute mineral acid Charged into a 1000 ml flask. Then, after heating at 90 ° C. for 3 hours, 8 g of clonanyl was added, and the mixture was further heated for 2 hours. The fire was then removed and cooled to room temperature.
After stirring the obtained mixture for several hours and allowing it to stand for one day and night,
Sodium hydroxide was added to neutralize the excess acid to a pH of about 7, and the temperature was kept below 20 ° C. Remove the bottom salt layer,
The product was dissolved in methylene chloride. The methylene chloride solution was washed four times with water, dried over sodium sulfate, then filtered and stripped to give a bluish green product having a maximum absorbance of 635 nm.

Example 66

[0379]

Embedded image 13 g (0.05 mol) of 80% o-formylbenzenesulfonic acid sodium salt (80% purity), 896 g (0.1 mol) of m-anisidine 200EO-H intermediate, 1 g of urea and 6 g of dilute mineral acid were added to 1000 ml of The flask was charged. Then, after heating at 90 ° C. for 3 hours, 8 g of clonanyl was added, and the mixture was further heated for 2 hours. The fire was then removed and cooled to room temperature. The resulting mixture was stirred for several hours, allowed to stand for one day and night, and then sodium hydroxide was added to neutralize the excess acid to a pH of about 7, and the temperature was adjusted to 2
It was kept below 0 ° C. The bottom salt layer was removed and the product was dissolved in methylene chloride. The methylene chloride solution was washed four times with water, dried over sodium sulfate, then filtered and stripped to give a bluish green product having a maximum absorbance of 635 nm.

Example 67

[0381]

Embedded image 257 g (1.3 g) of 4-nitrophthalimide in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel.
4 moles), 400 g of xylene and 0.1 ml of potassium hydroxide.
Charge 6g. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

298 grams (4.03 moles) of glycidol are slowly added dropwise via the addition funnel. The first few milliliters cause a slight drop in temperature and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 67A

[0385]

Embedded image In a 2 liter autoclave are charged 414 g (1 mol) of 4-nitrophthalimide 3-glycidol of Example 67 and 4 g of potassium hydroxide catalyst. The reactor was purged three times with nitrogen to 60 psi and then 5 psi
Heat to 250 ° F. under nitrogen pressure. Next, 1320 grams (30 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of 80 psi or less.

After the EO addition, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, 4-nitrophthalimide 3GL / 30EO-H
The intermediate had a gram molecular weight of 1734 and was ready for use.

Example 67B

[0389]

Embedded image In a 2 liter autoclave, add 4-
Nitrophthalimide 3GL / 30EO-H intermediate 867
g (0.5 mol), 800 ml of ethyl alcohol and 65 g of Raney nickel. The autoclave is purged three times with hydrogen gas and heated at 85-90 ° C. under a pressure of 1300 psi. After about 2 hours, the removal of hydrogen was completed. The sample was removed and the solvent was removed under vacuum. The IR spectrum of this sample showed no nitro band, indicating the presence of an amine band, indicating that the reaction was complete. The autoclave was cooled and ventilated. The product was separated by filtering the reaction mixture and the solvent was removed under reduced pressure.

Example 68

[0391]

Embedded image 363 g (1.34 mol) of N-benzylidene-4-hydroxyaniline, 400 g of xylene and 0 g of potassium hydroxide in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, a heating mantle, a mechanical stirrer, a temperature controller and an addition funnel. Charge 6 g. While stirring, the mixture is heated to 110 ° C. by a heating mantle and a temperature controller.
Heat to.

298 grams (4.03 moles) of glycidol are slowly added dropwise via the addition funnel. The first few milliliters cause a slight drop in temperature and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour. At this point, the number of hydroxyl groups of the N-benzylidene-4-hydroxyaniline 3-glycidol intermediate was measured and found to be 637 (theoretical, 671).

Example 68A

[0395]

Embedded image In a 2 liter autoclave are charged 418 g (1 mol) of the N-benzylidene-4-hydroxyaniline 3-glycidol intermediate of Example 68 and 4 g of potassium hydroxide catalyst. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure.

Next, 880 grams of ethylene oxide (2
0 moles) at such a rate as to maintain a reading vapor pressure of 80 psi or less.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours. At this point, the number of hydroxyl groups in the reaction mixture was measured and found to be 214 (theoretical, 225).

After vacuum stripping at 200 ° F. for 15 minutes, N-benzylidene-4-hydroxyaniline 3
The GL / 20EO-H intermediate had an average gram molecular weight of 1234 and was ready for use.

