JP2734676B2 - Ether derivative and method for producing the same - Google Patents

Description

The present invention relates to an organic electronic material, for example, an ether derivative useful as an intermediate of a liquid crystal compound.

<Prior Art> Various compounds have been developed as liquid crystal compounds. However, there are very few compounds which are excellent in characteristics such as high-speed response and which become ferroelectric liquid crystals in a low-temperature region. Has not yet been sufficiently developed, and an intermediate and an industrially advantageous production method thereof are desired.

<Problems to be Solved by the Invention> The present invention provides an ether derivative useful as an intermediate of a ferroelectric liquid crystal compound which becomes a ferroelectric liquid crystal in a low-temperature region and has the above characteristics, and a method for producing the same. Aim.

<Means for Solving the Problems> That is, the present invention provides a compound represented by the general formula (I): (In the formula, R ^* represents an optically active alkyl group or an alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom, and n represents an integer of 1 to 6.) And its manufacturing method.

 Hereinafter, the present invention will be described in detail.

The ether derivative represented by the above general formula (I) is a compound represented by the general formula (II): R ^* -OH (II) wherein R ^* is an optically active compound having 3 to 15 carbon atoms which may be substituted with a halogen atom. An alkyl group or an alkoxyalkyl group) represented by the general formula (III) in the presence of a basic substance: (In the formula, X represents a halogen atom or a general formula —OSO ₂ R ″, wherein R ″ represents a lower alkyl group or an optionally substituted phenyl group. N represents an integer of 1 to 6.) Can be produced by condensation with an acetophenone represented by

In the above reaction, as the basic substance, sodium hydride, alkali metal hydride such as potassium hydroxide, lithium, sodium, alkali metal such as potassium, sodium ethylate, alkali metal alcoholate such as sodium methylate, sodium carbonate, Examples thereof include alkali metal carbonates such as potassium carbonate, butyl lithium and the like.

Such a basic substance is required to be at least 1 equivalent times the optically active alcohol (II), and the upper limit is not particularly limited, but is preferably 3 equivalent times. The equivalent ratio of the amounts of the optically active alcohols (II) and the acetophenones (III) to be used is 1: 5 to 5: 1, preferably 1: 3 to 3: 1. In response to the above reaction, the reaction temperature is usually -50 ° C to 12 ° C.
0 ° C, preferably in the range of -30 ° C to 100 ° C.

Examples of the reaction solvent include aliphatic or aromatic hydrocarbons such as tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chloroform, chlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, dimethylformamide, hexane, ethers, and halogenated hydrocarbons. A solvent inert to the reaction such as hydrogen is used alone or as a mixture, and the amount of the solvent is not particularly limited.

Further, a polar solvent such as dimethylsulfoxide, hexamethylphosphorylamide, N-methylpyrrolidone and the like can also be used.

After completion of the reaction, usual separation means such as extraction, liquid separation,
The desired novel ether derivative (I) can be obtained in good yield by an operation such as concentration, and this can be further purified by column chromatography or the like, if necessary.

Optically active alcohols used in the above reaction (II)
Is an optically active alkyl group R ^* having 3 to 15 carbon atoms which may be substituted with a halogen atom as exemplified below ^.
Is an alcohol having

