KR820000900B1 - Process for the preparation of 1.4-bis-styrylbenzene derivatives - Google Patents

Abstract

1,4-Bis-styrylbenzene derivs. ≮I; R, R1 = H, halogen, lower alkyl, lower alkoxy; A, A1 = halogen, -OH, lower alkyl, substitutable lower alkylene; X, X1 = -COOM, -SO3M(M = H, alkali metals, alkali earth metals, organic ammonium, guanidium); R2 = lower alkyl, phenyl≉were prepd. by reaction of 1,4-xylene phosphoric ester derivs. (II), compd. (III) and benzaldehyde derivs. (IV). The compds. (I) are heat- and alkalistable fluorescent whiteners imparting a clear white appearance to natural and synthetic fibers, detergents, paper, and plastics.

Description

Method for preparing 1,4-bis-styrylbenzene derivative

The present invention relates to a process for the preparation of the novel 1,4-bis-styrylbenzene derivatives. More specifically, the present invention is the following general formula

(Wherein R and R ₁ are the same or different and are hydrogen, halogen, lower alkyl group or lower alkoxy group, A and A ₁ are the same or different, halogen hydroxyl group or lower alkyl group, lower alkylene group which may be substituted, and X and X ₁ are the same or different and represent a -COOM group or a -SO ₃ M group, where M represents hydrogen, an alkali metal, an algicarito metal, an organoammonium, guanidium) A method for producing a 1,4-bis-styryl benzene derivative useful as coloration agent).

Conventional optical brightening agents for 1,4-bis-styryl benzene derivatives are Japanese Patent Publication Nos. 1962-6715, 1962-l1678, 1965-580, 1970-31870 and 1976-19875 Although somewhat described in the foregoing, etc., it is not known at all about a compound having a -OAX group, that is, a type having an X group having water solubility through -OA- group, in a molecule represented by the aforementioned general formula (1).

The inventors have found that the 1,4-bis-styrylbenzene derivative represented by the general formula (1) described above is extremely excellent for various organic materials, in particular, cellulose fiber materials, nitrogen-containing fiber materials, synthetic resins, and detergents or soaps. It was found to be an optical brightening agent. Particularly, the compounds of the present invention give excellent brightening effect to cellulose fiber materials in the 1,4-bis-styrylbenzene derivatives described in Japanese Patent Application Laid-Open No. 1962-11678. It was unexpected at all, considering that the type of sulfonic acid group introduced at both ends of the phenyl group did not show a practical brightening effect on the cellulose fibers.

The compound of the present invention can be produced, for example, in the following manner. That is, the general formula (II)

(Wherein R ₂ represents a lower alkyl group or a phenyl group) 1,4-xylene phosphonic acid ester derivatives represented by the following general formula (III)

The same or different benzaldehyde derivatives represented by (wherein R, A and X represent the definitions above) are readily obtained by reacting in the presence of a proton acceptor, preferably in a hydrophilic organic solvent. The 1,4-xylene phosphonic acid ester derivative represented by the general formula (II) is obtained by reacting 1,4-xylene dichloride with an excess of phosphonic acid ester by a known method, but as the phosphonic acid ester, a corresponding lower alkyl ester, Especially methyl or ethyl esters are generally advantageous.

The benzaldehyde derivative represented by the general formula (III) preferably represents a hydroxy benzaldehyde derivative and a halogenated lower alkylsulfonic acid or a dehydrating cyclic compound of hydroxy lower alkylsulfonic acid, that is, a stone compound, when X represents a sulfonic acid group, respectively. Can be obtained in high yield by reaction in the presence of a basic catalyst in an inert organic solvent. In the case where X represents a carboxylic acid group, a dehydrating cyclic compound of a hydroxy benzaldehyde derivative and a halogenated lower fatty acid or hydroxy lower fatty acid, each of which has a molecular weight ratio, preferably a lactone compound, is preferably used in the aqueous or inert organic solvent. It is readily obtained as it is present and reacted.

