JP3146508B2 - Optically active compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel optically active compound and a method for producing the same. More specifically, a liquid crystal composition,
In particular, the present invention relates to a novel optically active ester derivative useful as an intermediate used for producing a ferroelectric liquid crystal composition and a method for producing the same.

[0002]

2. Description of the Related Art Since liquid crystal compounds have been used in electro-optical display devices, a large number of liquid crystal compounds have been synthesized, and nematic liquid crystals or nematic-cholesteric liquid crystals have been produced using STN.
It is widely used for a display device of the type, a nematic-cholesteric phase transition type display device, a display device utilizing the guest-host effect, and the like. Since the response speed of these display elements is at most on the order of several milliseconds, it has been considered that the response range of the liquid crystal display element is limited. However, in recent years, it has been found that when a ferroelectric liquid crystal is used, a high-speed response on the order of μsec can be obtained.

[0003] In 1975, an example of a conventionally known ferroelectric liquid crystal is disclosed in R.A. B. 4- (4-n-decyloxybenzylideneamino) cinnamic acid-2-methylbutyl ester synthesized by Meyer et al.
BAMBC). This material is characterized by exhibiting ferroelectricity in its chiral smectic C phase [J. Physique. , 36 , 69 (197
5)]. Also, in 1980, N. A. Clark et al. In a thin film cell using DOBAMBC
A high-speed response of the order can be obtained [A
ppl. Phys. Let. , 36 , 89 (198
0)].

[0004] However, despite the fact that many studies on the synthesis of ferroelectric liquid crystals have been made, no ferroelectric liquid crystal compound satisfying all the physical properties with a single compound has been found yet. At present, it is necessary to use a composition combining several types of ferroelectric liquid crystal compounds in order to satisfy all physical properties.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel optically active ester derivative which is useful as an intermediate used for producing a liquid crystal composition satisfying such requirements. Another object is to provide a method for easily producing the ester derivative.

[0006]

According to the present invention, there is provided a compound represented by the following general formula (1):

[0007]

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An optically active compound represented by the general formula (2):

[0009]

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An optically active compound represented by the general formula (3):

[0011]

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A compound represented by the general formula (4):

[0013]

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[0014] The present invention relates to a method for producing the above-mentioned optically active compound, which comprises esterifying with a fatty acid ester of p-hydroxyphenylethanol represented by the formula (1), followed by deacetoxylation.

Hereinafter, the present invention will be described in detail.

The optically active ester derivative of the present invention represented by the general formula (1) is, as specifically shown in Examples described later,
For example, it is produced by the following step (see Chemical formula 9).

That is, first, the general formula (5):

[0018]

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Phosphorus oxychloride, dimethylformamide, and then magnesium perchlorate are allowed to act on p-methoxyphenylacetic acid represented by the general formula (6):

[0020]

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The compound represented by the formula is obtained. Then, p-ethyloxycarbonylbenzamidine hydrochloride is allowed to act on (Chemical Formula 6) under basic conditions to obtain a compound of the general formula (7):

[0022]

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The compound represented by the formula is obtained. Further,
Is treated with aqueous hydrogen bromide and acetic acid to obtain a compound of the general formula (8):

[0024]

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The compound represented by the formula is obtained. Then, the hydroxyl group of (Chemical Formula 8) is protected, but it is better to protect it with an acetyl group because the deprotection group reaction described later is easy.
Usually, the hydroxyl group is acetylated with acetic anhydride to obtain a compound represented by the general formula (3).

The thus-obtained (Chemical Formula 3) is obtained by combining the optically active fatty acid ester of p-hydroxyphenylethanol represented by the general formula (4) with the DCC method,
By performing an esterification reaction by a known method such as an acid chloride method, an optically active ester derivative (Formula 2) represented by the general formula (2) can be obtained. In addition,
Is an optically active ester derivative having a hydroxyl group represented by the general formula (1) by removing a protecting group (acetyl group) by reacting with benzylamine or the like.
Get.

[0027]

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As a step other than the above reaction step (Chem. 9), the following step (Chem. 15) can be exemplified.