3 carbon atoms which may be substituted by the above halogen atom
The following are examples of the optically active alkyl group R ^* of 1515. 1-methylethyl, 1-methylpropyl, 1
-Methylbutyl, 2-methylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,
2,2-trimethylbutyl, 1,2,3-trimethylbutyl, 2,
3,3-trimethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 1,2,2,3-tetramethylpentyl, 1-methylhexyl, 2-methylhexyl, 3
-Methylhexyl, 4-methylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1-methylheptyl, 2-methylheptyl, 3
-Methylheptyl, 4-methylheptyl, 5-methylheptyl, 1,3-dimethylheptyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl , 1,2-dimethyloctyl, 1,4-dimethyloctyl,
1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 1,2-dimethylnonyl, 1
-Methyldecyl, 2-methyldecyl, 3-methyldecyl, 4-methyldecyl, 5-methyldecyl, 6-methyldecyl, 7-methyldecyl, 8-methyldecyl, 1-methylundecyl, 9-methylundecyl, 1-methyldodecyl, 10- Methyl dodecyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl,
Methoxynonyl, methoxydecyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl,
Ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl, propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl, butoxyethyl, butoxypropyl , Butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl, butoxydecyl, pentyloxyethyl, pentyloxypropyl, pentyloxybutyl, pentyloxypentyl, pentyloxyhexyl, pentyloxyoctyl, pentyloxydecyl, hexyloxyethyl , Hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, Hexyl oxy hexyl, heptyloxy ethyl, heptyloxy propyl, heptyloxy butyl, heptyloxy pentyl, octyl oxyethyl, octyloxy propyl, decyl oxyethyl,
Decyloxypropyl, 2-trihalomethylpentyl,
2-trihalomethylhexyl, 2-trihalomethylheptyl, 2-halopropyl, 3-halo-2-methylpropyl, 2,3-dihalopropyl, 2-halobutyl, 3-halobutyl, 2,3-dihalobutyl, 2,4- Dihalobutyl, 3,4
-Dihalobutyl, 2-halo-3-methylbutyl, 2-halo-3,3-dimethylbutyl, 2-halopentyl, 3-halopentyl, 4-halopentyl, 2,4-dihalopentyl, 2,5-dihalopentyl, 2-halo- 3-methylpentyl, 2-halo-4-methylpentyl, 2-halo-3-
Monohalomethyl-4-methylpentyl, 2-halohexyl, 3-halohexyl, 4-halohexyl, 5-halohexyl, 2-haloheptyl, 2-halooctyl (provided that
The term "halo" in the above alkyl group means fluorine, chlorine, bromine or iodine, but fluorine or chlorine is preferred in practical use. )etc.

When the substituent R ^* in the general formula (II) is an optically active alkyl group containing a bromine or iodine atom, the acetophenones (III) generally include sulfates from the viewpoint of reaction yield. It is preferably used.

However, when the substituent R ^* is an optically active alkyl group containing a fluorine or chlorine atom, even if the acetophenones (III) are bromide or iodide, they can be used without any problem.

Some of these optically active alcohols (II) can be commercially available products, and are synthesized from the corresponding alcohols, carboxylic acids, amines, and the like through each step as necessary. It can be easily obtained by asymmetric metal catalysts, asymmetric reduction with microorganisms or enzymes. Others can be derived from optically active amino acids and optically active oxyacids as exemplified below, which are either naturally occurring or obtained by resolution.

Valine, leucine, isoleucine, phenylalanine, threonine, alosreonine, homoserine, alloisoleucine, tert-leucine, 2-aminobutyric acid, norvaline, norleucine, ornithine, lysine, hydroxylysine, phenylglycine, aspartic acid, glutamic acid, mandelic acid, tropha Acid, 3-hydroxybutyric acid, malic acid, oxalic acid, isopropylmalic acid and the like.

The other raw material, acetophenones (III), has the corresponding general formula (Wherein, n has the same meaning as described above).
It can be produced by converting to a sulfate using a sulfonyl chloride such as methanesulfonyl chloride or toluenesulfonyl chloride.

Here, the alcohol (IV) can be produced, for example, by a method represented by the following formula.

<Effect of the Invention> The above ether derivative (I) can be led to a novel liquid crystal compound (V) or (VI) by, for example, a method represented by the following formulas (1) and (2). It has very good properties.

(Here, Ar represents a phenylene group, a biphenylene group, a heterocyclic group, or the like, Y represents an alkyl group, an alkoxyl group, or the like. R ^* and n have the same meanings as described above.) Further, the ether derivative is an agricultural chemical. It can also be used as an intermediate for medicines and the like.

Further, according to the production method of the present invention, the ether derivative (I) can be produced industrially advantageously.

<Example> Hereinafter, the present invention will be described with reference to examples.

Example 1 In a four-necked flask equipped with a stirrer and a thermometer, 2.96 g (0.04 mol) of 2S-butanol and 15 m of dimethylformamide were placed.
l, cool to 5 ° C or less, and add 0.48 g of sodium hydride.
(0.02 mol) at the same temperature for 1 hour, and then at 20-25 ° C
For 2 hours. Next, 6.64 g (0.02 mol) of 3- (4-acetylphenyl) propyl tosylate was added at 20 to 25 ° C.
Over 1 hour. 2 hours at the same temperature, 30 more
Stirred at ~ 35 ° C for 3 hours. After completion of the reaction, the reaction solution was poured into ice water, extracted with 50 ml of toluene, and the organic layer was washed with water.
After drying over anhydrous magnesium sulfate, the solvent was distilled off. The concentrated residue was purified by column chromatography with toluene to obtain 3.04 g of 4- {3- (2S-butoxy) propyl} acetophenone (I-1).