Example 69

[0400]

Embedded image 176 g of N-benzylidene-2-amino-5-mercapto-1,3,4-thiadiazole (0.1 g) was placed in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel. 8
Mol), 400 g of xylene and 0.6 of potassium hydroxide
Add g. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

Glycidol 177 grams (2.4 moles)
Is slowly added dropwise via an addition funnel. The first few milliliters cause a slight drop in temperature and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 69A

[0404]

Embedded image In a 1 gallon autoclave, the N-benzylidene-2-amino-5-mercapto-1,3,4-
Charge 443 g (1 mol) of the thiadiazole 3-glycidol intermediate and 4 g of potassium hydroxide catalyst. The reactor was purged three times with nitrogen to 60 psi and then
Heat to 250 ° F under psi nitrogen pressure.

Next, 1320 grams (30 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of 80 psi or less.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, N-benzylidene-2-amino-5-mercapto-1,3,4-thiadiazole 3GL / 30EO-H
The intermediate had an average gram molecular weight of 1763 and was ready for use.

Embodiment 70

[0409]

Embedded image 98.5 g (0.5 mol) of N- (hydroxybenzylidene) aniline, 200 g of xylene and potassium hydroxide in a dry 1000 ml three-necked flask equipped with a nitrogen purge device, a heating mantle, a mechanical stirrer, a temperature controller and an addition funnel. Charge 0.6 g. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

Glycidol 111 grams (1.5 moles)
Is slowly added dropwise via an addition funnel. The first few milliliters cause a slight drop in temperature and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 70A

[0413]

Embedded image In a 2 liter autoclave, the N-
419 g (1 mol) of the (hydroxybenzylidene) aniline 3 glycidol intermediate and 4 grams of potassium hydroxide catalyst are charged. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure.

Next, 4400 grams (100 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of 80 psi or less.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, N- (hydroxybenzylidene) aniline 3G
The L / 100EO-H intermediate had an average gram molecular weight of 4819 and was ready for use.

Example 71

[0418]

Embedded image In a dry 1000 ml three-necked flask equipped with a nitrogen purge device, heating mantle, mechanical stirrer, temperature controller and addition funnel, 42.4 4-amino-naphthalimide.
g (0.2 mol), 300 g of xylene and 0.3 g of potassium hydroxide. While stirring, heat the mixture to 110 ° C. with a heating mantle and temperature controller.

187 g (2.5 mol) of glycidol
Is slowly added dropwise via an addition funnel. The first few milliliters cause a slight drop in temperature and the exotherm begins. Once the exotherm begins, the heating mantle may be removed and the exotherm can be controlled by the rate of addition. The temperature is maintained at 110-125 ° C by the rate of addition.

After all the glycidol has been charged, the reaction mixture is post-heated for 1 hour.

Example 71A

[0422]

Embedded image In a 2 gallon autoclave, 4-amino-naphthalimide 12.5 glycidol intermediate 11 of Example 71
37 g (1 mol) and 4 g of potassium hydroxide catalyst are charged. The reactor is purged three times with nitrogen to 60 psi and then heated to 250 ° F. under 5 psi nitrogen pressure.

Next, 6600 grams (150 moles) of ethylene oxide are added at a rate to maintain a reading vapor pressure of less than 80 psi.

After the addition of EO, the reaction mixture was heated at 120 ° C. for 2 hours.
Post-heat for hours.

After vacuum stripping at 200 ° F. for 15 minutes, 12.5 GL of 4-amino-naphthalimide /
The 150EO-H intermediate had an average gram molecular weight of 7737 and was ready for use.

Example 72

[0427]

Embedded image Aminoaniline 4GL / 200EO-H of Example 19B
2297 g (0.5 mol) of the intermediate were added to 39 g (0.3 mol) of sodium carbonate dissolved in 300 ml of water to form a mixture. The mixture is cooled to 10-15 ° C,
48.3 4-acetamidobenzenesulfonyl chloride
g was added over 1.5 hours. The mixture was then warmed to 50 ° C. for another 2 hours to complete the reaction. 10 g (0.25 mol) of sodium hydroxide was added to the mixture, and the mixture was heated to reflux for 1 hour. The mixture was then cooled and the product was extracted into methylene chloride. The methylene chloride solution was separated from the aqueous salt solution, washed several times with water to neutral pH, and dried over anhydrous magnesium sulfate. The dried solution was filtered and stripped at 90 ° C. under reduced pressure to obtain an intermediate.