First, the general formula (10):

[0030]

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The compound represented by the general formula (11) is reacted with phosphorus oxychloride, dimethylformamide, and then magnesium perchlorate to obtain a compound represented by the general formula (11):

[0032]

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The compound represented by the formula is obtained. Then, (Chemical 1
1) p-ethyloxycarbonylbenzamidine hydrochloride is allowed to act on the compound under basic conditions to obtain a compound of the general formula (12):

[0034]

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The compound represented by the formula is obtained. Furthermore, (Chemical 1
2) is hydrolyzed with potassium hydroxide in ethanol to give a compound of the general formula (13):

[0036]

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The compound represented by the formula is obtained. And (Chemical 1
3) is obtained by subjecting (Chemical Formula 4) to an esterification reaction by a known method such as a DCC method or an acid chloride method to obtain a compound of the general formula (14):

[0038]

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The compound represented by the formula: Finally, a deprotection group reaction is performed by reacting palladium / carbon on (Chem. 14) to obtain an optically active ester derivative (Chem. 1) having a hydroxyl group represented by the general formula (1).

[0040]

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The above optically active compound {fatty acid ester of p-hydroxyphenylethanol, (Chem. 4)}
Is a fatty acid ester of racemic 1- {4- (1-ethoxyethoxy) phenyl} ethanol and 2,2,2-trichloroethanol (having 2 to 16 carbon atoms in the fatty acid) or a compound represented by the general formula (16): H _The vinyl ester represented by 2C = CR ² OCOR ¹ (wherein R ¹ is the same as above and R ² represents a hydrogen atom or a methyl group) cannot be synthesized using an enzyme having esterase activity in an organic solvent. It is obtained by removing the 1-ethoxyethoxy group after asymmetric transesterification (see JP-A-2-262536).

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 5- (hydroxyphenyl) -2-[[4 '-{1 ""
Synthesis of-(decanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine

(First stage) 81.8 g (1.1 mmol) of dimethylformamide
Then, 102.6 (0.67 mmol) of phosphorus oxychloride was added dropwise at 0 ° C., and 66 g of p-methoxyphenylacetic acid was added.
At a temperature of -10C. The mixture was stirred at 20 ° C. for 1 hour, 60 ° C. for 2 hours, and 80 ° C. for 5 hours. Dimethylformamide was distilled off under reduced pressure, and the residue was cooled and poured into a saturated aqueous solution of magnesium perchlorate. The precipitated crystals were separated by filtration and washed with ether to obtain 61 g of a perchlorate (yield: 81.2%).

23.9 g (72 mmol) of this salt and p-
Ethoxycarbonylbenzamidine hydrochloride was refluxed for 8 hours in 250 ml of ethanol in the presence of 14.8 g (0.2 mol) of sodium ethylate.

After completion of the reaction, ethanol was distilled off under reduced pressure, and 500 ml of an aqueous solution containing 18 g (0.3 mol) of acetic acid was added and stirred. The precipitate was separated by filtration, washed with water and dried to obtain 15.2 g (yield 63%) of 5- (methoxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine.

(Second stage) A mixture of 7.6 g (23 mmol) of 5- (methoxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine, 50 g of hydrobromic acid and 100 ml of acetic acid was used for 60 hours. Refluxed. Most of the acetic acid was distilled off under reduced pressure, and then water was added. The precipitate was sufficiently washed with water and dried to obtain 7.1 g of 5- (hydroxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine (yield: 99%).

