JPH04321643A - Diacetylene-containing benzoic acid derivative - Google Patents

Abstract

PURPOSE:To obtain a new diacetylene-containing benzoic acid derivative useful as a non-linear optical material, showing electrical and optical functions of higher order by solid-phase polymerization as a polydiacetylene synthetic material. CONSTITUTION:A diacetylene-containing benzoic acid derivative shown by formula I (substitution position of XCO may be any of ortho-, meta- or para- position; X is OR<2> or NR<3>R<4>; R<2> to R<4> are H or alkyl; R<1> is alkyl, phenyl or substituted phenyl) such as meta(octa-1,3-diynyl)benzoic acid. The compound is synthesized by subjecting a compound shown by formula II and a compound shown by formula III or a compound shown by formula IV and a compound shown by formula V to asymmetric coupling reaction and optionally esterifying or amidating.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a novel benzoic acid derivative containing a diacetylene group, which is a polydiacetylene synthetic material that is promising as a nonlinear optical material.

0002

BACKGROUND OF THE INVENTION Hitherto, as a symmetrical diacetylene compound, for example, a bistosil compound represented by the following formula 2 has been used as a typical polyacetylene synthetic material.

0003

[Case 2]

Schulz et al. also synthesized diacetylene represented by the following formula 3 (Mac-romol.
m. , Rapid Commun. ,3,249-2
54 (1982)).

[0005]

[Chemical formula 3]

(In the formula, R represents an alkyl group, etc.) On the other hand, as an asymmetric diacetylene compound, for example, G
arito et, al, ACS Symposia
um Series, 223, 1 (1083) contains a compound represented by the following formula 4, and JP-A No. 61-134345 contains a compound represented by the following formula 5.
475 or JP-A-62-288612, a diacetylene compound represented by the following formula 6 is disclosed in JP-A-62-288612.
A compound represented by the following formula 7 is proposed in Japanese Patent Publication No. 43149-43149, and a compound represented by the following formula 8 is proposed in JP-A-61-43149.

[0007]

[C4]

[0008]

[C5]

[0009]

[C6]

0010

[C7]

[0011]

[Chemical formula 8]

0012

[Problems to be Solved by the Invention] The above compounds have improved electrical and optical functions, but there is a need for monomers for nonlinear optical materials that exhibit even higher-order electrical and optical functions. It has been done. In view of the above points, an object of the present invention is to have an electron-withdrawing substituent such as a carbonyl group or a carboxyl group on one side and an electron-donating substituent such as a phenyl group on the other side, thereby achieving a higher order. The present invention aims to provide a diacetylene-containing ben derivative that exhibits electrical and optical functions and is useful as a material for synthesizing polydiacetylene.

[0013]

[Means for Solving the Problems] The diacetylene-containing benzoic acid derivative of the present invention is represented by the following formula (1).

[0014]

[Chemical formula 9]

In the formula, the substitution position of X-CO- is ortho,
It may be either meta or para, and X is OR2(R2
is hydrogen or alkyl group) or NR3 R4 (
R3 and R4 are each hydrogen or alkyl group)
and R1 represents an alkyl group, a phenyl group or a substituted phenyl group. Examples of the substituted phenyl group include phenyl groups substituted with an alkyl group or an alkoxy group.

The diacetylene-containing benzoic acid derivative of the present invention basically follows the following reaction formula (9) or reaction formula (1).
It can be synthesized by an asymmetric coupling reaction as shown in 0).

[0017]

[Chemical formula 10]

Note that in order to obtain a diacetylene-containing benzoic acid derivative in which X is OH or OR (R is an alkyl group), the diacetylene-containing benzoic acid derivative obtained from the above reaction formula (9) or (10) is used. It can be esterified. Furthermore, the benzoic acid amide compound can be synthesized by amidation of a benzoic acid derivative, and it is also possible to select reaction conditions such that the amine used in the asymmetric coupling reaction directly serves as an amidating agent.