Example 73

[0429]

Embedded image Amine 4GL / 200EO-H intermediate 5 of Example 19B
55 g (0.125 mol) of concentrated hydrochloric acid 45 ml, water 90
ml together with the flask. This mixture is kept at 0-5 ° C.
And the mixture was cooled to 10 ° C.
While keeping the addition. After several hours, the excess nitrite was destroyed with sulfamic acid. This diazo solution was added to 94 g of a sodium sulfite solution dissolved in 250 g of water, stirred at room temperature for 1 hour, and then 50 g of concentrated sulfuric acid was added.
The mixture was heated at 100 ° C. for 1 hour. After cooling, the pH was adjusted to 10 with sodium hydroxide. The organic layer was separated and extracted into methylene chloride. The methylene chloride solution was separated from the aqueous salt solution, washed several times with water to neutral pH,
It was dried with anhydrous magnesium sulfate. The dried solution was filtered and stripped at 90 ° C. under reduced pressure to obtain an intermediate.

Example 74 Temporary Colorability Test of Glycidol Polymer Colorant and Its Linear Analogs This test mimics the actual processing conditions encountered when heat setting, tufting and continuously dyeing nylon yarns. And the temporary coloring properties of various colorants were tested.

First, an undyed nylon carpet was cut into a square of 4 inches × 4 inches, and the degree of color on the carpet was measured using a Hunter Labscan colorimeter. Then, each sample was sprayed with a colorant at a rate of 0.5% by weight. Each sample was dried one day and night and measured again with a chromaticity meter. Each sample was heat set in an autoclave under conditions commonly used by customers. Here, each sample was measured again with a chromaticity meter and aged for one week in a dark place.

Next, each sample was placed in a solution of pH 5 for 30 minutes.
After immersion for two seconds, vacuuming, and further immersing in a solution having a pH of 2.2, the solution was poured out, sprayed twice more, and vacuumed again. Each sample was then steamed for 4 minutes and evacuated again. The wet sample was dried in an oven at 60 ° C. for 1 hour. Each sample was then finally measured with the chromaticity meter and the value compared to the first measured value. In this case, a 5-point scale is used.
In the case of 00, all the colorants were removed and the carpet was completely white.

In the following, the results for the glycidol polymer colorant are shown in comparison with those of the linear homolog of approximately equal molecular weight without glycidol. Sample No. Example No. E Glycidol Colorant E Isotope 151 3.60-251A-2.84 365 3.88-465A-2.49 519C 2.34-619D-1.39752 2.00-852A-0.13950A 2.79-1050B-2.22 11622.62-1262A-2.0313542.69-14454A-1.19 In any case, Glycidol polymer colorants are superior to their linear analogues.

Example 75 This example demonstrates that the glycidol polymer colorant is superior to its linear analogue for non-extractability. The polymer colorant of Example 6 and its linear analogue (Example 6A) were evaluated with the following composition.

Component * Composition A Composition B 12MF polypropylene 5000 g 5000 g (Norchem 831060, 25-35% ethylene) Irganox 168 (Ciba Geigy) 5.0 g 5.0 g Calcium stearate 2.5 g 2.5 g glycidol colorant (Example 6) 2.5 g Linear homolog (Example 6A) 2.5 g * For comparison, the concentration of the colorant was adjusted so that each composition had a hue having substantially the same depth.

The additives were mixed mechanically, melt mixed at 440 ° F. via a 1 inch extruder, and cut into pellets. Injection molded stepped plaques were made for each composition. The stepped plaque was 2 × 3 inches in size and had a step thickness of 0.05 inches and 0.85 inches. Each plaque had a total surface area of 12.5 square inches.

[0437] An 8 oz glass jar was used as the extraction vessel. The glass jar was 2.2 inches in diameter and 3.5 inches in height. The total volume of this container is 218m
l. Four plaques were placed in the extraction vessel, 200 ml of isopropanol was added, and the glass jars were sealed. This container was left in an oven at 50 ° C. for 23 days. After that, the container was taken out, isopropanol was transferred, and concentrated to 20 ml. These concentrates were recorded on a Beckman UV / Vis spectrophotometer. 1cm for Beckman DU-7 Spectrophotometer
A length cell was used. The linear homologous coloring composition “B” is 5
It showed an absorbance of 0.04 AU at 12 nm (relative to the baseline). The glycidol colorant composition “A” is 51
It showed an absorbance of 0.01 AU at 2 nm. Both of these colorants had the same chromophore. The coloring composition “B” has an absorbance at the maximum wavelength of 4 compared to the coloring composition “A”.
I met twice. Thus, the colorant composition "A" showed a one-fourth extractability as compared to the color composition "B".