As hydroxy benzaldehyde derivative which can be used for the said reaction, for example

(1) salicylic aldehyde,

(2) 3-hydroxy benzaldehyde,

(3) 4-hydroxy benzaldehyde,

(4) 5-chloro-2-hydroxy benzaldehyde

(5) 2-chloro-4-hydroxy benzaldehyde

(6) 5-bromine-2-hydroxy benzaldehyde

(7) 3-brom-4-hydroxy benzaldehyde

(8) 3-methyl-2-hydroxy benzaldehyde

(9) 4-methyl-2-hydroxy benzaldehyde

(10) 5-methyl-2-hydroxy benzaldehyde

(11) 2-methyl-4-hydroxy benzaldehyde

(12) 5-tert-butyl-2-hydroxy benzaldehyde

(13) 4-methoxy-2-hydroxy benzaldehyde

(14) 5-methoxy-2-hydroxy benzaldehyde

(15) 2-methoxy-4-hydroxy benzaldehyde

(16) 3-ethoxy-4-hydroxy benzaldehyde

(17) 3-isopropoxy-4-hydroxy benzaldehyde

(18) 4-methoxy-3-hydroxy benzaldehyde

Etc. can be mentioned. These hydroxy benzaldehyde derivatives and the benzaldehyde derivatives represented by the aforementioned general formula (III) may be of the corresponding acetal type.

Moreover, as a dehydration cyclic compound of halogenated lower alkyl sulfonic acid or hydroxy lower alkyl sulfonic acid, for example,

Etc. can be mentioned.

As a dehydration cyclic compound of halogenated lower fatty acid or hydroxy lower fatty acid, for example

Etc. can be mentioned.

The 1,4-bis styryl benzene derivative of the present invention is useful for optically brightening various organic materials.

For example, cellulose fibers, woven cotton fabrics are brightened to excellent whiteness. As a dyeing method, it is especially suitable by high temperature continuous lightening methods, such as a pad steam method and a dry heat fixing method (pad backing method), in addition to a normal dipping method. Moreover, the well-known dyeing method applicable to cellulose fiber, such as the so-called solvent dyeing using an organic solvent, can be used.

A compound of the present invention, for example the following formula obtained according to Example 1 described below

The compound represented by following formula described in Unexamined-Japanese-Patent No. 1962-11678.

The reflectance of the fluorescence at 435 mμ of the bright colored canvas obtained by padding the cotton textile browood fabric with a salt bath (0.2 wt% aqueous solution) adjusted to the same concentration at each optical density by the known compound represented by When 100% is as shown in the table below.

The compounds of the present invention can brighten natural or synthetic nitrogen fiber materials, such as silk, wool or nylon, to excellent whiteness.

The compounds of the present invention have extremely good heat resistance and are therefore particularly suitable for high temperature continuous dyeing of synthetic polyamide fiber materials. The high temperature continuous dyeing here is a method of padding a thin aqueous solution of a brightening agent into a synthetic polyamide fiber material and preliminarily drying, then treating and soaping at a high temperature (about 1-3 minutes at about 150-200 ° C) for a predetermined time.

Conventionally known 4,4'-bistriazolyl stilbene-2,2'-disulfonic acid derivatives (Branco Pore CL Bayer) suitable for this salt method and the compounds of the present invention obtained in Example 1 described later are respectively When the reflectance of the fluorescence at 440 was compared with that of the light-colored fabric obtained by subjecting the nylon Daputa to the same concentration, the reflectance of the untreated fabric was compared. It was like

Moreover, the compound of this invention gives the outstanding brightening effect also about wool. As a brightening agent for wool, for example, wool is known by using a known dyeing method using known Tinopearl WG (Ciba-Gaigyi-made pydorarin-type compound) and Yuritex NFW (Ciba, Gaisie-made bis, Stilbene-type compound). When the cloth is brightened, the former gives a brightening effect with the hue of fluorescence being quite green, and the latter has a slightly redizing effect on the contrary.

On the other hand, when using the compound of the present invention, an extremely clear neutral white lightening effect is obtained, and the visual whiteness is much better than those mentioned above. The reflectance of the fluorescence at 440 m mu of these bright color fabrics was as follows for the untreated cloth.

Furthermore, the compound of the present invention can also brighten the base of soaps, detergents, fats and oils, and the like with excellent whiteness. In particular, the industrial or household detergents used for washing or washing textile products are brightened to increase the value of the products and at the same time sharpen the textile products treated with the detergent containing the compound of the present invention. Therefore, the compounds of the present invention are suitable as brightening agents for the addition of these detergents.

Well-known formula as a brightening agent for detergent formulation

10 g of a detergent powder having the following composition for the compound represented by the present invention and the compounds of the present invention obtained in Examples 17 and 8 to be described later.

At a concentration of 0.2% and 0.5% (per weight of detergent), respectively, which was slurried with a small amount of water and evaporated to dryness in a water-based evaporating dish, and then dried at 440 mμ for the clear detergent powder obtained. The reflectance of the fluorescence was measured. The untreated detergent powder is shown in the following table.

In addition to the excellent heat resistance as described above, the compound of the present invention was found to be stable even at high temperatures under alkaline conditions. Therefore, it is excellent in the point which it can mix | blend with the alkaline detergent mentioned above, and can endure this high temperature drying especially spray drying sufficiently, and does not yellow the detergent substance.

The compounds of the present invention can be used to brighten pulp or paper. As a usage form for this purpose, well-known usage methods, such as a pulp internalization method, the surface coating method, or the size press method, can be applied, but the surface of the paper is especially important among these. In other words, starch, casein, white pigment or synthetically available surface coating agents may be used before or after coating the surface of the paper or in combination with these surface coating agents. It can be added as a flashing agent with white pigments such as titanium oxide or by brightening the case layer or photo paper for the use of company's own clothing or super sensitization.

The compound of the present invention is not only urea resins, melamine resins, benzoguanamine resins, urea, melamine resins, but also various synthetic or semi-synthetic organic polymer materials such as polyamides, polyurethane polyvinyl alcohols, polycarbonates, epoxide resins, and the like. Or it is useful also for the brightening of the material which consists of amino-type resins, such as resin of these mixtures, or a cellulose ester, a cellulose ether, etc. Application of the compounds of the invention to these materials can be carried out at any stage. That is, it can be added before or during molding of the above resin material. Thus, for example, the compounds of the present invention can be added to molding formulations when making films or other shaped articles. It may also be finely divided by dissolution, dispersion or other method in the spinning compound before spinning. The brightening agent can also be added to the raw materials, reaction mixtures or intermediates used in the preparation of the above-described synthetic or semisynthetic organic materials, ie before or during the polycondensation, polymerization or polyaddition chemical reaction.

When using the compound of the present invention, the concentration of the material to be treated can be changed in a wide range. Very thin concentrations, such as 0.001% by weight, can achieve good brightening effects, but many actual concentrations can range from 0.01-1% by weight, or approximately 2%.

When using the compound of the present invention, it can be used in combination with known dyeing aids, for example, forget-me-not, salt, urea, acetic acid or surfactant. It can also be used in combination with dyes, pigments or other types of optical brightening agents. The compounds of the present invention are stable against, for example, reducing agents such as sulphide, or chemical fabrics, in particular chlorine-based fabrics, which makes them more advantageous for use as brightening agents for various textile materials.

Moreover, it can use with various resin additives, for example, antioxidant, an antistatic agent, an ultraviolet absorber, a heat stabilizer, or a filler.

The form of the brightening agent which contains the compound of this invention as an active ingredient can take arbitrary arbitrary forms according to the purpose of use, such as powder form, granule form, paste form, dispersion form, emulsion form, or thick liquid form. In the case of powdery granular form, the alkaline earth metal salt or organic amine salt of the general formula (1) described above may be used, but in many cases, the alkali metal salt may be used. In the case of paste or acid form, it is preferably prepared by mechanically atomizing and dispersing the poorly soluble salt of the general formula (1), especially poorly soluble alkylamine salt or guanidine salt, in the presence of a suitable surfactant. do. In the case of the thick liquid form, the alkyl metal salt of the compound of the present invention may be liquefied with the aid of a suitable known dissolution enhancer, but preferably the water-soluble organic amine salt of the compound of the present invention, in particular, It is advantageous to use alkanolamine salts. The elimination of coexisting inorganic salts as much as possible is a condition for obtaining a stable rich liquid product.

In order to obtain the poorly soluble or soluble organic amine salt of the compound of the present invention, the corresponding free acid is easily obtained by neutralizing the preferred organic amine. At this time, even if the organic amine is used in excess, there is no lower obstacle.

The present invention will be described in more detail with reference to the following Examples.

Example 1

To 17.5 g of 1,4-xylene dichloride, 50 g of triethyl phosphite (P (OC ₂ H ₅ ) ₃ ) was added and mixed under reflux for 9 hours, and excess triethyl phosphite was distilled off under reduced pressure, and the residue was dried. After dilution with ligron and allowed to cool, crystals are precipitated. This was separated by filtration, washed with a small amount of ligroin, and dried to obtain white crystals (melting point 71-73.5 ° C.) of the phosphonic acid ester derivative corresponding to the above formula.

61 g of salicylic aldehyde is dissolved in 400 ml of ethanol, and 20 g of caustic soda is dissolved in a small amount of water, and the sodium salt of salicylic aldehyde is precipitated. The whole was heated, refluxed and mixed with 65 g of propanestone for about 20 minutes, followed by mixing for 2 hours, and then a small amount of water was added to the reaction mixture to completely dissolve the precipitate. After cooling, the precipitated crystals are filtered off, washed well with ethanol and dried to obtain a benzaldehyde derivative represented by the above formula.

7.6 g of the phosphonic acid ester derivative obtained in the foregoing (A) and 12.8 g of the aldehyde derivative obtained in (B) are dissolved in 100 ml of N, N-dimethyl formamido and 10 g of powdered potassium hydroxide is added at 20 ° C. or lower. At this time, the temperature is slightly increased, but the mixture is mixed at 20-25 ° C for 2 hours, and then reacted at 40 ° C for 30 minutes. 300 ml of water is added to the reaction mixture, slightly heated to dissolve the contents and a small amount of insolubles is filtered off. Hydrochloric acid is added to the filtrate to adjust the alkalinity, and 40 g of salt is added to salt the salt. Thus, the precipitated flaky crystals are separated, washed with a small amount of water and dried. Elemental analysis of the pure product obtained by subjecting the obtained 1,4-bis styrylbenzene derivative represented by the above formula to water through crystallization is as follows.

Example 2

In Example 1- (B), if the same amount of 3-hydroxybenz aldehyde is reacted in the same manner instead of salicylic aldehyde,

A benzaldehyde derivative represented by is obtained.

When 12.8 g of this benzaldehyde derivative was reacted with 7.6 g of a phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C),

The 1,4-bis styrylbenzene derivative shown is obtained. Elemental analysis of the pure product obtained by recrystallizing these in water was as follows.

Example 3

In Example 1- (B), when 68 g of 2-methyl-4-hydroxy benzaldehyde is reacted instead of salicylic aldehyde,

A benzaldehyde derivative represented by is obtained. When 13.6 g of this benzaldehyde derivative and 7.6 g of phosphonic acid ester derivative obtained in Example 1- (A) were reacted according to the method of Example 1- (C),

The 1,4-bis styryl benzene derivative shown is obtained. Elemental analysis of the pure product obtained by recrystallizing this in water is as follows.

Example 4

In Example 1- (B), 77 g of 3-methoxy-4-hydroxy benzaldehyde instead of salicylic aldehyde was reacted in the same manner using 72 g and 1,4 butane sltone instead of propane slate.

A benzaldehyde derivative represented by is obtained.

14.9 g of this benzaldehyde derivative was reacted with 7.6 g of the phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C).

The 1, 4-bis styrylbenzene derivative represented by is obtained. The elemental analysis value of the pure product obtained by recrystallizing this in water was as follows.

Example 5

6.4 g of the benzaldehyde derivative obtained in Example 1- (B), 6.4 g of the benzaldehyde derivative obtained in Example 2, and 7.6 g of the phosphonic acid ester derivative obtained in Example 1- (A) were obtained from Example 1- (C). Reaction according to the method

A mixture of compounds represented by is obtained. Such mixtures can also be used similarly as optical brightening agents.

Example 6

This alkaline solution in which 96.2 g of 1-chloroethanesulfonic acid and 24 g of sodium hydroxide were dissolved in 250 ml of water while 61 g of salicylaldehyde and 20 g of sodium hydroxide were dissolved in 300 ml of water, and the solution was heated and mixed to about 70 ° C. Add about 30 minutes. Subsequently, the mixture was heated to 95-100 ° C. and reacted for about 3 hours. After cooling, the reaction mixture was strongly acidified with concentrated hydrochloric acid, and the precipitated precipitate was filtered and washed with water.

A benzaldehyde derivative represented by is obtained. 11. g of this benzaldehyde derivative was reacted with 7.6 g of the phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C).

The 1,4-bis styrylbenzene derivative represented by is obtained. Elemental analysis of the pure product obtained by recrystallization from water was as follows.

In the present example, the benzaldehyde derivative obtained by using 81 g of 2-chloro-1-hydroxy ethanesulfonic acid instead of 1-chloroethane sulfonic acid in the same manner as the phosphonic acid ester derivative was

A mixture of 1,4-bis-styrylbenzene derivatives represented by is obtained.

Example 7

In Example 1- (B), the same reaction was carried out using 78 g of 5-chloro salicyaldehyde instead of salicyaldehyde.

A benzaldehyde derivative represented by is obtained.

7.2 g of this benzaldehyde derivative and 6.4 g of benzaldehyde derivative obtained in Example 1- (B) were reacted with 7.6 g of the phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C) If you let

A mixture of compounds represented by is obtained.

Example 8

(A) Alkaline, in which 61 g of salicyaldehyde and 20 g of sodium hydroxide were dissolved in 300 ml of water, and the solution was heated and mixed at around 70 ° C. while 47.3 g of monochloroacetic acid and 20 g of sodium hydroxide were dissolved in 200 ml of water. The solution is added dropwise for about 30 minutes. The mixture was then heated to 95-100 ° C. for about 3 hours, allowed to cool, and the reaction mixture was strongly acidic with concentrated hydrochloric acid. The precipitated precipitate was filtered off, washed with water and dried.

A benzaldehyde derivative represented by is obtained.

(B) When 8.6 g of the benzaldehyde derivative described above was reacted with 7.6 g of the ester derivative with the method of Example 1- (C), the phosphonic acid obtained in Example 1- (A)

The 1,4-bisstyrylbenzene derivative represented by this is obtained. Elemental analysis of the pure product obtained by recrystallizing these in water is as follows.

Example 9

In Example 8- (A), the reaction was performed in the same manner using 61 g of 2-chloropropionic acid instead of monochloroacetic acid.

The benzaldehyde derivative shown in

9.4 g of this benzaldehyde derivative was reacted with 7.5 g of the phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C), and

1,4-bisstyrylbenzene derivatives were obtained. The elemental analysis of pure products obtained by recrystallization from water is shown in the table below.

Example 10

In Example 8- (A), the reaction was performed in the same manner using 61 g of 1-chloropropionic acid instead of monochloroacetic acid.

A benzaldehyde derivative represented by the above was obtained. 9.4 g of this benzaldehyde derivative was reacted with 7.6 g of the phosphonic acid ester derivative obtained in Example 1- (A) according to the method of Example 1- (C),

Obtained 1,4-bisstyrylbenzene derivative. Elemental analysis of the pure product obtained by recrystallizing this in water is shown in the following table.

Example 11

The method of phosphonic acid ester derivative 7.6 obtained in Example 1- (A) and 4.2g of benzaldehyde derivative obtained in Example 8- (A) and 4.7g of benzaldehyde derivative obtained in Example 9 were obtained. According to the following equation

A mixture of compounds represented by is obtained.

