JPH05140144A - New alcohol and its production and new ester and production of rooting induction substance of carrots from new alcohol - Google Patents

Abstract

PURPOSE:To obtain a new alcohol useful as a starting raw material of (4R,5R)-5- hydroxy-6-phenyl-4-hexanoride which is a rooting induction substance of carrots. CONSTITUTION:(4R,5R)-3-(2,2-Dimethyl-5-phenylmethyl-1,3-dioxolane-4-yl) propane-1-ol of formula II. The compound of formula I is obtained by reducing a compound of formula II to afford a compound of formula III, then lactonating only racemic modification of the compound of formula III using lipase, protecting primary OH with a protecting group and further epoxydizing the group, subjecting the epoxy group to reductive ring opening reaction to form acetonide and subjecting only protecting group of primary OH to selective desilylation or by passing from a compound of formula IV through a new compound of formula V and finally hydrolyzing the compound of formula V with an alkali.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alcohol, a novel ester thereof, a method for producing them, and a method for producing a root-inducing substance for carrots from the novel alcohol. (4R, 5R) -5-Hydroxy-6-phenyl-4-hexanolide, which is a root-inducing substance for carrots, can be conveniently prepared by providing a production method capable of producing this alcohol with high purity and its ester. And to synthesize in good yield.

[0002]

BACKGROUND OF THE INVENTION In recent years, various plant physiologically active substances such as plant hormones, plant growth regulators and growth inhibitors have been found, and their industrial use is progressing. For example, 19
Gibberellin, which was discovered in 38 as a growth promoting substance for higher plants in a product of the rice scabbard disease pathogen (Gibberella fujikuroi) , was subsequently studied, and in addition to the elongation effect of plant cells, gibberellin was used to break dormancy of seeds and buds. It has been found that there are actions such as promotion of flowering, priority of apical shoots, and prevention of aging, and these actions are widely used for the purpose of increasing the yield and improving the quality of agricultural products. In addition, application of plant hormones to biotechnology has come to be attempted, and along with the progress of biotechnology, cultivation of plant cells and plant tissues has been industrially carried out, and in the differentiation of these cultured plants,
Plant bioactive substances play an important role.

[0003]

[ Prior Art] Carrot ( Allium tuberosum ROTTLER )
The rooting of the lateral roots of the genus is the carrot ( Allium tuber
osum ROTTLER ). For this reason,
A major issue is how to induce the rooting of these lateral roots.In 1989, Sims et al. Found carrots ( Allium tuberosum ROTTLER ) and turnips found in Erwinia quercina culture medium. (Brassica campes
The structure of lateral rooting inducers such as tris L.) and beet (Beta vulgaris L.) was determined to be 5-hydroxy-6-phenyl-4-hexanolide. (AEWright, M.Schafer, SM
idlond, DEMunnecke and JJSims, Tetrahedron Let
t., 30 , 5699 (1989)). Furthermore, this 5-hydroxy-6-
Four stereoisomers of phenyl-4-hexanolide have been synthesized, and the non-natural (4R, 5R) form has the highest root-inducing activity of lateral roots such as carrot ( Allium tuberosum ROTTLER ). Was found.

[0004]

[Problems to be Solved by the Invention] However, this Si
The synthetic method found by ms et al. is insufficient for practical industrial use due to the yield and the number of steps, and in particular, only the (4R, 5R) form with the highest root-inducing activity can be easily obtained. It was not a possible manufacturing method.

[0005]

[Means for Solving the Problems] In view of the above problems, the present inventors have conducted diligent research, and as a result, have found that a new alcohol (4R, 5
R) -3- (2,2-Dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol and new ester (4R, 5R) -3- (2,2-dimethyl- 5-phenylmethyl-1,3
By providing -dioxolan-4-yl) propyl 3,5-dinitrobenzoate, the above-mentioned problems are alleviated and the root-inducing substance (4R, 5R) -5-hydroxy-6 of carrots is eliminated.
The inventors have found that phenyl-4-hexanolide can be easily obtained in high yield, and completed the present invention.