[0019] This asymmetric coupling reaction
It is called the ot-Chodkiewicz reaction and can be carried out under the following conditions. That is, a bromine compound as shown in the above formula is gradually dropped into a mixed solution prepared by adding a catalyst and hydroxylamine hydrochloride to an amine-based aqueous solution of a terminal acetylene compound as shown in the above formula. The reaction is allowed to proceed. In addition, in order to avoid a homocoupling reaction between acetylenes, the inside of the system should be replaced with an inert gas.

In the above reaction, the catalyst, hydroxylamine solution, amine aqueous solution and organic solvent used,
The reaction conditions, etc. are as follows. As the catalyst, various monovalent copper compounds are preferably used, and cuprous chloride is particularly preferably used. The amount used is preferably in the range of 0.5 to 60 mol% of the acetylene compound used.

Hydroxylamine hydrochloride Hydroxylamine hydrochloride is used to maintain the activity of the catalyst, and can be added at any time during the reaction when the reaction solution turns blue, which is the color of divalent copper ions. It is preferable to do so. Amine Aqueous Solution Aqueous solutions of amines such as methylamine, ethylamine, propylamine, etc. are preferably used. It is usually used in excess of the reaction substrate.

Organic Solvent Reaction To assist in dissolving the substrate, for example, the following polar solvents are used. That is, alcohol solvents such as methanol, ethanol, and propanol, aprotic polar solvents such as tetrahydrofuran, dioxane, and dimethyl formaldehyde, and the like are preferably used.

Reaction conditions: The reaction temperature is 0 to 50°C, and the dropwise addition time is controlled to prevent the temperature of the system from rising suddenly. Usually, the time can be appropriately determined within the range of 30 to 20 hours. In addition, the reaction time ranges from several hours to 2 to 2 hours after the completion of the dropwise addition.
Continue stirring for 3 days to complete the reaction.

Treatment after completion of the reaction By adding a small amount of potassium cyanide or sodium cyanide to the reaction mixture, the copper catalyst is converted into a water-soluble compound, and then poured into a large excess of acidic aqueous solution to obtain the desired benzoin. An acid derivative is precipitated, or an acidic aqueous solution is poured into the residue obtained by distilling off the solvent from the reaction mixture, and this is extracted with an organic solvent such as chloroform or benzene. This extract is dried with a dehydrating agent such as anhydrous magnesium sulfate, and then the solvent is distilled off to obtain the desired benzoic acid derivative.

[0025] The acids preferably used here are inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Purification The crude product is purified by recrystallization from a suitable organic solvent. Synthesis of derivatives An esterification reaction can be performed to obtain a benzoic acid ester using a conventional method, and an amidation reaction can be performed using a conventional method to obtain a benzoic acid amide.

[0026] Some of the diacetylene-containing benzoic acid derivatives obtained above are easily polymerized by light or heat, so it is desirable to store them in a cool, dark place protected from light. The diacetylene-containing benzoic acid derivatives of this invention were analyzed by nuclear magnetic resonance analysis (NMR) as described in the following examples.
Its structure has been confirmed by instrumental analysis methods such as , infrared absorption spectroscopy (IR), and elemental analysis.

[0027]

[Embodiments] Examples of the present invention will be described below. Example 1 14.6 g of metaethynylbenzoic acid was added to 5 g of sodium hydroxide.
An aqueous solution of sodium salt of metaethynylbenzoic acid was obtained by dissolving it in 100 ml of an aqueous solution containing g. On the other hand, 16 g of bromine was gradually added to 70 ml of an aqueous solution containing 13 g of sodium hydroxide under a nitrogen stream at a temperature range of 5 to 10°C, and the above sodium salt solution of metaethynylbenzoic acid was added to the obtained solution under a nitrogen stream. was gradually added to the solution while stirring. Stir for 5 to 20 hours, then add 200 to 500 ml of water to dissolve, remove the insoluble portion by filtration, add 50% acetic acid to the filtrate to make it acidic, filter the precipitate, wash with water, and dry under reduced pressure at room temperature. , yellow powder crystals with a melting point of 153-155°C were obtained in a yield of 88%.

The reaction formula at this time was as shown in Reaction Formula 11 above, and the obtained bromine product was as shown in Formula 11.

[0029]

[Chemical formula 11]

[0030] 15 g of the bromine compound thus obtained was
In addition to 70% ethylamine aqueous solution (ml), a small amount of methanol or tetrahydrofuran (THF) was added and dissolved. Add this to 8g of 1-octyne, 10ml of 70%
Add a mixture of ethylamine aqueous solution, 20 ml of THF, 10 ml of methanol, 0.2 g of cuprous chloride, and 0.5 g of hydroxylamine hydrochloride under a nitrogen stream while stirring to prevent the temperature from rising rapidly. Added. When the reaction system turns blue, add a small amount of hydroxylamine hydrochloride to maintain the yellow color and allow the reaction to proceed for 5 to 20 hours. After the reaction is complete, add 1 to 2 g of sodium cyanide.
After addition, pour the reaction into 500-100 ml of water,
The precipitated solid is filtered and thoroughly washed with aqueous ammonia until the filtrate no longer turns blue. 20% of the solid obtained
The salt was converted to acid by treatment in acetic acid.

[0031] It was filtered, washed with water and dried. The yield was 65%, and the meta(octa-1,3-diynyl) was a pale yellow crystalline powder.
Benzoic acid was obtained. The reaction formula at this time is as shown in the following formula (12).

[0032]

[Chemical formula 12]

The elemental analysis values and calculated values of this meta(octa-1,3-diynyl)benzoic acid (C17H18O2) are as follows:
The results are as follows, and the two are in good agreement, and the results of infrared absorption spectrum analysis are as shown in FIG. Example 2 14.6 g of paraethynylbenzoic acid was added to 70% ethylamine.
After dissolving in a mixed solution of 30 ml of aqueous solution and 20 ml of methanol and adding 0.3 g of cuprous chloride and 0.5 g of hydroxylamine hydrochloride, 19 g of 1-bromo-1-octyne was dissolved in 10 ml of THF. The mixture was gradually added to the solution with stirring under a nitrogen stream. After completion of dripping, 5 to 10
The reaction continued for hours. After the reaction is complete, 2 g of potassium cyanide is added to the reaction mixture, which is added to 500 ml of hydrochloric acid acidified water, and the precipitate is filtered, washed, and dried to obtain meta(octa-1,3-diynyl) as a white to pale yellow crystalline powder. Benzoic acid was obtained (yield about 80%).

The reaction formula at this time is as shown in the following formula (13).

[0035]

[Chemical formula 13]

The melting point of the obtained meta(octa-1,3-diynyl)benzoic acid (C17H18O2) is 194°C, and the elemental analysis values and calculated values are as follows, and they are in good agreement. Further, the results of infrared absorption spectrum analysis were as shown in FIG. Example 3 α-chloro-para-n-butylstyrene obtained by the reaction of para-n-butylacetophenone and phosphorus pentachloride was treated with caustic soda in dimethyl sulfoxide (DMSO) to form para-n-butylphenylacetylene. I got it. This para-n-butylphenylacetylene was brominated with sodium hypobromite (NaOBr) to obtain 1-bromo-para-n-butylphenylacetylene.

The reaction formula at this time is as shown in the following formula (14).

[0038]

[Chemical formula 14]

Next, under the same reaction conditions as in Example 2,
14.6 g of paraethynylbenzoic acid and 24 g of the above 1-
By reacting with bromo-para-n-butylphenylacetylene, a yellow crystalline powder of para(para-butylphenylbutylene) was obtained.
1,3-diynyl)benzoic acid was obtained (yield: 86%), which was recrystallized from a mixed solvent of methanol and benzene. The reaction formula at this time is as shown in the following formula (15).