(Third Stage) 5- (Hydroxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine 31 g (106 mmol), pyridine 310 ml, acetic anhydride 38 g (35 g)
(0 mmol) was reacted at 70 ° C. for 10 hours, and 100 ml of ice water was added. The deposited precipitate is separated by filtration,
After washing with water and drying, 5- (acetyloxyphenyl) -2-
32 g (yield 90%) of [4- (1-ethoxycarbonyl) phenyl] pyrimidine was obtained. 32 g (95 mmol) of the obtained 5- (acetyloxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine
Was suspended in 100 ml of thionyl chloride and heated under reflux for 15 hours, and then excess thionyl chloride was distilled off under reduced pressure. Without isolating the acid chloride, 80 ml of pyridine was added, and 35 g (120 mmol) of decanoic acid ester of (S) -1- (p-hydroxyphenyl) ethanol was further added and reacted for 5 hours. After adding 300 ml of chloroform to the reaction mixture and washing with a 5% aqueous hydrochloric acid solution, water and a 10% aqueous sodium carbonate solution, the organic layer was dried over magnesium sulfate, and 10.4 g (150 mmol) of benzylamine was added. The mixture was stirred at room temperature for 20 hours to perform deacetoxylation. After concentrating the reaction mixture, silica gel chromatography (CH ₃
The mixture was purified with Cl: acetone = 15: 1) to give 44 g of 5- (hydroxyphenyl) -2-[[4 ′-{1 ″-(decanoyloxy) ethyl} phenyloxycarbonyl] phenyl] pyrimidine (yield: 82). %).

The obtained 5- (hydroxyphenyl) -2
-[[4 '-{1 "-(decanoyloxy) ethyl}
The analysis results of the specific rotation and NMR spectrum of phenyloxycarbonyl] phenyl] pyrimidine were as follows.

Specific rotation: [α] ²⁰ _D = −32.8 ° (c
= 1.0, CHCl ₃ )

¹ H-NMR (300 MHz, δ value pp
_{m, CDCl 3): 0.85 (} t, 3H), 1.23
(Br.s, 12H), 1.49 (d, 3H), 1.5
8 (m, 2H), 2.27 (t, 2H), 5.82
(M, 1H), 6.62 (br.s, 2H), 6.98
(D, 2H), 7.20 (d, 2H), 7.49 (d,
2H), 7.67 (d, 2H), 8.14 (d, 2
H), 8.52 (d, 2H), 8.97 (s, 2H)

Example 2 5- (hydroxyphenyl) -2-[[4 ′-{1 ″ ”
Synthesis of-(butanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine

(S) -1- (p-hydroxyphenyl)
Instead of decanoate of ethanol, (S) -1-
The same operation as in Example 1 was carried out except that butanoic acid ester of (p-hydroxyphenyl) ethanol was used.
5- (hydroxyphenyl) -2-[[4 ′-{1 ″ ”
-(Butanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine 38.5 g (84% yield)
I got

The obtained 5- (hydroxyphenyl) -2
-[[4 '-{1 "-(butanoyloxy) ethyl}
The analysis results of the specific rotation and NMR spectrum of phenyloxycarbonyl] phenyl] pyrimidine were as follows.

Specific rotation: [α] ²⁰ _D = −50.7 ° (c
= 1.0, CHCl ₃ )

¹ H-NMR (300 MHz, δ value pp
m, CDCl ₃ ): 0.91 (t, 3H), 1.54
(D, 3H), 1.62 (m, 2H), 2.26 (t,
2H), 5.83 (m, 1H), 6.70 (br.s,
1H), 6.98 (d, 2H), 7.20 (d, 2
H), 7.49 (d, 2H), 7.67 (d, 2H),
8.14 (d, 2H), 8.52 (d, 2H), 8.9
7 (s, 2H)

Example 3 5- (hydroxyphenyl) -2-[[4 ′-{1 ″ ”
Synthesis of-(decanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine

(First stage) 81.6 g (1.1 mmol) of dimethylformamide
Then, 102.6 (0.67 mmol) of phosphorus oxychloride was added dropwise at 0 ° C., and 66 g (290 mmol) of p-benzyloxyphenylacetic acid was added little by little at a temperature of −10 ° C. The mixture was stirred at 20 ° C. for 1 hour, 60 ° C. for 2 hours, and 80 ° C. for 5 hours. Dimethylformamide was distilled off under reduced pressure, and the residue was cooled and poured into a saturated aqueous solution of magnesium perchlorate. The precipitated crystals were collected by filtration and washed with ether to obtain 61 g of perchlorate (yield: 52%).