▲ [α] ²⁰ _D ▼ + 7.5 ゜ (c = 1, CHCl ₃ ) ▲ n ²⁰ _D ▼
1.5123 Example 2 5.21 g (0.04 mol) of 2R-octanol, 15 ml of N-methylpyrrolidone and 3 ml of tetrahydrofuran were added, and
Cool to below ℃, sodium hydride 0.5g (0.025 mol)
Was added, and the mixture was stirred at the same temperature for 1 hour and further at 20 to 25 ° C for 2 hours. Next, 6.64 g (0.02 mol) of 3- (4-acetylphenyl) propyl tosylate was added at 20 ° C. or lower over 1 hour, and the mixture was stirred at the same temperature for 2 hours and further at 30 to 35 ° C. for 2 hours. . After the completion of the reaction, the reaction solution was poured into ice, extracted with 50 ml of toluene, and purified according to Example 1 to obtain 4- {3- (2R-octyloxy) propyl}.
3.48 g of acetophenone (I-2) was obtained.

▲ [α] ²⁰ _D ▼ -4.1 ゜ (c = 1, CHCl ₃ ) ▲ n ²⁰ _D ▼
1.5027 Examples 3 to 8 The reaction was carried out according to Example 1, except that the optically active alcohol (II) shown in Table 1 was used instead of 2R-butanol.
Work-up and purification gave the results shown in Table 1.

Example 9 In the same apparatus as in Example 1, 4.4 g of 2R-methylbutanol was added.
(0.05 mol) and dimethylformamide (20 ml)
Add 0.48 g (0.02 mol) of sodium hydride below,
The mixture was stirred at the same temperature for 1 hour and further at 20 to 25 ° C for 2 hours.
Next, 3- (4-acetylphenyl) propyl bromide
4.82 g (0.02 mol) was added at 15-20 ° C, and 2
Incubated for 1 hour at 35-45 ° C. After completion of the reaction, the reaction solution was poured into ice and extracted with 50 ml of toluene. Thereafter, purification was carried out according to Example 1 to give 4- {3- (2R-methylbutoxy) propyl} acetophenone (I-9) 1.84. g
I got

Example 10 3.52 g (0.04 mol) of 2R-methylbutanol and 15 ml of dimethylformamide were added, and then 0.48 g (0.02 mol) of sodium hydride was added at 5 ° C. or lower, and the same temperature was maintained for 1 hour.
Further, the temperature was kept at 20 to 25 ° C for 2 hours. Next, 2- (4-
6.36 g (0.02 mol) of acetylphenyl) ethyl tosylate was added at 20 ° C. or less, and at the same temperature for 1 hour,
The mixture was stirred at 3030 ° C. for 1 hour, and further at 20-30 ° C. for 1 hour.

After completion of the reaction, post-treatment and purification were conducted in the same manner as in Example 1 to obtain 1.36 g of 4- {2- (2S-methylbutoxy) ethyl} acetophenone (I-10).

▲ [α] ²⁰ _D ▼ + 4.6 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.5115 Example 11 2R-octanol 5.21 instead of 2S-methylbutanol
The reaction, work-up and purification were carried out according to Example 10, except for using g (0.04 mol), to give 4- {2- (2R-
Octyloxy) ethyl @ acetophenone (I-11) 1.
33 g were obtained.

▲ [α] ²⁰ _D ▼ -6.3 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.5051 Example 12 Example 10 except that 3.54 g (0.03 mol) of 2S-propoxypropanol was used instead of 2S-methylbutanol.
The reaction, work-up and purification according to
8.86 g of {2- (2R-propoxypropoxy) ethyl} acetophenone (I-12) was obtained.