[0006]

The structure of the present invention will be described below. Novel alcohol represented by the general formula 12 (Chemical formula 12) according to the present invention
(4R, 5R) -3- (2,2-Dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol is a colorless, transparent and viscous oily substance.

[Chemical 12]

This new alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl)
The method for producing propan-1-ol will be described below.

New alcohol (4R, 5R) -3- (2,2-dimethyl
As a starting material for producing -5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol, a compound of the general formula
Methyl 4-oxo-6-phenyl-5-hexinoate represented by the formula 13 is used.

[Chemical 13]

This methyl 4-oxo-6-phenyl-5
-Hexinoate is synthesized by conventional methods,
Specifically, it is easily synthesized by the method disclosed in Japanese Patent Laid-Open No. 63-156754 disclosed by the applicant.

First, methyl 4-oxo- which is a starting material
By reducing 6-phenyl-5-hexinoate, a compound of the general formula 14
Methyl 4-hydroxy-6-phenyl-5-hexinoate represented by the formula:

[Chemical 14]

The reducing agent used is one that does not reduce the ester portion but only the ketone portion, and sodium borohydride is particularly preferably used. As the solvent, alcohol solvents such as methanol, ethanol, propanol and butanol are preferably used.

Then, this methyl 4-hydroxy-6-
Only the (R) form of phenyl-5-hexinoate is lactonized to form (R) -6-phenyl represented by the general formula 15
-5-hexyne-4-olide.

[Chemical 15]

This lactonization can be carried out by hydrolyzing the ester and then using an acid catalyst, but in the present invention, it is carried out using lipase. As described above, lactonization in an organic solvent using lipase can lactonize only the (R) form. Various types of lipase are used, and in this reaction, porcine pancreas-derived lipase is particularly preferably used. The porcine pancreas-derived lipase is not particularly limited whether it is a purified product or a crude enzyme product.

The organic solvent used in this reaction is not particularly limited, but it is a hydrocarbon solvent such as heptane or octane, an aromatic solvent such as toluene, benzene or xylene, or an ether solvent such as diethyl ether or isopropyl ether. A solvent or the like is preferably used.

The obtained (R) -6-phenyl-5-hexyne-4-
Oleide is converted again to the above-described methyl 4-hydroxy-6-phenyl-5-hexinoate without degrading the optical purity by, for example, a methanolysis reaction using a methanol / triethylamine solution. By further lactonizing this methyl 4-hydroxy-6-phenyl-5-hexinoate with lipase, (R) -6-phenyl-5-hexyne with higher optical purity is obtained.
-4-Olide can be adjusted. In the present invention, this operation is repeated about twice to obtain an optical purity
97% ee of (R) -6-phenyl-5-hexyne-4-olide.

The obtained (R) -6-phenyl-5-hexyne-4-
Olide is then reduced with lithium aluminum hydride or the like, and only the primary hydroxyl group is protected with t-butyldimethylsilyl chloride to give a compound represented by the general formula 16:
Is represented by (R, Z) -6-t-butyldimethylsilyloxy-1-phenyl-1-hexen-3-ol.

[Chemical 16]

The obtained (R, Z) -6-t-butyldimethylsilyloxy-1-phenyl-1-hexen-3-ol was further oxidized to the epoxy group at the double bond portion to give a compound of the general formula 17 (3R) -6-t-butyldimethylsilyloxy-1,2-epoxy-1-phenylhexan-3-ol shown in 17).

[Chemical 17]

The oxidation method is not particularly limited, and examples include metachloroperbenzoic acid, monomagnesium monoperphthalate, vanadium oxide acetylacetonate, and t-peroxide.
It is carried out by Sharpless oxidation using butyl or the like, and more preferably, the use of monomagnesium monoperphthalate is suitably selected in terms of yield, productivity and the like. As the solvent used in this reaction, an alcohol-water mixed solvent system is used, and an isopropyl alcohol-water system is particularly preferably used.

