JPS61186347A - Novel sorbitol oleic acid ester - Google Patents

Abstract

NEW MATERIAL:The compound of formula (R1 is acyl group derived from oleic acid, i.e. 9-octadecenoyl; R2 is R1 or H). USE:A non-toxic nonionic surfactant for food, cosmetic and medicinal use. It has valuable bioactivity such as antitumor activity, immunoactivating effect, antibacterial effect, plant-growth suppressing effect, etc. PREPARATION:Sorbitol and oleic acid are incubated in the presence of a hydrolase, especially lipase until the reaction progresses to the equilibrium state, when the reaction is terminated and the compound of formula is separated from the reaction liquid and purified.

Description

[Detailed description of the invention] The present invention is based on the formula: (Margin below) CHzO-R1 HCO [( 1 (OCR C.O.R. COH CH2O-Rz The present invention relates to a novel sorbitol oleate ester.

In the formula, R1 represents an acyl group derived from oleic acid, that is, a 9-octadecenoyl group, and R2 is the same as R1 or represents hydrogen.

Carbohydrates, especially fatty acid esters of sucrose and sorbitan, are typical nonionic surfactants, and because they themselves and their decomposition products are nontoxic, they are widely used as food additives and as emulsifiers in cosmetics and pharmaceuticals. ing.

Since all of these industrial manufacturing methods include a heating process,
It has disadvantages such as coloring of the product and formation of a complex mixture when heated. In particular, sorbitol undergoes intramolecular dehydration to form sorbitan and sorbite through transesterification using conventional pure chemical methods, making it difficult to synthesize higher fatty acid esters of pure sorbitol.

The present inventors developed a method for biochemically synthesizing carbohydrate higher fatty acid esters from higher fatty acids and carbohydrates using the enzyme lipase, and tried this method for the reaction of sorbitol and oleic acid. could be esterified without cyclization. The product is mainly composed of monoesters and diesters, and is characterized by the fact that the reactivity of the -class OH group is specifically very high compared to the secondary OH group. We succeeded in isolating the sorbitol monooleate and sorbitol dioleate.

These mono- and diesters are new compounds that could not be synthesized by conventional transesterification methods or acylation methods using acid chlorides, and are useful as nonionic surfactants for non-toxic foods, cosmetics, and pharmaceuticals. However, it has useful biological activities such as antitumor, immunostimulatory, antibacterial, and plant growth inhibitory effects.

The sorbitol oleate ester of the present invention can be produced by incubating sorbitol and oleic acid in the presence of an enzyme.

As the enzyme, a hydrolytic enzyme, especially a lipase, is used. As is well known, there are lipases of animal origin and those of microbial origin; either of these may be used. For example, Asper is derived from pig pancreas, and Asper is derived from microorganisms.
gillus, Rh1zopus+ Pseu-do
monas+ Enterobacterium, C
hromobacterium.

Geotrichum, Penicillium,
Some are derived from microorganisms such as Mucor and Candida. These enzymes do not necessarily need to be isolated and used; for example, as a crude enzyme such as pancreatin,
Alternatively, a commercially available enzyme preparation containing lipase can be used as is.

The amount of enzyme added varies depending on the origin, type, potency, etc. of the enzyme, but it is sufficient as long as the reaction mixture contains a predetermined enzyme activity.

Since this reaction is reversible, equilibrium is reached after the reaction progresses to some extent. In this state, the reaction is stopped, and sorbitol oleate is separated and purified from the reaction solution by a conventional method to recover unreacted fatty acids.

Separation of monoester and diester can be carried out, for example, by preparative gel permeation chromatography.

Example 1 Commercially available lipase preparation (Candida Cylindra)
cea-derived lipase MY, Meito Sangyo) 12g at pH 5
, dissolved in 4 phosphate buffer 61, sterilized with a sterilizing filter, and placed in a 1 (l) jar fermenter.

Then sorbitol (Wako Pure Chemicals reagent grade) 109.3g
and dissolve at 35°C.

Next, 169.2 g of oleic acid (Extra 01eic 90+ Nippon Oil & Fats) was gradually added dropwise using a dropping funnel.
Form a microemulsion.

Incubate for 72 hours at 35 rpm and 35°C. The reaction mixture is freeze-dried, the resulting freeze-dried product is extracted with chloroform, and the extract is concentrated under reduced pressure.

The chloroform extract is dissolved in tetrahydrofuran (without the stabilizer BIT), centrifuged at 3000 rpm, and separated into a tetrahydrofuran-soluble fraction and a tetrahydrofuran-insoluble fraction.

A monoester fraction and a diester fraction are separated from the tetrahydrofuran soluble fraction by preparative gel permeation chromatography, and each is concentrated under reduced pressure to obtain pure monoester and diester fractions.

The gel permeation chromatography chart and preparative range of the reaction mixture are shown in FIG. 1, and the same chart for monoester and diester alone is shown in FIG.

Monoester structural formula, (blank below) C)lzO-C-(CH2)7CH=CI((CH2)
7CH3■ COH 1-place OCR COH COH HzOH Melting point near 0.5℃~71.0℃ Yield: 64.30g Elemental analysis: Theoretical value C64,57;) (10,31 Experimental value C64,13; Hlo, 13 IR characteristics Absorption (cm-'): 1720 (RC
OOR'), 1470 (CH2).

1060 (C-0), 715 (-CH2-),
3300 (OR), 1110 (secondary alcohol), 1050 (primary alcohol); 3030 (as CH shoulder) as absorption based on oleic acid
), 1660-1640 (C=C), ? 2
0 (cis double bond) 1 NMR signal attributed nioleic acid skeleton carbon CH3, -CHz-, 14-38
ppm question above cmC, 135ppm Oleic acid skeleton carbon C=0. 174pp
mSorbitol skeleton carbon, 662-78ppCH20-C-(CH2)7C■=CH(CH2)7C
)+3C0II ■ OCH 〜COH Melting point: 58.5℃～59.5℃ Yield: 33.18g Elemental analysis: Theoretical value C70,98; Hlo, 99 Experimental value C71,10; Hlo, 87 IR characteristic absorption (value - : 1720 (RCOOR
'), 1470 (CH2).

1060 (C-0), 715 (-CHz~),
3300 (OH), 1110 (secondary alcohol), 1050 (primary alcohol); 3030 (as CH shoulder) as absorption based on oleic acid
), 1660-1640 (C=C), 72
0 (cis double bond) 13c NMR signal assignment nioleic acid skeleton carbon CH3, -C) lz-, 14-3
8ppm above question C=C, 135ppm above question C-0, 174ppm Sorbitol skeleton carbon, 662-78ppExample 2 In Example 1, except that 282.47 g of oleic acid was used instead of 169.2g of oleic acid. In the same manner, sorbitol monooleate 36.34
g and sorbitol dioleate 76.66
I got g.

A gel permeation chromatography chart of the tetrahydrofuran soluble fraction is shown in FIG. 3, and the same chart of the purified monoester and diester is shown in FIG. 4.

[Brief explanation of drawings]

The drawings are charts of gel permeation chromatography, in which Fig. 1 shows the tetrahydrofuran soluble portion of Example 1, Fig. 2 shows the monoester and diester obtained in Example 1, and Fig. 3 shows Example 2. FIG. 4 is a chart of the monoester and diester obtained in Example 2.

Claims (1)

[Claims] There are formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is an acyl group derived from oleic acid,
That is, it represents a 9-octadecenoyl group, and R_2 is R_
1 or representing hydrogen).