▲ [α] ²⁰ _D ▼ + 4.8 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.5003 Example 13 4- (4-acetylphenyl) butyl tosylate instead of 3- (4-acetylphenyl) propyl tosylate
Except for using 6.93 g (0.02 mol), the reaction, post-treatment, and purification were conducted in the same manner as in Example 1 to obtain 3.13 g of 4- {4- (2S-butoxy) butyl} acetophenone (I-13).

▲ [α] ²⁰ _D ▼ + 9.1 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.5030 Examples 14 to 17 The reaction, post-treatment and purification were carried out according to Example 9, except that the optically active alcohol (II) shown in Table 2 was used instead of 2S-butanol, to obtain the results shown in Table 2. Was.

Reference Example 1 Production Example of Acetophenones (III) 84.0 g (0.63 mol) of aluminum chloride and 450 ml of dichloromethane were charged into a four-necked flask equipped with a stirrer and a thermometer, and 51.8 g (0.66 mol) of acetyl chloride was added at 10 to 15 ° C. Mol) was added over 2 hours. 10 hours after keeping at the same temperature for 1 hour
At 20 ° C., 53.4 g (0.3 mol) of 3-phenylpropyl acetate was added over 3 hours. After keeping the temperature at 25 ° C. for 4 hours, the reaction solution was poured into ice water, 100 ml of dichloromethane was added, the organic layer was separated, and washed sequentially with water, 3% aqueous sodium carbonate and water. The organic layer is dried over magnesium sulfate and concentrated under reduced pressure to give 4- (3-acetoxypropyl).
62.4 g of acetophenone (94.5% yield) was obtained.

55.0 g (0.25 mol) of 4- (3-acetoxypropylacetophenone) obtained here, 65 g of 10% potassium hydroxide, 20 ml of tetrahydrofuran and 60 ml of methanol were charged and stirred at room temperature for 5 hours. The organic layer was further washed with water and concentrated under reduced pressure to obtain 43.9 g (yield 98.5%) of 4- (3-hydroxypropyl) acetophenone.

Then: To a mixture of 17.8 g (0.1 mol) of 4- (3-hydroxypropyl) acetophenone obtained here and 50 ml of pyridine was added toluenesulfonyl chloride 2 at 10 ° C. or lower.
1.7 g (0.105 mol) was added dropwise over 2 hours. After keeping the temperature at the same temperature for 2 hours, the reaction solution was poured into ice water, made weakly acidic with 20% aqueous hydrochloric acid, and extracted with 100 ml of toluene. The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 32.7 g (yield 98.5%) of 3- (4-acetylphenyl) propyl tosylate.

Also: 4- (3-hydroxypropyl) previously obtained
17.8 g (0.1 mol) of acetophenone was dissolved in 7.91 g of pyridine and 70 ml of toluene, and phosphoric tribromide was dissolved at 0 to 10 ° C in a temperature of 27.1 g.
g (0.1 mol) was added. After keeping it at the same temperature for 3 hours,
The reaction solution was poured into ice water, washed with water, washed with 2% sodium bicarbonate, and washed with water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give 2- (4-acetylphenyl) propyl bromide 21.7%. g (90% yield) was obtained.

Hereinafter, instead of 3-phenylpropyl acetate, 4
-(4-acetylphenyl) butyl tosylate, 4- (4-acetylphenyl) butyl bromide and 2- (4-acetylphenyl) butyl tosylate were obtained by using -phenylbutyl acetate and 2-phenylethyl acetate, respectively. (4-Acetylphenyl) ethyl tosylate and 2- (4-acetylphenyl) ethyl bromide were obtained.

Reference Example 2 Production Example of Liquid Crystal Compound (V) Example of a four-necked flask equipped with a stirrer and thermometer
2.34 g (0.01 mol) of (I-10) obtained in Step 10 and 20 ml of dichloromethane were charged and reacted at 20 to 30 ° C for 24 hours.

The reaction solution is washed with 3% sodium carbonate, further washed with water, concentrated, and the concentrated residue is purified by column chromatography with toluene to give 4- {2- (2S-methylbutoxy).
2.25 g of ethyl diphenylacetate (VII-1) (yield 90
%).