In the same manner, 1,4-bisstyrylbenzene derivatives as described below were synthesized. Unless otherwise specified in the following table, R = R ₁ and -OAX = -OA ₁ -X ₁ , the number showing the position of each of these substituents is for the -CH = CH- group and the elemental analysis is calculated at the top. , Bottom shows actual measurements.

Next, some examples of use of the compounds of the present invention are given.

1. (A) Padding on cotton cloth

The colorant is dissolved in water at a concentration of 0.2-0.4% by weight (solution concentration) to prepare a salt bath, and the material of the salt bath is 1 dip and 1 nip. At this time, the pick-up is adjusted to 70%. Drying this at 60-65 ° C. for 30 minutes gives a cotton cloth dyed to vivid whiteness.

(B) Infestation to cotton cloth (meriyasu)

The material is immersed in a salt bath of the above formulation, treated at 25 ° C. for 20 minutes, squeezed and dried at 60-65 ° C.

2. High temperature dyeing of nylon

1 dip and 1 nip of the material are dissolved in water to a level of 5 g / l, and the pick up is 70% in the prepared salt bath. This was pre-dried at 80 ° C.-100 ° C. for about 3 minutes, followed by dry heat treatment at 180-190 ° C. for 1-0.5 minutes. In addition, soupic bath of prescription to do this

It is rinsed and dried for 30 minutes at 70 ° C. in water.

3. Infestation of wool (mosrin) with hydrogen sulfide

The material is immersed in the salt bath of the formulation, treated at 60 ° C. for 30 minutes and washed with water.

4. Coloration of Amino Resin

To the resin liquid obtained by heating

Add to mix well in Nader. The present invention is dried in a hot air dryer at 80 ° C. for 90 minutes and then ground with a pot mill.

In addition, the fine powder (preferably poorly soluble organic amine salt of general formula (1) mentioned above, especially triethylamine salt guanidine salt etc.) of this invention is mix | blended so that it may become 0.1 weight% of the whole. The urea resin rampant obtained by molding this composition by a known method was brightly colored with extremely bright whiteness.

The poorly water-soluble organic amine acid of the compound of the present invention used in the above use example is prepared as follows. For example, the compound (sodium salt) obtained in Example 1- (C) is dissolved in water, and excess concentrated hydrochloric acid is added to this solution to make it strongly acidic. After cooling, the resulting precipitate is filtered off and washed with water to remove excess hydrochloric acid, and the filter cake is then dispersed in water again. A slight excess of triethylamine is added to this, which is retained alkaline and heated to 70-80 ° C. while stirring. After cooling, the resulting precipitate was filtered off, washed with water and dried to obtain a white powder of the corresponding triethylamine salt.

5. Surface coating of printing paper

Is dissolved with 300 g of water, and water is added to make the whole to 1000 g.

66 g of casein solution of the above composition is mixed, diluted with water, and the total amount is 250 g. 0.2 g of the compound of the present invention (Example 12) is added to this mixture to prepare a coating solution. It is coated on a certain size of printing paper and dried. The printing paper thus obtained was brightened with vivid whiteness.

6. Brightening Photo Paper (How to Apply on Variety Paper)

Each of the above components is mixed, 0.03 g of the compound of the present invention (Example 13) is added thereto, dissolved, and applied to a lighter paper and dried. The veriter paper thus obtained was brightened with very clear whiteness.

Claims (1)

1,4-bisstyrenebenzene derivative of formula (I), characterized by reacting a 1,4-xylenephosphonic acid ester derivative of formula (II) with a benzaldehyde derivative of formulas III) and (IV) Manufacturing method.

Wherein R and R ₁ are the same as or different from each other and are hydrogen, halogen, lower alkyl group or lower alkoxy group; A and A ₁ are the same or different from each other, and are lower alkylene groups which may be substituted with halogen, hydroxyl group or lower alkyl group; X and X ₁ are the same as or different from each other, and are -COOM group or -SO ₃ M group (M is hydrogen, alkali metal, alkaline earth metal, organic ammonium, guanidium, etc.); R ₂ is a lower alkyl group or a phenyl group.