The thus obtained (3R) -6-t-butyldimethylsilyloxy-1,2-epoxy-1-phenylhexan-3-ol is then reductively opened to give a compound of the general formula 18 ( Conversion 1
8) (2R, 3R) -6-t-butyldimethylsilyloxy-
It is 1-phenylhexane-2,3-diol.

[Chemical 18]

This reduction is not particularly limited, and can be performed by a known reduction method such as hydrogenation, and can be suitably performed in a hydrogen atmosphere using palladium carbon in an ethanol solution, for example.

(2R, 3R) -6-t-butyldimethylsilyloxy-1
-Phenylhexane-2,3-diol is then acetonide-protected by protecting the diol moiety to give (4R, 5R) -1-t-butyldimethylsilyloxy-3- ( 2,
2-dimethyl-5-phenylmethyl-1,3-dioxolane-4-
Il) Propane.

[Chemical 19]

This reaction is carried out, for example, by reacting 2,2-dimesoxypropane in the presence of an acid catalyst for 1 to 12 hours.

The obtained (4R, 5R) -1-t-butyldimethylsilyloxy-3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propane is then of primary A new alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3 represented by general formula 20 by selective desilylation of
-Dioxolan-4-yl) propan-1-ol.

[Chemical 20]

The selective desilylation used in this reaction is preferably carried out under the condition that only the silyl ether moiety is decomposed without decomposing acetonide, for example, by reacting with tetrabutylammonium fluoride in terorahydroxyfuran. Be seen. Thus, the novel alcohol (4R, 5R) -3- (2,2-dimethyl-5) according to the present invention is
-Phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol is methyl 4-oxo-6-phenyl-5
It can be easily produced using hexinoate as a starting material.

Further, the novel alcohol thus obtained
A mixture containing (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol and its derivatives is further represented by the general formula 21 After reacting with the 3,5-dinitrobenzoic acid chloride shown in 21) for 0.5 to 12 hours to obtain the 3,5-dinitrobenzoic acid ester shown in the general formula 22 (Chemical Formula 22), it is treated with a polar solvent and nonpolar. A new alcohol (4R, 5R)-with higher optical purity is obtained by recrystallization from a mixed solvent with a solvent and hydrolysis with an alkali.
It can be 3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol.

[Chemical 21]

[Chemical 22]

This recrystallization is carried out in a mixed solvent of a polar solvent and a nonpolar solvent, and examples of the polar solvent include ether, tetrahydroxyfuran, ethyl acetate, methanol, ethanol, chloroform and methylene chloride.
Non-polar solvents include hexane, pentane, benzene,
Toluene and the like are preferably used, but are not particularly limited.

By repeating this recrystallization, a new alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl
The optical purity and chemical purity of -1,3-dioxolan-4-yl) propan-1-ol can be improved. As a specific example, 100% of a mixture having an optical purity of 97% ee can be obtained by recrystallization using, for example, hexane / ethyl acetate.
It can be ee's new alcohol.

Next, the novel ester according to the present invention will be described. The novel ester according to the present invention is represented by the general formula 23 (Chemical formula 23): (4R, 5R) -3- (2,2-dimethyl-5-
Phenylmethyl-1,3-dioxolan-4-yl) propyl-
It is 3,5-dinitrobenzoate.

[Chemical 23]

The novel ester (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propyl-3,5-dinitrobenzoate has the general formula
The new alcohol (4R, 5R) -3- (2,2-
Starting from dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol as a starting material, a compound of the general formula 25
3,5-dinitrobenzoic acid chloride represented by the formula
It is easily produced by reacting for about 12 hours.
The obtained novel ester is easily obtained as a novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-) with high optical purity.
1,3-dioxolan-4-yl) propan-1-ol, and a root-inducing substance for carrots can be produced in an extremely short process.

[Chemical 24]

[Chemical 25]

Next, a method for producing a root-inducing substance for carrots according to the present invention will be described. In the present invention, the novel alcohol (4R,
5R) -3- (2,2-Dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol is used as a starting material, and the carrots of the general formula 27 A rooting inducer (4R, 5R) -5-hydroxy-6-phenyl-4-hexanolide is produced in an extremely short process.

[Chemical 26]

[Chemical 27]

First, a novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol is oxidized to the primary hydroxyl group to give a general compound. A carboxylic acid represented by the formula 28 (Chemical Formula 28), which is a deprotection group (acetonide moiety) and lactonized with an acid catalyst to be a root-inducing substance for carrots (4R, 5R)-
5-hydroxy-6-phenyl-4-hexanolide is obtained.

[Chemical 28]

[0032]

As described in detail above, the present invention provides a novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,
3-Dioxolan-4-yl) propan-1-ol and new ester (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propyl 3,5 -Dinitrobenzoate and new alcohol (4R, 5R) -3- (2,
2-Dimethyl-5-phenylmethyl-1,3-dioxolane-4-
(4R, 5R) -5-Hydroxy-6-phenyl-4, a carrot root-inducing substance characterized by oxidizing propane-1-ol to carboxylic acid and then lactonizing it with an acidic catalyst. Since it is a method for producing hexanolide, it exhibits an excellent effect that a root-inducing substance for lateral roots, which plays a major role in the growth of carrots, can be synthesized very simply and in high yield.

[0033]

The present invention will be described in more detail below with reference to examples. The present invention is not limited to this embodiment.

Example 1 (1) Methyl 4-hydroxy-6-phenyl-5-hexyl
Synthesis of sinoate . To a methanol solution of 6 g of methyl 4-oxo-6-phenyl-5-hexinoate was added 564 mg of sodium borohydride under ice cooling, and the mixture was reacted at room temperature for 1 hour. After adding 200 ml of phosphate buffer to this reaction solution, extraction with ether was performed, and the ether layer was dried, concentrated, and purified by silica gel column chromatography to obtain methyl 4-hydroxy-6.
5.20 g (yield 86%) of -phenyl-5-hexinoate was obtained.

(2) (R) -6-phenyl-5-hexyne-4-o
Ride synthesis. 5.0 g of methyl 4-hydroxy-6-phenyl-5-hexinoate and 2.5 g of lipase derived from pig pancreas were reacted in ether at room temperature for 48 hours. After completion of this reaction, it is filtered, concentrated, and subjected to silica gel chromatography (R)-
Separation of 6-phenyl-5-hexyne-4-olide and unreacted product, (R) -6-phenyl-5-hexyne-4-olide 1.78 g
(Yield 42%) was obtained. This (R) -6-phenyl-5-hexyne
-4-Oleide was converted into methyl 4-hydroxy-6-phenyl-5-hexinoate again with a methanol / triethylamine solution, and similarly reacted with lipase to obtain (R) -6-phenyl-5- with an optical purity of 97% ee. Hexin-4-olide was used.

(3) (R, Z) -6-t-butyldimethyl silyloxy
Synthesis of cy-1-phenyl-1-hexen-3-ol. (R) -6-Phenyl-5-hexyne-4-olide (4.70 g) was mixed with lithium aluminum hydride (1.9 g) in tetrahydrofuran and refluxed for 20 hours under an argon atmosphere. After cooling, 100 g of water and 2N sulfuric acid were added, the mixture was extracted with ether, and the ether layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and sodium chloride. The solution was dried, concentrated, and then purified by silica gel column chromatography to obtain 3.9 g of diol (yield 81%). Dissolve this in dimethylformamide,
Under ice cooling, 2.65 g of imidazole and 2.8 g of t-butyldimethylsilyl chloride were added, and after reacting for 1 hour, water was added,
It was extracted with ether. After drying, concentration, and purification by column chromatography, 5.0 g of (R, E) -6-t-butyldimethylsilyloxy-1-phenyl-1-hexen-3-ol (yield 66%) was obtained.

(4) (3R) -6-t-butyldimethyl silyloki
Compound of Si-1,2-epoxy-1-phenylhexan-3-ol
Success. (R, E) -6-t-Butyldimethylsilyloxy-1-phenyl-1-
Hexen-3-all 2.76 g in isopropyl alcohol /
It was dissolved in water (45 ml / 35 ml), 7.37 g of monomagnesium monoperphthalate salt was added, and the reaction was carried out at room temperature while maintaining pH 5.5. After the reaction, saturated saline was added, and the mixture was extracted 5 times with ether. The ether layer was washed, dried, concentrated and purified by column chromatography to give 2.7 g of (3R) -6-t.
-Butyldimethylsilyloxy-1,2-epoxy-1-phenylhexan-3-ol (yield 93%) was obtained.

(5) (4R, 5R) -3- (2,2-dimethyl-5-phen
Nylmethyl-1,3-dioxolan-4-yl) propane-1-
Synthesis of all. (3R) -6-t-Butyldimethylsiloxy-1,2-epoxy-1
-Phenylhexane-3-ol 1.455g to ethanol 15ml
It was dissolved in the solution, 10% palladium carbon (375 mg) was added, and the mixture was vigorously stirred under a hydrogen atmosphere. After filtration and concentration, it was dissolved in 15 ml of 2,2-dimethyloxypropane, and a catalytic amount of p-toluenesulfonic acid was added. After reacting for 2 hours, the reaction was stopped with saturated sodium hydrogen carbonate, water was added, and the mixture was extracted with ether. The ether layer was dried, concentrated, and purified by column chromatography to give (4R, 5R) -1-t-butyldimethylsilyloxy-3- (2,2-dimethyl-5-2-phenylmethyl-1,3-). 1.378 g (yield 80%) of dioxolan-4-yl) propane was obtained. Dissolve this in 27 ml of tetrahydrofuran and
Tetrabutylammonium fluoride was added and reacted for 1 hour. The reaction was quenched with saturated sodium hydrogen carbonate and concentrated. Water was added to this concentrated solution, extracted with ether, the ether layer was washed, concentrated, and purified by silica gel column chromatography to give 755 mg of a new alcohol.
(Yield 64%) was obtained.

The obtained novel alcohol has a specific optical rotation of [[
α] ²⁴ _D ＋ 26.5 ° (C = 1.02, CHCl ₃ ), infrared absorption spectrum absorption wave number (cm ^-1 ) is 3450,1605,150
It was 0, 1450, 1380, 1240, 1050, 890, 845, 750, 700 (see Fig. 1). Also, the proton magnetic resonance spectrum ¹ HNM
Σ value of R (400MH ₂ ) is 1.37 (3H.S), 1.39 (3H.S), 1.40-1.5
0 (2H.m), 1.60-1.70 (2H.m), 2.83 (1H.dd, J = 5.4, 14.2H
z), 2.97 (1H, dd, J = 6.8, 14.2Hz), 3.71 (1H, ddd, J = 3.4,
8.0,8.0Hz), 3.88 (1H, ddd, J = 5.4,6.8,8.0Hz), 7.20-7.
It was 35 (5 H.m) (see FIG. 2). Furthermore, mass spectrometry MS
Results of m / z is, 235 [9, M + -CH 3] 175 [23], 159 [68, M
＋ -C ₇ H ₇ ], 101 [100], 91 [74, C ₇ H ₇ ], 57 [77]
From these analysis results, (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propane-
Identified as 1-ol.

Example 2 (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-di
Oxolan-4-yl) propyl 3,5-dinitrobenzoate
The synthesis of G. (4R, 5R) -3- (2,2-Dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propane-1- in 8 ml of pyridine
Dissolve all 1.5 g and use 3,4-dinitrobenzoic acid chloride 1.74
g and a catalytic amount of 4- (N, N-dimethylamino) pyridine were added. After reacting for 1 hour, water was added and the mixture was extracted with ether. The ether layer was washed with an aqueous solution of copper sulfate and a saturated saline solution, dried and concentrated. The obtained residue was recrystallized with hexane / ethyl acetate to obtain 2.36 g (yield 84%) of a new ester of red-yellow prism crystals.