▲ [α] ²⁰ _D ▼ + 3.8 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.4982 Next, 1.25 g (5 mmol) of (VII-1) obtained here,
1.5 g (7.5 mmol) of 20% caustic soda and methanol 5
Then, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, methanol was distilled off, the mixture was made weakly acidic with 2N-hydrochloric acid aqueous solution, extracted with 20 ml of ethyl acetate, and the organic layer was washed with water and concentrated under reduced pressure. The concentrated residue was purified by chromatography with toluene: ethyl acetate = 5: 1 to give 0.92 g of 4- {2- (2S-methylbutoxy) ethyl} phenol (VIII-1) (yield: 96).
%).

▲ [α] ²⁰ _D ▼ + 6.1 ゜ (c = 1, CHCl ₃ ) 、 ▲ n ²⁰ _D ▼
1.5130 Next, 0.52 g (2.5 mmol) of (VIII-1) obtained here, 0.84 g (3 mmol) of 4-decyloxybenzoic acid
And 15 ml of anhydrous dichloromethane, and 0.61 g (3 mmol) of N, N'-dicyclohexylcarbodiimide and 50 mg of 4-pyrrolidinopyridine were added thereto, followed by stirring at room temperature for 24 hours.

After the completion of the reaction, the resulting precipitate was separated and diluted with 200 ml of toluene. The organic layer was formed of water, 5% acetic acid aqueous solution, water, 5% aqueous sodium bicarbonate solution,
After washing with water in that order, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-ethyl acetate) to give (+)-4-decyloxybenzoic acid 4- [2
1.05 g (90% yield) of-{2 (s) -methylbutoxy} ethyl] phenyl ester was obtained.

▲ [α] ²⁰ _D ▼ + 2.5 ゜ (c = 1, CHCl ₃ ) Phase series (℃) Reference Example 3 Production Example of Liquid Crystal Compound (VI) Example of a four-necked flask equipped with a stirrer and thermometer
2.34 g (0.01 mol) of (I-10) obtained in Step 10 was previously
11 g (0.07 mol) of bromine was added to 16 g of 0% caustic soda water, and 30 ml of dioxane was further added to the mixed solution at room temperature.
Stirred for hours. After the reaction is completed, pour the reaction solution into ice water and add 10%
The mixture was made weakly acidic with sulfuric acid, extracted with 100 ml of ethyl acetate, the organic layer was separated, washed with water and concentrated. The concentrated residue was purified by chromatography with toluene-acetic acid (20: 1) to give 4- ｛. 2.1 g (yield 90%) of 2- (2S-methylbutoxy) ethyl dibenzoic acid (IX-1) was obtained.

{[Α] ²⁰ _D ▼ + 6.1} (c = 1, CHCl ₃ ) Melting point 60-62 ° C. Then, 1.18 g (5 mmol) of (IX-1) obtained above, 4-
1.96 g of decyloxy-4'-hydroxybiphenyl (6
Mol)) and 30 ml of dichloromethane.
-Dicyclohexylcarbodiimide (1.22 g, 6 mol) and 4-pyrrolidinopyridine (0.1 g) were added, and the mixture was stirred at room temperature for 24 hours.

After the completion of the reaction, the resulting precipitate was separated and diluted with 200 ml of toluene. The organic layer was formed of water, 5% acetic acid aqueous solution, water, 5% aqueous sodium bicarbonate solution,
After washing with water in that order, the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent; toluene-ethyl acetate) to give (+)-4- {2- (2s-methylbutoxy).
2.47 g (yield 90.5%) of ethyl 4-benzoyl oxybiphenylyl benzoate was obtained.

▲ [α] ²⁰ _D ▼ + 2.8 ゜ (c = 1, CHCl ₃ ) Phase series (℃)

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09K 19/46 C09K 19/46 (72) Inventor Masayoshi Minami 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical (72) Inventor Kiyoshi Imamura 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd.

Claims (2)

(57) [Claims] (1) General formula (In the formula, R ^* represents an optically active alkyl group or an alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom, and n represents an integer of 1 to 6.) . 2. An optical system represented by the general formula R ^* -OH (wherein R ^* represents an optically active alkyl group or alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom). Active alcohols can be converted to a compound of the general formula in the presence of a basic substance. (In the formula, X represents a halogen atom or a general formula —OSO ₂ R ″, wherein R ″ represents a lower alkyl group or an optionally substituted phenyl group. N represents an integer of 1 to 6.) 3. The method for producing an ether derivative according to claim 1, wherein the method is condensed with an acetophenone represented by the formula: