JPH06135901A - Production of diphenylacetylene derivative - Google Patents

Abstract

PURPOSE:To simply obtain a diphenylacetylene derivative having nitro group and OH at the o-position thereof under mild conditions according to one-stage reaction by treating a stilbene derivative with a specific amount of t- butoxypotassium. CONSTITUTION:A stilbene derivative of formula I (R1 is diarylamino or halogen) is treated with t-butoxypotassium in an amount of >=2mol equiv. based on the compound of formula I in a polar solvent to afford the objective diphenylacetylene derivative of formula II (R2 is H or OH). Furthermore, the stilbene derivative of formula I is treated with the t-butoxypotassium in an amount of >=5mol equiv. based on the compound of formula I to provide the diphenylacetylene derivative of formula III (e.g. 4-diphenylamino-3'-hydroxy-4'- nitrodiphenylacetylene). Dimethylformamide is preferred as the polar solvent. The compounds of formulas II and III are important substances as nonlinear optical materials, intermediates for various coloring matters and liquid crystal compound, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a diphenylacetylene derivative (tolan derivative). More specifically, the present invention relates to a novel method for producing a corresponding diphenylacetylene derivative and / or a hydroxyl group-introduced diphenylacetylene derivative from a stilbene derivative.

[0002]

2. Description of the Related Art As a conventional technique for producing a corresponding diphenylacetylene derivative from a stilbene derivative, a method of brominating the ethylene group of the stilbene derivative with bromine and then dehydrobrominating with a base is generally used. However, this method is complicated because it is a two-step reaction of "bromination" and "dehydrobromination", and bromine used for bromination eventually becomes a waste, which is expensive.

Among the diphenylacetylene derivatives, compounds having a nitro group and a hydroxyl group at the ortho position are important substances as nonlinear optical materials, various dye intermediates, liquid crystal compound intermediates, etc. It is difficult to introduce a hydroxyl group at the ortho position of the group.

[0004]

The object of the present invention is to introduce a hydroxyl group from the stilbene derivative into the ortho position of the corresponding diphenylacetylene derivative and / or the nitro group by a one-step reaction under simple and mild reaction conditions. The present invention provides a novel method for producing a diphenylacetylene derivative.

[0005]

The object of the present invention is to provide a stilbene derivative represented by the following general formula (I) in a polar solvent,
achieved by treatment with potassium t-butoxy,
At least one diphenylacetylene derivative represented by the following general formula (II) can be obtained by a one-step reaction.

[0006] (In the formulas (I) and (II), R ₁ represents a diarylamino group or a halogen atom, and R ₂ represents a hydrogen atom or a hydroxyl group.) In the formulas (I) and (II), R ₁ is As the diarylamino group, those in which the aryl group is a phenyl group which may have an alkyl group, an amino group, a substituted amino group or an alkoxy group as a substituent are preferable. When R ₁ is a halogen atom, a chlorine atom and a bromine atom are preferable.

The method of the present invention in which a diphenylacetylene derivative represented by the formula (II) is obtained from a stilbene derivative in a one-step reaction is achieved by using a polar solvent and a specific base. Specific examples of the polar solvent used in the present invention include dimethylformamide, dimethylsulfoxide, quinoline, tetrahydroquinoline,
Examples include methylpyrrolidone, dimethylimidazolidinone, hexamethylphosphoramide, and the like. Preferably,
Dimethylformamide and dimethylsulfoxide are used, with dimethylformamide being particularly preferred.

Further, in the method of the present invention, the diphenylacetylene derivative represented by the formula (II) is specifically obtained by treating the stilbene derivative with t-butoxypotassium in the polar solvent. Therefore, when another metal alkoxide such as sodium methoxy, methoxylithium or sodium ethoxy is used instead of potassium t-butoxy, the diphenylacetylene derivative represented by the formula (II) cannot be obtained.

In the method of the present invention, the amount of potassium t-butoxy used affects the composition ratio of the R ₂ species in the compound of formula (II) produced. In order to convert the ethylene bond of the stilbene derivative into the acetylene bond of the diphenylacetylene derivative, the amount of potassium t-butoxy used must be at least 2 molar equivalents of the stilbene derivative. Therefore,
In order to obtain a compound in which R ₂ is hydrogen among the diphenylacetylene derivatives represented by the formula (II), t-butoxy potassium is used in an amount of 2 molar equivalents or more, preferably 3 molar equivalents or more of the stilbene derivative. When the amount of potassium t-butoxy used is less than 3 molar equivalents of the stilbene derivative, the amount of unreacted stilbene compound remaining increases. Further, R of the diphenylacetylene derivative of the formula (II) produced when the amount of potassium t-butoxy used is 4 molar equivalents or more, preferably 5 molar equivalents or more of the stilbene compound.
_{Although 2} is a hydroxyl group, the production amount increases.

In the method of the present invention, the detailed elucidation of the reaction mechanism has not been completed, but in the reaction for converting an ethylene bond into an acetylene bond and the reaction for introducing a hydroxyl group, dissolved oxygen in the solvent is involved in the progress of the reaction. Have the knowledge to In the present invention, the reaction is completed at room temperature with a reaction time of several minutes to several hours. The reaction may be carried out by heating if necessary.

In the method of the present invention, the simultaneous use of crown ether has the effect of activating potassium t-butoxy by trapping potassium in t-butoxypotassium. The stilbene derivative represented by the formula (I) used in the present invention can be prepared by various known methods such as Bu.
ll. Chem. Soc. Jpn., 46, 2828 (1973).

[0012]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

Example 1 4-diphenylamino-
Preparation of 3'-hydroxy-4'-nitrodiphenylacetylene 0.39 g (1 mmol) 4-diphenylamino-
After dissolving 4'-nitrostilbene in 20 ml of dimethylformamide, 2.23 g (19.9 mmol) of t-
Potassium butoxy was added and stirred at room temperature for 1 hour. The reaction solution was discharged into 70 ml of water, adjusted to pH 3 by adding 2N hydrochloric acid, and then extracted with 125 ml of benzene. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off from the extract under reduced pressure, the residue was purified by column chromatography (Wakogel C-200, solvent benzene: hexane = 1: 1), and then recrystallized from acetone to give a mixture of 0. 14 g (35% yield) of 4-diphenylamino-3′-hydroxy-4′-nitrodiphenylacetylene as red plate crystals (mp 135-137 ° C.)
Got as. It was confirmed from the following analysis results that the target compound was obtained.

MS (m / z): 406 (M ⁺ ) IR (Nujol): 2200 cm ^-1 (C≡C) ¹ H N. M. R. (CDCl ₃ ): 7.00 (ppm) (2H, d, J = 8.79Hz, A
rH) 7.07 (1H, dd, J = 1.47, 8.79, Ar
H) 7.12 (5H, m, ArH) 7.25 (1H, d, J = 1.47, ArH) 7.30 (5H, m, ArH) 7.38 (2H, d, J = 8. 79, ArH) 8.07 (1H, d, J = 8.79, ArH) 10.65 (1H, OH) Elemental analysis value: C (%) H (%) N (%) measured value 76.804 .58 6.85 calculated _{(C 26 H 18 N 2 O} 3) 76.83 4.46 6.89

Example 2 Preparation of 4-bromo-3'-hydroxy-4'-nitrodiphenylacetylene 0.30 g (0.99 mmol) 4-bromo-4'-
Nitrostilbene was dissolved in 30 ml of dimethylformamide, 1.11 g (9.9 mmol) of potassium t-butoxide was added, and the mixture was stirred at room temperature for 20 minutes. 70 reaction mixture
The mixture was discharged into ml of water, 2N hydrochloric acid was added to adjust the pH to 3, and the mixture was extracted with 125 ml of benzene. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off from the extract under reduced pressure, the residue was purified by column chromatography (Wakogel C-200, solvent benzene: hexane = 1: 1), and then recrystallized from ethanol to give a mixture of 0. 14 g (45% yield) of 4-bromo-
3′-Hydroxy-4′-nitrodiphenylacetylene was obtained as orange crystals (mp 172 to 175 ° C.).
It was confirmed from the following analysis results that the target compound was obtained.

MS (m / z): 317, 319
(M ⁺ ) IR (Nujol): 2200 cm ⁻¹ (C≡C) ¹ H N. M. R. (CDCl ₃ ): 7.10 (ppm) (1H, dd, J = 1.5 Hz,
8. ArH) 7.29 (1H, d, J = 1.5, ArH) 7.41 (2H, d, J = 8, ArH) 7.52 (2H, d, J = 8, ArH) 10. 62 (1H, s, OH) Elemental analysis value: C (%) H (%) N (%) measured value 52.95 2.69 4.44 calculated value (C ₁₄ H ₈ BrNO ₃ ) 52.85 2. 53 4.40

[0017]

According to the production method of the present invention, a corresponding diphenylacetylene derivative and / or a diphenylacetylene derivative having a further hydroxyl group introduced can be produced from various stilbene derivatives in a one-step reaction and by a simple method.

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[Procedure amendment]

[Submission date] April 5, 1993

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[Name of item to be corrected] Claim 1

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[Name of item to be corrected] Claim 2

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In the method of the present invention, the simultaneous use of crown ether has an effect of activating potassium t-butoxy by trapping potassium in t-butoxy potassium. The stilbene derivative represented by the formula (I) used in the present invention can be prepared by various known methods, for example,
Bull.Chem.Soc.Jpn., 46 , 2828 (1973) can be easily synthesized.

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[Name of item to be corrected] 0015

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[0015] (Example 2) 4-Bro Mo-3'-hydroxy-4'-nitro diphenyl acetylene preparation 0.30g of (0.99 mmol) 4-bromo-4'-
Nitrostilbene was dissolved in 30 ml of dimethylformamide, 1.11 g (9.9 mmol) of potassium t-butoxide was added, and the mixture was stirred at room temperature for 20 minutes. 70 reaction mixture
The mixture was discharged into ml of water, 2N hydrochloric acid was added to adjust the pH to 3, and the mixture was extracted with 125 ml of benzene. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off from the extract under reduced pressure, the residue was purified by column chromatography (Wakogel C-200, solvent benzene: hexane = 1: 1), and then recrystallized from ethanol to give a mixture of 0. 14 g (45% yield) of 4-bromo-
3′-Hydroxy-4′-nitrodiphenylacetylene was obtained as orange crystals (mp 172 to 175 ° C.).
It was confirmed from the following analysis results that the target compound was obtained.

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Claims (3)

[Claims] 1. A stilbene derivative represented by the following general formula (I) is treated with 2 mol equivalent or more of potassium t-butoxide of the stilbene derivative represented by the general formula (I) in a polar solvent. A method for producing a diphenylacetylene derivative represented by the following general formula (I): (In the formulas (I) and (II), R ₁ represents a diarylamino group or a halogen atom, and R ₂ represents a hydrogen atom or a hydroxyl group.) 2. A stilbene derivative represented by the following general formula (I) is treated in a polar solvent with t-butoxypotassium at 5 molar equivalents or more of the stilbene derivative represented by the general formula (I). A method for producing a diphenylacetylene derivative represented by the following general formula (I): (In the formulas (I) and (II), R ₁ represents a diarylamino group or a halogen atom.) 3. The method according to claim 1, wherein the polar solvent is dimethylformamide.