JPS591750B2 - Method for producing 3-[3',4'-dichloro-6'-alkyl-phenyl]-Δ-pyrazoline derivative - Google Patents

Description

Detailed description of the invention: 1,3-diphenyl-pyrazoline compound - This compound has a phenyl group at the 1-position and an alkylsulfonyl group at the P-position - This compound is used as an optical brightener, for example in French Patent No. 1354629. , No. 1431233, No. 1449
163 and 1535821.

In the case of these pyrazoline compounds, the substitution of the alkylsulfonyl group has practically no effect on the fluorescent action. That is, the chemical state of the aliphatic residue has no significance at all with respect to whitening properties, but merely affects the ability to dye the substrate. However, it has been found that the fluorescence ability and therefore the whitening effect is significantly influenced by the substitution of the phenyl nucleus at the 31-position. In the case of known pyrazoline compounds of the above-mentioned type 3
A large number of groups are mentioned as possible substituents for the phenyl nucleus present in the - position, in particular also halogen atoms and lower alkyl groups. However, only 3-phenyl and 3-(p-chlorophenyl) compounds are described in detail. These compounds exhibit fluorescence in the shortwave blue to violet region and produce a somewhat reddish whitening. In this *, R is a lower alkyl group, preferably having up to 4 carbon atoms, and w means a hydrogen atom or an optionally substituted phenyl group, preferably a sulfophenyl group. A method for producing the compound shown,
In this case, the following formula or (wherein R and w have the above meanings and Z
represents a nogen atom or a dialkylamino group.

) is reacted with a hydrazine compound of the following formula.

It is often undesirable for the compound of general formula (1) to have a color like R in the general formula.

It has now been found that known brighteners can be improved both in terms of their color and also in terms of their lightfastness. The present inventors have found that the above-mentioned improvement can be achieved when a group of the following formula (wherein R represents a lower alkyl group) is introduced as the aryl group at the 31-position.

The object of the present invention is therefore a ketone represented by the following general formula (1) in which w has the above meaning and Z represents a halogen atom, preferably a Cl atom or a dialkylamino group.
-Hydrazinophenyl (hydroxy-alkyl)-
It is advantageously prepared by condensation with sulfones according to the method described in French Patent No. 1,354,629.

The ketone itself with the general formula () is, for example, 1-alkyl-3,
It is obtained by a Friedel-Crafts reaction from 4-dichlorobenzole and an acid chloride of the formula [Z has the meaning given above].

Compounds in which w is not a hydrogen atom are advantageously prepared in the following way: acetyl chloride is condensed with 1-alkyl-3,4-dichlorobenzole in a Friedel-Crafts reaction to give the formula R has the meaning given above.

], and then the ketone of the formula () is optionally substituted by a known method to form a compound of the following formula (W-CHO(V
]) is condensed with benzaldehyde to form an unsaturated ketone of formula (1), which is condensed with hydrazine of formula (1V)117 to form pyrazoline of formula (1).

The compounds of formula (1) according to the invention exhibit strong fluorescence in a very slightly reddish blue to almost pure blue color in the dissolved state and are suitable for the optical brightening of a wide variety of organic materials. They show good results, for example, in the whitening of solid or synthetic fibers (for example fibers made of acetylcellulose, polyamide, polyurethane or polyacrylonitrile) and films, foils, bands or moldings made from these materials. The water-insoluble compounds can be used dissolved in organic solvents or in the form of aqueous dispersions, especially with the aid of dispersants. Suitable dispersants are, for example, soaps, fatty alcohols, polyglycol ethers such as fatty amines or alkyl phenols, cellulose sulfite waste liquors or condensation products of formaldehyde with optionally alkylated naphthalene sulfonic acids, as well as partially acetylated Polyvinyl-alcohol and the like can be used. Water-soluble anionic compounds are particularly suitable for the optical brightening of acetyl cellulose, wool and especially synthetic polyamide fibers.

This compound shows excellent whiteness on these materials and
The compounds are used in particular in the acidic range with a pH of about 3 to about 6. The compounds according to the invention can also be added to the high molecular weight organic materials before or during shaping. It can therefore be added to the forming mixture during the production of films, foils, bands or moldings, or alternatively to the spinning mixture before spinning into threads. A suitable compound is polyamide-6,6
It can also be added to the low molecular weight starting materials before the polycondensation as in the case of or before the polymerization. The amount of compound of general formula (1) used according to the invention (relative to the material to be optically brightened) can vary within a wide range.

This amount can be easily ascertained by preliminary testing and is generally about 0.01 to about 1%. The compound of general formula (1) can also be used in combination with dyes, reducing bleaches, finishing agents, softeners, detergents and post-washing treatment agents.

When applied to textile products, such as fleeces, knitted fabrics, woven fabrics, in particular those consisting of synthetic polyamide fibres, acetylcellulose or copolymers with a polyacrylonitrile content of at least 85%, the compounds according to the invention can A particularly high degree of whiteness can be obtained if impregnated with a solution or dispersion of the compound and then pressed between rolls in the customary manner so that the textile material still contains about 20 to 150% of the dry weight of water. Show degree.

In this case, the compound of formula (1) is about 0.0% based on the weight of the product.
It should be applied to the fibers at a concentration of 1-1%. The textile material is then dried or thermosolized at a temperature of about 100 DEG to 220 DEG C., in particular about 150 DEG to 200 DEG C. The treatment time depends on the temperature used, but is generally about 20 to 300 seconds. According to this method, the auxiliary mixture is added to the padding bath as described in Pelkey Patent No. 7.
Particularly high degrees of whiteness are achieved when added in accordance with the description in No. 29261. having an unsubstituted phenyl group at the 31-position, or a halogen atom at the p-position, alkoxy-1,
Compared to compounds with a phenyl group substituted by an acylamino-alkylamino mono- or dialkylamino group, the compounds according to the invention are particularly suitable for SN (Swiss Standards Institute)
It is distinguished by a clearly improved lightfastness (DIN 45OO4) in simultaneous wetting or exposure conditions with 95808.

The following examples illustrate the invention in more detail:
The present invention is not limited thereto.

Example 1 3,3/,4 dissolved in 3,4-dichlorotoluol
A boiling suspension containing 71.4 parts by weight of 4-hydrazinophenyl-β5-hydroxyethylsulfone in 300 parts by volume of methanol with stirring of 163 parts by weight of a solution of /1-trichlor-6/-methyl-propiophenone. Drip inside.

The mixture was boiled under reflux for 4 hours, stirred well at room temperature, and then filtered under suction. Thus, after washing several times with methanol and water, 11[4''-(β-hydroxyethyl-sulfonyl)phenyl]-3-[3(4'-dichloro-6/-methyl-phenyl]-△2- 74 parts by weight of pyrazoline are obtained. This compound exhibits a melting point of 187-189° C. after recrystallization from dimethylformamide.
, 4-dichlorotoluol is prepared as follows: 145 parts by weight of 3,4-dichlorotoluol and aluminum. 38.1 parts by weight of β-chloropropionyl chloride is added dropwise to the mixture with 48.5 parts by weight of chloride at room temperature, and the mixture is thoroughly stirred until the generation of gas is completed.

This is then poured into a mixture of 300 parts by volume of 2N hydrochloric acid and 150 parts by weight of ice, stirred, separated and the organic phase is washed neutral with water. Example 24 - Hydrazinophenyl β-
8.4 parts by weight of hydroxyethyl sulfone and 3,3',
9 .8 parts by weight are boiled under reflux for 7 hours in 100 parts by volume of methanol, then stirred at room temperature and filtered with suction.

The product was then washed with methanol and dried to give 1-
6.4 parts by weight of [4''-(β-hydroxyethylsulfonyl)-phenyl]-3-[3',4'-dichloro-6'-ethylphenyl]-△2-pyrazoline are obtained. Melting point (from methanol) After recrystallization): 140
~141℃. Example 3 3,4-dichloro-n-propylbenzole [boiling point:
130~132°C/25mmHI,. nV: 1.
5 3 3 7 ; o-Dichlorobenzole was acylated with propionyl chloride by Friedel-Crafts reaction, and then the obtained ketone (melting point: 31-3
[2.5°C] was obtained by reducing 4
7.3 parts by weight are acylated in ethylene chloride using 3.4 parts by weight of β-chloropropionyl chloride 3 by Friedel-Crafts reaction.

The oily crude ketone obtained by conventional work-up is then reacted with 0.0 parts by weight of 4-hydrazinophenyl-β-hydroxyethylsulfone 6 in a known manner to form a compound of the following formula. This product exhibits a melting point of 150-151 DEG C. after recrystallization from isopropanol. Example 4 19.7 parts by weight of a compound of the following formula are boiled under reflux for 4 hours with 12.0 parts by weight of 4-hydrazinophenyl-β-hydroxyethylsulfone in aqueous ethanol with the addition of hydrochloric acid.

After the reaction solution is clarified with activated carbon, the filtrate is adjusted to pH 7-8 with a soda solution while hot and stirred well. The precipitated sodium sulfone salt of the following formula is collected by suction under ice-cooling.

It decomposes at 370°C. The ketones that serve as starting compounds are prepared as follows.

3,4-dichloro-6-methyl-acetophenone (melting point: 49-516C; prepared by Friedel-Craft-to-acetylation of 3,4-dichlorotoluol) 20
, 3 parts by weight of sodium benzaldehyde-2-sulfonate are condensed with 24.0 parts by weight of sodium benzaldehyde-2-sulfonate in aqueous ethanol at 20-40°C with the addition of a catalytic amount of alkali, and the isolated reaction product is recondensed from water. Crystallizes (melting point: 262-27'C)
Example 5 (Example of use) A fabric made of polyamide-6 is treated with a washing bath containing 6 g/l of detergent of the following composition in a bath ratio of 1:20:9.
8%: Isotridecanol-polyglycol ether (
Contains 8 moles of ethylene oxide per mole of isotridecanol) 30.0 (:Ff): Trisodium phosphate 15.0%: Tetrasodium pyrophosphate 5.001): Sodium metasilicate 2.0%: Carboxymethyl Cellulose 38%: Sodium sulfate 0.301): The compound fabric according to Example 1 is washed for 10 minutes in each case at 60 DEG C., then washed and dried as usual.

This process was repeated up to 10 times. After 1 treatment or 10 treatments, the polyamide fabric showed the following whiteness: Untreated WG: 67.7 1 wash WG: 149.2 10 washes WG: 182.0 Example 6 (Usage example) ) A fabric made of polyamide-6 is treated with a solution containing 0.0759/l of the compound according to Example 1 in a customary prewashing bath ratio of 1:20 on a skein tank.

The fabric was treated in this solution for 30 minutes at 80°C, then washed and dried as usual. This treatment gave the fabric a very good whiteness of 171, while the prewashed fabric only had a whiteness of 68.

Example 7 (Example of Use) A copolymer containing more than 85 (fl) polyacrylonitrile is dissolved in dimethylformamide and 0.02% of the compound according to Example 1, based on the copolymer, is added to this solution.

This polymer solution is spun in a conventional manner. At this time, the solvent is evaporated with hot air. The fiber cable which is coagulated, post-treated in a conventional manner, wrinkled and dried is 102.7
%, but a fiber cable made under the same conditions but without the addition of optical brightener had a whiteness of 47.7%. Example 8 3,4-dichloro-6-methyl-acetophenone 20.
3 parts by weight (melting point 49-5FC) (obtained by Friedel-Graft-to-acetylation of 3,4-dichlorotoluol).

) to dimethylamine hydrochloride 1 by Mannitz reaction.
The mixture is reacted with 4.0 parts by weight of paraformaldehyde, 0.2 parts by volume of concentrated hydrochloric acid, and 16 parts by volume of ethanol at reflux temperature for 3 hours. After distilling off 8 parts by volume of ethanol, adding 75 parts by volume of acetone, cooling and suctioning,
, 4-dichloro-6-methyl-ω-dimethylamino-pyropiophenone-hydrochloride is obtained. This was then stirred under reflux (124° C.) for 6 hours in 17.3 parts by weight of phenylhydrazine-4,β-hydroxyethyl sulfone and 960 parts by volume of ethylene glycol monoethyl ether. While cooling continues, 400 parts by volume of water are added dropwise. 2 more~
Stir for 3 hours, then vacuum off at room temperature and wash several times with methanol and water. 1-[4″-(β-hydroxyethylsulfonyl)-phenyl]-3-[3(4′-dichloro-6′-methyl-phenyl]-△2-pyrazoline 2
1.5 parts by weight are obtained.

Claims (1)

[Claims] 1 The following general formula (II) or (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In each of the above formulas R means a lower alkyl group, R' means a hydrogen atom or an optionally substituted phenyl group, and Z means a halogen atom or a dialkylamino group. There are tables etc. ▼The following general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R and R' have the above meanings.) A method for producing a compound.