[0040]

[Chemical formula 15]

The obtained para (para-butylphenyl but-
1,3-diynyl)benzoic acid (C21H18O2) is
At 130°C, a phase change occurred to form petal-shaped crystals, and when the temperature was further increased, it melted at 200°C or higher, and at the same time polymerized to become a brown resin-like (amorphous) state. The elemental analysis values and calculated values were as follows, and they matched well. Example 4 When 100 g of m-methoxyacetophenone was dissolved in 250 ml of benzene and 160 g of phosphorus pentachloride was gradually added and stirred, the reaction proceeded exothermically while generating hydrogen chloride. The reaction was allowed to proceed at room temperature for 24 hours, and the produced phosphorus oxychloride was removed by vacuum distillation.Then, the reaction product was poured into 1 liter of ice water and extracted with ether. This ether phase was washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain α-methyl-meta-methoxystyrene. This α-methyl-meta-methoxystyrene was directly dissolved in 85% ethanol, two equivalents of potassium hydroxide was added, and the mixture was refluxed for 30 hours with stirring. after that,
The ethanol was distilled off, poured into a large amount of ice, and the product was extracted with ether. After distilling off the ether, 9
A fraction between 5 and 100°C (approximately 7 Torr) was collected. m-methoxyphenylacetone was obtained in a yield of about 50% based on the starting material m-methoxyacetophenone.

This m-methoxyphenylacetone was gradually added to the NaOBr aqueous solution under a nitrogen stream and stirred. The molar ratio of acetylene and NaOBr is approximately 1/2.
And so. A small amount of glyme was added to improve mixing, and then stirred at room temperature for 15-20 hours. As the reaction progressed, the product separated into the lower layer. After the reaction was completed, the reaction mixture was poured into water and the product was extracted with ether. After drying this ether phase over anhydrous magnesium sulfate, the ether was distilled off to obtain the target product, 1-bromo-2-methoxyphenylacetylene, in a yield of about 63%.

By reacting this 1-bromo-2-methoxyphenylacetylene with 14.6 g of paraethynylbenzoic acid under the same reaction conditions as in Example 2, para(
Metamethoxyphenylbut-1,3-diynyl)benzoic acid was obtained as a pale yellow crystalline powder (yield about 60%). The reaction formula at this time is as shown in the following formula (16).

[0044]

[Chemical formula 16]

The elemental analysis values and calculated values of the obtained para(methoxyphenylbut-1,3-diynyl)benzoic acid (C18H12O3) are as follows, and both agree well. The spectrum analysis results were as shown in FIG. 3, and the nuclear magnetic resonance analysis (NMR) results were as follows (see FIG. 4). NMR results 1H-NMR (100MHz, CDCl3) δ(
ppm): 3.75 (S, 3H, O-CH3) 6.9
~7.5 (m, 4H, Hc, Hd, He, Hf) 7.7
(d, 2H, Hb) 7.95 (d, 2H, Ha)

[0046]

Effects of the Invention As described above, the diacetylene-containing benzoic acid derivative of the present invention is of an asymmetric type, and has an electron-withdrawing substituent such as a carbonyl group or a carboxyl group on one side, and a phenyl group on the other side. By having an electron-donating substituent, higher-order electrical and optical functions are exhibited after solid-phase polymerization as a polydiacetylene synthetic material, making it useful as a nonlinear optical material.

[Brief explanation of drawings]

FIG. 1 is an IR spectrum diagram of meta(octa-1,3-diynyl)benzoic acid.

FIG. 2 is an IR spectrum diagram of meta(octa-1,3-diynyl)benzoic acid.

FIG. 3 is an IR spectrum diagram of para(methoxyphenylbut-1,3-diynyl)benzoic acid.

FIG. 4 is a 1H-NMR chart of para(methoxyphenylbut-1,3-diynyl)benzoic acid.

Claims (1)

[Claims] 1. A diacetylene-containing benzoic acid derivative represented by the following formula 1. embedded image (wherein, the substitution position of X-CO- may be ortho, meta or para, and X is OR2 (R2 is hydrogen or an alkyl group) or NR3 R4 (R3,
R4 each represents hydrogen or an alkyl group),
R1 represents an alkyl group, a phenyl group or a substituted phenyl group. )