JPS5910677B2 - Phosphate ester halide and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new method for producing phosphoric ester halides and to new phosphoric ester halides obtained by this method.

It is known to prepare phosphoric acid ester chlorides by selective reaction of phosphoryl chloride with alcohols (
HoubenWeyl, 12th
Vol. 212, 1964).

A disadvantage of this method is that only a limited number of alcohols, especially primary alcohols, are used as starting materials. Therefore, the preparation of substituted compounds is accordingly limited and in some cases may even be carried out in a controlled manner, for example for phosphoric acid alkyl ester-halides in which the 11-position of the alkyl group is halogenated. This is achieved through a series of multi-step reactions. General formula 1 In the formula, the group R represents an alkoxy group having 1 to 8 carbon atoms, optionally substituted with halogen, and R1 represents a ClC8 alkoxy group, optionally substituted with halogen, or chlorine, bromine, ClC6 alkyl or phenyl, optionally substituted by halogen, is a halogenating agent and the groups R2 and R4 are the same, hydrogen, halogen or linear or branched, optionally substituted C1-C
l8 alkane, C1-C6 acyloxy or C2-C
12 represents an alkenyl group, and the substituents that can be shown are halogen, acyloxy or alkoxy group having 1 to 18 carbon atoms, isocyanate group, isocyanidodichloride group, chlorocarbonyl group, nitrile group or chlorosulfone group, carbon a carbalkoxy group having 1 to 8 atoms, or an optionally substituted carboamino group having up to 12 carbon atoms in the molecule, and also R2 and R4 are optionally halogen and/or a C,-C4 alkyl group. thus represents a substituted phenyl radical, and the radical R4 can also, in addition to the abovementioned radicals, be a chlorocarbonyl radical or a nitrile radical or in each case a carbalkoxy radical having up to 9 carbon atoms in the molecule or, if appropriate, a nitrogen radical. represents a carbamino group substituted on an atom, or in each case represents an alkylcarbonyl, alkylsulfonyl, arylcarbonyl or arylsulfonyl group with up to 7 carbon atoms in the molecule, or represents an aldehyde group, and optionally both R2 and R4 are preferably 4- to 12-membered, preferably 5- or 6-membered carbocycles or oxygen, sulfur or nitrogen as a result of the additional bond between the groups R2 and R4. is a member of a heterocyclic ring present as a heteroatom, and R3 and R5 are the same or different and represent hydrogen, halogen or a C1-C4 alkyl group, characterized in that they are reacted simultaneously to an olefin of A new method for producing phosphoric acid ester-halides has now been discovered.

Preferred phosphoric acid esters of general formula 1 which can be represented are those in which R represents a C1-C6 alkoxy group, preferentially a methoxy and ethoxy group, and R1 represents a C1-C4 alkoxy group or a C1-C3 alkyl group, a chlorine , bromine, fluorine or phenyl and preferentially methoxy, ethoxy, propoxy, isopropoxy, methyl or ethyl and X is chlorine.

Examples that may be mentioned are phosphoric acid dimethyl ester monochloride, phosphoric acid diethyl ester monochloride, phosphoric acid diethyl ester monobromide, phosphoric acid dimethyl ester monofluoride, phosphoric acid dibutyl ester monochloride, phosphoric acid dimethyl ester monochloride Monomethyl ester dichloride, phosphoric acid monoethyl ester dichloride, phosphoric acid monoethyl ester difluoride, phosphoric acid monomono(2-chloroethyl) ester dichloride, phosphoric acid monoisopropyl ester dichloride, phosphoric acid monopropyl ester dichloride , methanephosphonic acid monomethyl ester-chloride, ethanephosphonic acid monomethyl ester-chloride, and phenylphosphonic acid monomethyl ester-chloride. The phosphoric acid esters used for this process are known and can be prepared, for example, by reacting the corresponding phosphoric acid chloride, such as phosphoryl chloride, with a suitable alcohol (Hoben-Weyl)
Houben-Weyl), [Methods of Organic Chemistry (Met
hOdenderOrganischenChemie
), Volume 2, p. 211, Stu
ttgart), 1964).

Preferred olefins of the general formula which can be represented are in which R2 and R4 are the same or different and hydrogen, fluorine, chlorine, bromine or optionally substituted C1-C
5 acyloxy group, ClC6 alkane group or C2-C
6 represents an alkenyl group, and the substituents of these groups which may be represented are chlorine, bromine, isocyanate, isocyanidodichloride, chlorocarbonyl, nitrile or chlorosulfonyl, in each case 1 in the molecule.
carbalkoxy, acyloxy or alkoxy groups having ~5 and preferentially 1 to 3 carbon atoms, and carboamino groups preferably substituted on the nitrogen atom by methyl or ethyl, R2 preferentially represents fluorine, chlorine or bromine, and R4 has the meaning within the range given above, but does not represent fluorine, chlorine or bromine at the same time as R2.

More preferred olefins which can be represented include R4 in which R4 is a chlorocarbonyl group, a nitrile group, a carbalkoxy group having 1 to 5 carbon atoms in the molecule, or a monoalkylated or dialkylated carboamino group, 1 to 4 in the molecule.
represents an alkylcarbonyl or alkylsulfonyl group having 5 carbon atoms, and also an arylcarbonyl or arylsulfonyl group containing as aryl group a phenyl group, and preferentially R2, R3 and R5 are the same or or is different and represents hydrogen, chlorine, bromine or a C, to C6 alkane group,
And at least one of the groups R2, R3 and R5 represents hydrogen.

Examples which may be mentioned of the olefins used for this process are branched and unbranched alkenes, in particular ethylene, propylene, but-1-ene and but-2-ene.
-ene, isobutene, hex-1-ene, dotese-1-ene
ene, tri- and tetrapropylene, tetraisobutene, oct-1-ene, octadec-1-ene, 1-phenyl-3,3,4,4-tetrafluorocyclobutene,
Cyclobenzene, cyclohexene, cyclooctene, cyclododecene, styrene, α-methylstyrene, α- and β-pinene and camphenyl diolefin, especially but-1,3-diene, isoprene, 2,3-dimethyl-but-1,3-diene , vinylcyclohexene and cycloocta-1,4-dienelihalogenated olefins, such as allyl chloride, methallyl chloride and vinyl chloride 1
- and 2-chloropropene, 1,4- and 3,4-
Dichlorobut-2-ene, vinyl bromide and allyl bromide, vinyl fluoride, 1,1-dichloroethylene, 1,1-
Difluoroethylene and trifluoromonochloroethylene, 1-chlorocyclohexene and 3-chlorocyclohexene; esters, mono- and dialkylamides, unsaturated carboxylic acids, especially acrylic acid, methacrylic acid, crotonic acid, β-β-dimethylacrylic acid, β-chloroacrylic acid, β・β-dichloroacrylic acid, vinylacetic acid, undecenecarboxylic acid, oleic acid, linoleic acid, cyclohexene-1-carboxylic acid and cyclohexene-3-carboxylic acid, maleic acid, itaconic acid and fumaric acid. Chlorides and nitriles: unsaturated alcohols,
In particular esters and ethers of allyl alcohol, butene-1,4-diol and methylene-propane-1,3-diol, such as ethyl vinyl ether, butyl vinyl ether, vinyl acetate and isopropenyl acetate and 1,3-dioxolene-2-onelyolefin. Isocyanates and isocyanide dichlorides with bonds, in particular allyl isocyanate and allyl isocyanide dichloride, 4-chlorobutenyl isocyanate and 4-chlorobutenyl isocyanide dichloride and isopropenyl isocyanate; ketones and sulfones with olefin bonds, especially Methyl vinyl ketone, medityl oxide, phenyl vinyl sulfone, sulfolene and 3-methyl sulfolene; and olefinic sulfonic acid derivatives, especially β-chlorovinyl-, allyl- and methylallyl-, vinyl mono- and β·β-dimethylvinyl -sulfonyl chloride.

Very particularly preferred olefins are those in which R2 and/or R3 represent fluorine, chlorine or bromine, in particular fluorine or chlorine, and R3 can also represent hydrogen, and the radicals R4 and R5 are in each case hydrogen, It is of the general formula representing a C1-C6 alkane group or a phenyl group.

Examples that may be mentioned are monofluoroethylene, monochloroethylene, monobromoethylene, 1,1-difluoroethylene, 1,1-dichloroethylene, 1-fluoro-
2-methylethylene, 1-fluoro-2-ethylene, 1
-fluoro-2-phenylethylene, 1-chloropropen-1-ene and 2-chloropropen-1-ene.

The vinyl fluoride and vinylidene fluoride used for this process are either known or prepared using known methods, such as the addition reaction of one molecule of HF with a suitable acetylene or two molecules of HF and acetylene, followed by chlorination and desorption. It can be produced with hydrochloric acid. The phosphoric acid ester chloride obtained by this method has the general formula R1, . R2, R3
, R4, R5 and X each have the same meaning as the starting material of general formula 1 or, and Y represents chlorine or bromine depending on the halogenating agent used for this process. can.

= Examples of phosphoric acid ester-halides that can be shown according to the general formula are as follows.

The novel compounds which can be obtained and shown by this invention are: X represents fluorine, chlorine or bromine; Y represents chlorine or bromine; represents a phenyl group, R2 and R4 are the same or different, and hydrogen, halogen or a linear or branched, optionally substituted C1-C
l8 alkane, C1-C6 acyloxy or C2-C
12Alkenyl represents a substituent which may be represented by halogen, an acyloxy or alkoxy group having 1 to 18 carbon atoms, an isocyanate group, an isocyanidodichloride group, a chlorocarbonyl group, a nitrile group or a chlorosulfone group, an alcohol group a carbalkoxy group having 1 to 8 carbon atoms in the group or an optionally substituted carboamino group having up to 12 carbon atoms in the molecule, and also R2 and R4 optionally halogen and/or C1-C4 alkyl a phenyl group substituted by a group, and the group R4 can also represent, in addition to the abovementioned groups, a chlorocarbonyl or nitrile group or in each case a carbalkoxy group having up to 9 carbon atoms in the molecule or, as appropriate represents a carboamino group substituted on the nitrogen atom, or in each case represents an alkylcarbonyl, alkylsulfonyl, arylcarbonyl or arylsulfonyl group with up to 7 carbon atoms in the molecule, or represents an aldehyde group; , and optionally the radicals R2 and R4 can both be 4- to 12-membered, preferably 5- or 6-membered carbocycles or oxygen, sulfur or nitrogen atoms as a result of the additional bond between the radicals R2 and R4. members of a heterocycle, preferably present as heteroatoms, and R3 and R5 are the same or different, and hydrogen, halogen or ClC
4 alkyl group, and also in which X represents fluorine, chlorine or bromine, Y represents chlorine or bromine, R1 represents a ClC8 alkoxy group optionally substituted by halogen, or Fluorine,
Compounds of the general formula represent chlorine or bromine, R2 represents fluorine, R3 represents fluorine or hydrogen, and R4 and/or R5 represent hydrogen, ClC4 alkyl or phenyl.

The compounds shown in Table 1 may be mentioned as examples.

The subject of the present invention is the most preferred embodiments of the above, namely the general formulas (1), (11) and , X is a halogen, Y is a halogen, R is a C1-C4 alkoxy group, and R1 is a C1-C4 alkoxy group.
A phosphoric acid ester halide which is a 1-C4 alkyl group, a C1-C4 alkoxy group or a halogen, R2 is a halogen, R3 is a halogen or hydrogen, and R4 and R5 are hydrogen, and a method for producing the same.

Elemental halogens, especially chlorine or bromine, can be used as halogenating agents for the process of the invention.

Of course, compounds which cleave chlorine or bromine under the reaction conditions, such as sulfuryl chloride, can also be used.
The reaction temperature for the reaction of the process of the invention is not critical per se and can be varied within a wide range.

Generally, the reaction is carried out between -50 and +120°C, suitably between about -10 and +100°C, and preferably between -10 and +120°C.
Perform at +50°C. Generally, the reaction is carried out under normal pressure.

The process of the invention is preferably carried out in the presence of a solvent or diluent.

Solvents and diluents that can be used are, for example, aliphatic and aromatic chlorinated hydrocarbons, organic solvents which are inert towards the reactants, such as dichloromethane, chloroform, chlorobenzene or dichlorobenzene, but which are also liquid under the reaction conditions. Excess of its phosphoric acid ester-
It is halide. In some cases it has also proven advantageous to add small amounts of Friedel-Crafts catalysts to the reaction mixture, in particular, for example iron chloride, zinc chloride or aluminum chloride.

In order to obtain good yields, the process of the invention is suitably carried out using equivalent amounts of halogenating agent and at least equivalent amounts of phosphoric acid ester-halide used as starting material, these amounts being based on the olefin. ing.

In general, particularly good results are obtained when the phosphoric ester-halide used is used in excess, for example in a molar ratio of 1:1 to 5:1 relative to the amount of olefin used. Using as an example the reaction of phosphoric acid monomethyl ester dichloride with vinyl chloride as olefin and chlorine as halogenating agent, the process of the invention can be explained in detail by the following equation.

When the phosphoric acid ester used as starting material contains two alkoxy groups as substituents R and R1, the reaction according to the method of the invention can be carried out, for example, when an appropriate excess of olefin and halogenating agent are present. Using the reaction of phosphoric acid dimethyl ester-monohalide with vinyl fluoride as an olefin and chlorine as a halogenating agent,
The stepwise progression can be continued by substitution of both alkoxy groups to give two new phosphodiester monochlorides, as illustrated in more detail by the following formula.

In this case, the phosphoric acid ester halide obtained as product contains a group instead of the group R1.

To carry out the process of the invention, the phosphoric acid ester-halide initially used is added, if necessary, to an inert solvent or diluent, and the halogenating agent and olefin are added simultaneously to this solution at the indicated temperature. The internal temperature of the mixture is adjusted by external cooling.

After the reaction has subsided, the batch is stirred for a while while being warmed (preferably at 40 to 100°C) in order to complete the reaction. The reaction mixture is then cooled to room temperature and treated in conventional manner, such as by vacuum fractionation. The product obtained by the process of the invention is generally obtained in the form of a colorless to pale yellow oil, which is insoluble in water and can generally be distilled under reduced pressure without decomposition and is purified by this method. be able to.

When mixtures of different isomers are obtained as products, these can be resolved by fractional distillation. The advantage of the process of the invention is that the production of the known phosphoric acid ester halides is considerably simplified and many new compounds of this type are available which cannot be produced by hitherto known processes.

Further advantages are that the process according to the invention has universal applicability, can be carried out industrially in a simple manner, and that the necessary starting materials are readily available.

The high purity and good yield of the products obtained by the process of the invention are also advantageous. The phosphoric acid ester halide of the present invention is used as an intermediate for the production of insecticides.

For example, by reacting the phosphoric acid ester chloride of the present invention represented by the formula with the amine represented by the formula,
An insecticidal compound of the formula is obtained.

The insecticidal activity of this compound and other compounds obtained from the compound of the present invention according to a similar method is illustrated in the following reference example (see Example A of JP-A-53-5122). Concentration Test/Soil Insect Test Insects: Larvae of TenebriOmOlitOr in Soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable formulation of the active compound, 1 part by weight of The active compound was mixed with the above amount of solvent, the above amount of emulsifier was added, and the concentrate was diluted with water to the desired concentration.

The active compound formulation was thoroughly mixed with the soil.

The concentration of active compound in the formulation is virtually unimportant; P
The weight of active compound per unit volume of soil, given in pm (=η/l), is important. The soil was filled into the container and the container was left at room temperature. After 24 hours, test insects were added into the treated soil and after a further 2-7 days.
The degree of effectiveness (%) of the active compound was determined by counting the number of dead and live test insects.

The degree of death is 100 when all test insects die.
%, and the case where exactly the same number of test insects were alive as in the blank test was defined as O%. The active compounds, amounts used and results are shown in the table below.

Of the four active compounds, the first one is a known active compound and the second to fourth ones are active compounds derived from the compounds of the invention.

Example 1 Vinyl fluoride 557 and chlorine 707 are stirred and passed simultaneously into phosphonic acid dimethyl ester monochloride (CH3O)2P0C1308V at -5°C to 0°C with cooling.

After the reaction has taken place, the mixture is first degassed under vacuum at room temperature,
Next, it is subjected to fractional distillation. Boiling point range of 143t (69% of theoretical value)B. Formula C1-PO(0
CH3) (0CHF-CH2Cl) phosphoric acid 0-methyl-0-(2-chloro-1-fluoroethyl) ester-
Boiling range of monochloride and 117 (8% of theory)B.
P. O. 285 (~90 °C formula Cl-PO(0CHF-
CH2Cl)2 phosphoric acid di(2-chloro-1-fluoroethyl) ester-monochloride is obtained.

Example 2 The reaction is carried out in the same manner as in Example 1 except that (CH3O)2P0C16007, Cl21957 and vinyl fluoride 140f are used in place of the amounts shown in Example 1.

In this case, the compound Cl- of 307y (52% of theory)
PO(0CH3)(0CHF-CH2-C1) and 7
21 (=21.5%) of the compound Cl-PO(0CHF-
CH2Cl)2 is obtained.

Example 3 Chlorine 717 and vinyl chloride 90f7 were converted into phosphoric acid diethyl ester monochloride Cl-PO (0C2H5
) 2172r.

The temperature is maintained at approximately 0°C by cooling. The reaction mixture is warmed to 50° C. to remove ethyl chloride and then subjected to fractional distillation in vacuo. Boiling pointB. p. O. Formula C1-P with l72°C
0-ethyl-0-(1,2-dichloroethyl)ester phosphate of O(0C2H5)(0CHC1-CH2Cl)-monochloride 1057 (43.5% of theory) and boiling point B. P. O. Phosphate di(1,2-
dichloroethyl) ester-monochloride Cl-PO(
0CHC ℃H2Cl) 252f7 (theoretical value 33.4
%).

Example 4 70r of vinyl fluoride was stirred and passed through 2212t of Cl-PO(0CH3) at about 0°C while cooling to remove bromine 11
Add 7r at the same time.

The mixture is then degassed under a water pump vacuum and subjected to fractional distillation. Boiling point rangeB. p. O. Phosphate 0-methyl-0-(2-bromo-1-fluoroethyl)ester-monochloride 120r (theoretical value of 65
%) and boiling point range 1000-105 (/0.15mmHg
The compound C1-PO(0CHF-CH2Br)2 with
Get 14f7.

Example 5 Chlorine 20f7 and vinyl fluoride 20y at -10
Phosphoric acid monopropyl ester dichloride C at °C to 0 °C
Pass through 12PO-0-Nc3H,2Ot.

Formula C with boiling point range 462-48°C/0.2mmHg
Phosphoric acid (2-chloro-1-fluoroethyl) ester dichloride of 1,PO-0CHF-CH,Cl 20.2
P (85% of theory, based on the phosphoric acid propyl ester dichloride used) is obtained by fractional distillation. Example 6 Vinyl fluoride 30r and chlorine 40? is passed through phosphoric acid monoethyl ester-dichloride 80f7 at about 0°C.

After treatment by fractional distillation, boiling point range 430-46℃/0.1
Compound Cl2PO-0-CHF-CH, with Hg
Cl75? (77.5% of theory based on the phosphoric acid ethyl ester chloride used).

Example 7 20f of vinyl chloride and 20V of chlorine are passed through 20r of phosphoric acid monopropyl ester dichloride, and the reaction temperature is maintained between 0°C and 10°C by cooling.

Treatment by distillation has a boiling point range of 560-60℃/0.1U1
This gives phosphonic acid (1,2-dichloroel) ester dichloride 16r (62.5% of theory) with Hg. Example 8 Vinyl bromide 807 is added dropwise to phosphoric acid monoethyl ester dichloride 80f at -5°C to 0°C, and chlorine 45y is simultaneously passed through, the heat of reaction being compensated by a cooling bath.

Compound C having a boiling point of 66, ~68°C/0.1 mmHg
H2Cl-CHBr-0-POCl252r (40% of theory) is obtained by fractional distillation of the product mixture obtained.
Example 9 100y of chlorine and 65r of vinyl fluoride are added simultaneously to 135r of ethanephosphonic acid ethyl ester chloride.

The temperature is maintained between -10°C and 0°C by cooling. After treatment by fractional distillation, ethanephosphonic acid (2-chloro-1-fluoroethyl ester) chloride 120f7 (67% of theory) with boiling point range 65-67 °C/0.2 fin Hg
get. Example 10 Chlorine 60r, vinylidene fluoride 3
9r and in addition FeCl, O.9r. Add 5V to phosphoric acid methyl ester dichloride 67r.

Claims (1)

[Claims] 1 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a halogen, Y represents a halogen, and R^1 is a C_1-C_4 alkyl group, a C_1-C_4 alkoxy group, or The compound represents a halogen, R^2 represents a halogen, R^3 represents a halogen or hydrogen, and R^4 and R^5 represent hydrogen. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) In the formula, R is C
_1-C_4 represents an alkoxy group, R^1 is C_1-
Represents a C_4 alkyl group, a C_1-C_4 alkoxy group, or a halogen, and X represents a halogen. , R^3 represents halogen or hydrogen, and R^4 and R^5 represent hydrogen.There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼(III ) in the formula, R
^1, R^2, R^3, R^4, R^5 and X are as described above, and Y represents halogen.