[0438]

[Table 1]

[0439]

[Table 2]

[0440]

[Table 3]

[0441]

[Table 4]

[0442]

[Table 5]

[0443]

[Table 6]

[0444]

[Table 7]

[0445]

[Table 8]

[0446]

[Table 9]

[0447]

[Table 10]

[0448]

[Table 11]

[0449]

[Table 12]

[0450]

[Table 13]

[0451]

[Table 14]

[0452]

[Table 15]

[0453]

[Table 16]

[0454]

[Table 17]

[0455]

[Table 18]

[0456]

[Table 19]

[0457]

[Table 20]

[0458]

[Table 21]

[0459]

[Table 22]

[0460]

[Table 23]

[0461]

[Table 24]

[0462]

[Table 25]

[0463]

[Table 26]

[0464]

[Table 27]

[0465]

[Table 28]

[0466]

[Table 29]

[0467]

[Table 30]

[0468]

[Table 31]

[0469]

[Table 32]

[0470]

[Table 33]

[0471]

[Table 34]

[0472]

[Table 35]

[0473]

[Table 36]

[0474]

[Table 37]

[0475]

[Table 38]

[0476]

[Table 39]

[0477]

[Table 40]

[0478]

[Table 41]

[0479]

[Table 42]

[0480]

[Table 43]

[0481]

[Table 44]

[0482]

[Table 45]

[0483]

[Table 46]

[0484]

[Table 47]

[0485]

[Table 48]

[0486]

[Table 49]

[0487]

[Table 50]

[0488]

[Table 51]

[0489]

[Table 52]

[0490]

[Table 53]

[0490]

[Table 54]

[0492]

[Table 55]

[0493]

[Table 56]

[0494]

[Table 57]

[0495]

[Table 58]

[0496]

[Table 59]

[0497]

[Table 60]

[0498]

[Table 61]

[0499]

[Table 62]

[0500]

[Table 63]

[0501]

[Table 64]

[0502]

[Table 65]

[0503]

[Table 66]

[0504]

[Table 67]

[0505]

[Table 68]

[0506]

[Table 69]

[0507]

[Table 70]

[0508]

[Table 71]

[0509]

[Table 72]

[0510]

[Table 73]

[0511]

[Table 74]

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────────────────────────────────────────────────── ─── Continued on front page (72) Inventor David Jesse Moody, Garden Grove Court, Spartanburg, 29302, South Carolina, USA 409 (72) Inventor Edward William Kruger South Carolina, United States State 29374, Paulin, Highway 56 4295 (56) References JP 5-97994 (JP, A) JP 5-194865 (JP, A) JP 4-263677 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C09B 69/10 C08G 65/26

Claims (5)

(57) [Claims] A colorant comprising a compound having the general formula C (Z) 1-8, wherein C is mono-, bis-, tris, or tetrakis-azo, methine, azomethine, And a chromophore selected from compounds containing at least one chromophoric group selected from triphenylmethane chromophoric groups, having 1 to 8 nucleophilic site residues to which the Z component is bonded, The Z component contains at least 60% by weight of a poly (oxyalkylene), wherein the poly (oxyalkylene) comprises: (a) a glycidol segment of 2-6 glycidol residues attached to the nucleophilic site of C above. (B) the poly (oxyalkylene) further comprises at least one glycidol residue having three separate poly (oxyalkylene) branches. It includes a segment, the glycidol residue segment ethylene oxide (EO), propylene oxide (PO)
Or one or more residues of other epoxide reactants of butylene oxide (BO) or a mixture thereof, and the poly (oxyalkylene) is EO, P
O or BO residues or mixtures thereof for a total of 10-60
A colorant containing 0 (at least about 75 mol% of which is an EO residue). 2. A colorant according to claim 1, wherein the total number of said other epoxide reactant residues is 150-400. 3. The coloring of claim 1 wherein the EO residues comprise 90-100 mole% of said other epoxide reactant residues.
Agent . 4. The method according to claim 1, wherein the poly (oxyalkylene) component is 3
2. The colorant of claim 1, comprising at least one glycidol residue segment having two separate poly (oxyalkylene) branches. 5. The colorant according to claim 4 , wherein the poly (oxyalkylene) branch ends in a hydrogen atom.