The novel ester obtained has a melting point of 121-122.
°, [α] ²⁵ _D + 9.07 ° C (C = 1.14, CHCl ₃ ), infrared absorption spectrum absorption wave number (cm ^-1 ) is 3150,2970,17
It was 25,1625,1595,1540,1340,1270,1160,1070,720,7700 (see FIG. 3). Also, the proton magnetic resonance spectrum
Σ value of ¹ HNMR (400MH ₂ ) is 1.38 (3H.S), 1.39 (3H.S), 1.40.
-1.50 (2H.m), 1.80-2.00 (2H.m), 2.81 (1H.dd, J = 6.4, 14.
2Hz), 3.04 (1H, dd, J = 6.4, 14.2Hz), 3.76 (1H, ddd, J = 3.
4, 8.3, 8.3Hz), 3.90 (1H, ddd, J = 6.4, 6.4, 8.3Hz), 4.40
(2H, t, J = 6.6), 7.13-7.28 (5H.m), 9.12 (2H, d, J = 2.0Hz), 9.
It was 24 (1H, d, J = 2.0Hz) (see FIG. 4). Furthermore, the results of elemental analysis are: measured value C: 59.71%, H: 5.44%, N:
Calculated value at 6.27% C: 59.40%, H: 5.44%, N: 6.30
% (C ₂₂ H ₂₄ N ₂ O ₈ ) and from these analysis results
It was identified as (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propyl-3,5-dinitrobenzoate.

Example 3 (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-di
Synthesis of oxolan-4-yl) propan-1-ol. 2.41 g of 3,5-dinitrobenzoic acid ester in 20 m of ethanol
1 and dissolved in 25 ml of tetrahydrofuran, and 3 ml of 2N potassium hydroxide aqueous solution was added. After reacting for 20 minutes, the mixture was concentrated, water was added, and the mixture was extracted with ether. After drying, purified by silica gel chromatography, new alcohol 1.
We got 38g.

The specific rotation of the obtained novel alcohol is [
α] ²⁴ _D + 27.2 ° C (C = 1.26, CHCl ₃ ), infrared absorption spectrum absorption wave number (cm ⁻¹ ), proton magnetic resonance spectrum ¹ HNMR (400 MH ₂ ) σ value, and mass spectrometry m / z
Was the same as in Example 1, and was identified as (4R, 5R) -3 (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol.

(Example 4) (4R, 5R) -5-hydroxy-6-phenyl-4-hexanolide
Of synthesis. Oxalyl chloride 1.38 g, dimethylsulfoxide 1.
Swern reagent prepared from 72 g and 29 ml of methylene chloride at -70 ° C
Then, (4R, 5R) -3 (2,2-dimethyl-5 obtained in Example 3 was obtained.
1.38 g of -phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol were reacted for 1 hour. After the reaction,
3.34 g of triethylamine and water were added, and the mixture was extracted with ether. After the extract is dried and purified by column chromatography, the reaction product is the primary hydroxyl group as an aldehyde.
1.27 g was obtained (yield 93%). The obtained reaction product was dissolved in methanol, and a solution of 1.5 g of silver nitrate / 22 ml of water and 980 mg of potassium hydroxide / 15 ml of water were added. At 0 ° C
After reacting for 30 minutes, acidify the solution with hydrochloric acid and
And reacted for 30 minutes. After the reaction, insoluble matter is filtered off, concentrated,
Ether extraction was performed. After drying the ether layer,
Concentrate, silica gel chromatography and distillation (150 ° C
/0.8 mmHg) to obtain a reaction product.

The obtained reaction product is [α] ²⁶ _D −54.4 °
(C = 1.25, CHCl ₃ ), infrared absorption spectrum absorption wave number (cm ^-1 ) is 3450,3075,3040,2940,1770,1600,149
5,1450,1420,1370,1340,1260,1190,1095,1045,1000,94
It was 5,920,825,750,700. Further, the σ value of the proton magnetic resonance spectrum ¹ H NMR (400 MH ₂ ) is 2.20-2.30 (2 H, m),
2.52 (1H, ddd, J = 8.9, 8.9, 17.7Hz), 2.66 (1H, ddd, J =
6.4,9.3 17.7Hz), 2.93 (2H, d, J = 6.8Hz), 3.84 (1H, ddd,
J = 3.4, 6.8, 6.8Hz), 4.46 (1H, ddd, J = 3.4,6.87.3Hz),
It was 7.20-7.40 (5H, m). ^B H NMR (100 MH ₂ ) σ values are 23.94, 28.55, 39.88, 74.33, 81.13, 126.79, 128.
Since it was 69 (× 2), 129.35 (× 2), 137.07,177.50, it was identified as (4R, 5R) -5-hydroxy-6-phenyl-4-hexanolide.

[Brief description of drawings]

FIG. 1 is a novel alcohol (4R, 5R) -3- (2, according to the present invention.
2-Dimethyl-5-phenylmethyl-1,3-dioxolane-4-
FIG. 3 is an infrared absorption spectrum diagram of (yl) propan-1-ol.

FIG. 2 is a proton magnetic resonance spectrum diagram of the above.

FIG. 3 is a novel ester (4R, 5R) -3- (2,2-
FIG. 3 is an infrared absorption spectrum diagram of dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propyl-3,5-dinitrobenzoate.

FIG. 4 is a proton magnetic resonance spectrum diagram of the above.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiromichi Ota, 8-32-32 Kinuta, Setagaya-ku, Tokyo (72) Inventor, Wei Sugai 895 Kiyotsuki Minegishi, 895 Kizuki, Nakahara-ku, Kawasaki-shi, Kanagawa

Claims (5)

[Claims] 1. A novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3 represented by the general formula 1 (Formula 1)
-Dioxolan-4-yl) propan-1-ol. [Chemical 1] 2. Methyl 4-represented by the general formula 2
Reducing oxo-6-phenyl-5-hexinoate,
Methyl 4-hydroxy-6 represented by the general formula 3
-Phenyl-5-hexinoate, represented by the general formula 3
Only the R-form of the methyl 4-hydroxy-6-phenyl-5-hexinoate represented by (Chemical Formula 3) is lactonized with lipase, and then this primary hydroxyl group is protected with t-butyldimethylsilyl chloride and reduced. Further, after epoxidation, the epoxy group is reductively opened to acetonide, and only the protective group of primary hydroxyl group is selectively desilylated. (4R, 5R) -3- (2,2-Dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propane-1-
All manufacturing method. [Chemical 2] [Chemical 3] [Chemical 4] 3. (4R, 5R) -3-represented by the general formula 5 (formula 5)
(2,2-dimethyl-5-phenylmethyl-1,3-dioxolane
-4-yl) Propan-1-ol and a derivative thereof are mixed with 3,5-dinitrobenzoic acid chloride represented by the general formula 6 (Chemical formula 6) to be represented by the general formula 7 (Chemical formula 7) A general formula 8 characterized in that it is a 5-dinitrobenzoic acid ester, and the 3,5-dinitrobenzoic acid ester represented by the general formula 7 is recrystallized and then hydrolyzed with an alkali.
A method for producing a novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-dioxolan-4-yl) propan-1-ol represented by the chemical formula (8). [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] 4. A novel ester (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3-represented by the general formula 9:
Dioxolan-4-yl) propyl 3,5-dinitrobenzoate. [Chemical 9] 5. A novel alcohol (4R, 5R) -3- (2,2-dimethyl-5-phenylmethyl-1,3 represented by the general formula 10:
-Dioxolan-4-yl) propan-1-ol is oxidized to a carboxylic acid and then lactonized with an acidic catalyst to induce roots of carrots represented by the general formula 11 (4R, 5R) -5-Hydroxy-6-phenyl
-4-Method for producing hexanolide. [Chemical 10] [Chemical 11]