23.9 g (58.5 mmol) of this salt and p-ethoxycarbonylbenzamidine hydrochloride were added for 8 hours in 250 ml of ethanol in the presence of 14.8 g (64.7 mmol) of sodium ethylate. Heated to reflux.

After completion of the reaction, ethanol was distilled off under reduced pressure, and 500 ml of an aqueous solution containing 18 g (0.3 mol) of acetic acid was added and stirred. The precipitate was collected by filtration, washed with water and dried, and then 15.2 g of 5- (benzyloxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine (yield 63.
4%).

(Second stage) 7.6 g of 5- (benzyloxyphenyl) -2- [4- (1-ethoxycarbonyl) phenyl] pyrimidine (1
(8.5 mmol) A mixture of 500 ml of ethanol containing 1 N potassium hydroxide was refluxed for 10 hours. After completion of the reaction, most of the ethanol was distilled off under reduced pressure, and then water was added. The precipitate was sufficiently washed with water and dried to obtain 15.2 g of 5- (benzyloxyphenyl) -2- [4- (1-carboxy) phenyl] pyrimidine (yield: 99%).

(Third stage) 31 g (81.2 mmol) of 5- (benzyloxyphenyl) -2- [4- (1-carboxy) phenyl] pyrimidine was suspended in 100 ml of thionyl chloride, and the mixture was heated under reflux for 15 hours. The excess thionyl chloride was distilled off under reduced pressure. Add 80 ml of pyridine without isolating the acid chloride,
Further, 35 g (120 mmol) of decanoic acid ester of (S) -1- (p-hydroxyphenyl) ethanol was added, and the mixture was reacted for 5 hours. 300 m chloroform in the reaction mixture
After washing with 5% aqueous hydrochloric acid, water and 10% aqueous sodium carbonate, the organic layer was dried over magnesium sulfate, concentrated, dissolved in 500 ml of tetrahydrofuran, 3 g of 5% palladium-carbon was added, and the mixture was added under a stream of hydrogen. The mixture was stirred for 20 hours and debenzylated by catalytic hydrogenation. The reaction mixture was filtered and concentrated, and then purified by silica gel chromatography (CH ₃ Cl: acetone = 15: 1).
(Hydroxyphenyl) -2-[[4 ′-{1 ″-
42.3 g (92% yield) of (decanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine were obtained.

The obtained 5- (hydroxyphenyl) -2
-[[4 '-{1 "-(decanoyloxy) ethyl}
The analysis results of the specific rotation and the NMR spectrum of phenyloxycarbonyl] phenyl] pyrimidine were the same as those in Example 1.

Example 4 5- (hydroxyphenyl) -2-[[4 '-{1 ""
Synthesis of-(butanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine

(S) -1- (p-hydroxyphenyl)
Instead of decanoate of ethanol, (S) -1-
The same operation as in Example 3 was carried out except that butanoic acid ester of (p-hydroxyphenyl) ethanol was used.
5- (hydroxyphenyl) -2-[[4 ′-{1 ″ ”
-(Butanoyloxy) ethyl {phenyloxycarbonyl] phenyl] pyrimidine 34.9 g (89% yield)
I got

The obtained 5- (hydroxyphenyl) -2
-[[4 '-{1 "-(butanoyloxy) ethyl}
The analysis results of the specific rotation and NMR spectrum of phenyloxycarbonyl] phenyl] pyrimidine were the same as those in Example 3.

[0066]

Industrial Applicability The ester derivative of the present invention is useful as an intermediate used for producing a liquid crystal composition, particularly a ferroelectric liquid crystal composition.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 239/26 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. General formula (1): An optically active compound represented by the formula: 2. General formula (2): An optically active compound represented by the formula: 3. A compound of the general formula (3): A compound represented by the general formula (4): 2. The method for producing an optically active compound according to claim 1, wherein the esterification is carried out by esterification with an optically active fatty acid ester of p-hydroxyphenylethanol represented by the formula: