Method of preparing myrtenic acid or the same with an ester thereof

FIELD: organic synthesis.

SUBSTANCE: synthesis involves oxidation of substrate with chlorine dioxide in organic solvent at 40-50°C, said selected from myrtenal or myrtenol and said organic solvent from acetone, benzene, and alcohol at molar ratio of myrtenal or myrtenol to chlorine dioxide 1:(0.5-3.5). Thus formed myrtenic acid is isolated in the form of its water-soluble salt and, when alcohol is used as solvent, in the form of ester.

EFFECT: increased yield of product to 66%, reduced expenses, and shortened reaction time.

3 cl, 1 tbl, 2 ex

 

The invention relates to the field of organic chemistry, in particular to a method of obtaining Martinovi acids and esters used as odoriferous substances and synthons for the production of biologically active compounds.

It is well known that for obtaining carboxylic acids using the corresponding primary alcohols or aldehydes, using as oxidant compounds chromium (VI), permanganate, silver oxide, manganese dioxide, compounds of ruthenium, copper, platinum, vanadium.

A method of obtaining Martinovi acid (Kuchin AV and other chlorine Dioxide - new soft oxidant allylic alcohols. Proceedings of the Academy of Sciences, series of chemical, 1996, No. 7, str-1872), including oxidation myrtenol chlorine dioxide in the environment of an organic solvent, such as CCl4at a temperature of 50°followed by separation of the crude acid and Mertens. Output Martinovi acid is 4%, and the output of Mertens - 41%, with the degree of conversion of myrtenol - 61%.

The disadvantages of this method are very low yield of the target product and incomplete conversion of myrtenol.

The challenge is to develop new and more effective way to get Martinovi acid.

The present invention allows to increase the raw output of the target product to 66% in the calculation of the original substrate, to reduce the cost of technology is Holocene Martinovi acid, to reduce the reaction time.

The technical result is achieved in that a method of obtaining Martinovi acid or Martinovi acid and its ether complex, involving oxidation of the substrate by chlorine dioxide in the environment of an organic solvent, according to the invention the substrate is selected from Mertens or myrtenol and the oxidation is carried out at a temperature of 40-50°With, in the environment of an organic solvent selected from the group of: acetone, benzene, alcohol, in a molar ratio myrtenol or Mertens to chlorine dioxide of 1:(0.5 to÷3,5) with subsequent transfer to the water-soluble salt and allocation Martinovi acid, and, if use as a solvent of the alcohol - ether complex Martinovi acid. In addition, the oxidation exercise control over the course of the reaction by TLC until the disappearance of the spot of the original substrate; raw montenovo acid optionally purified by chromatography or by crystallization from light hydrocarbons, type, hexane, pentane.

While receiving Martinovi acid also get the corresponding ester provided the oxidation of substrate in the medium of alcohol.

The method is as follows.

As the substrate take myrtenal or myrtenol. The process is conducted in the medium of an organic solvent at a temperature of 20-50°C. the solvent is sportsouth acetone, or benzene, or alcohol.

Through the substrate miss gaseous chlorine dioxide, at a molar ratio of substrate: chlorine dioxide 1:0,5÷a 3.5. Control over the course of the reaction is carried out by TLC until the disappearance of the spot of the original substrate. After the reaction mixture was washed with water, dried to remove solvent. Then from the reaction mass produce acid in a known manner, by translation in a water-soluble salt [Petrova L.N., Zeleneckaya A.A., Skvortsova A.B. Analysis of synthetic aromatic substances and essential oils. - M.: the Food industry. in 1972, is str]. The resulting mass is shaken in a separating funnel or intensively stirred on a magnetic stirrer with a 5%aqueous solution of NaHCO3or 3%aqueous NaOH solution at a molar ratio of acid: NaHCO3(NaOH), is equal to 1:1,5÷5,0. Then the aqueous layer was separated from the oil, washed with diethyl ether, acidified with dilute (5-10%) H2SO4and extracted with ether. The ether extracts washed with water until neutral, dried and distilled off extragent. Raw miranova acid is secreted in the form of a thick viscous oil dark color.

Further purification of the acid is carried out by chromatography or by crystallization from light hydrocarbons (hexane, pentane).

Below are schemes for explaining the method.

Scheme 2 shows the process of obtaining Martinovi acid using as a solvent of alcohol, in particular ethanol. When doing this process simultaneously produces 20-40% of ester, in particular itermittent. When using other alcohols receive the corresponding esters.

The resulting ester allocate chromatography on SiO2the oil layer after separation Martinovi acid.

The time required to obtain Martinovi acid, is 5-11 hours.

Example 1

of 0.47 g (0,0038 mol) myrtenol dissolved in 10 ml of acetone, heated to 50°and with stirring, let the current ClO2within two hours. The molar ratio of myrtenol: ClO21:1,6. After removal of acetone, the reaction mass is shaken in a separating funnel with 10 ml of 3% NaOH solution, extracted with diethyl ether and the aqueous layer was separated. After acidification of the aqueous layer with 10% solution of H2S04, extraction with ether, washing with water, drying and removal of solvent to obtain 0.31 g of crude acid (yield of 66% on the original myrtenol or 61% of theoretically possible).

Example 2

is 4.93 g (to 0.032 mol) myrtenol dissolved in 50 ml of EtOH, skip the current ClO2for 5 hours with stirring and heated to 50°C. the Ratio of alcohol: ClO21:1. Upon completion of the reaction Bo the greater part of the solvent is evaporated, the reaction mass is transferred into a separating funnel, diluted with water and extracted with diethyl ether (3×50). After drying and removal of solvent mass is treated with 50 ml of 5% aqueous NaHCO3when the molar ratio of acid: NaHCO31:4. Get 1,11 g Martinovi acid (22,5% of the original alcohol). Oil fraction (3,35 g)remaining after separation of the acid, has a pleasant smell and contains GC 61,0% (41,1% myrtenol) of ester, which is etymonline.com.

After chromatographic purification, the structure of the ether was established using IR, NMR1H and13With spectroscopy.

Physico-chemical characteristics.

Miranova acid:

With10H14About2, TPL 53-54 .5°, [α]D20+18.6° (C 1.0, EtOH).

IR-spectrum: 2500-3100 (OH), 1690 (C=O), 1630 (C=C), 1430, 1280 (C-O), 1080, 960 (O-H), 790, 760, 720.

An NMR spectrum13From: 171.8 (C10), 139.8 (C2), 139.3 (C3), 40.8 (C1), 40.2 (C5), 37.6 (C6), 32.3 (C4), 31.2 (C7), 25.8 (C8), 20.9 (C9).

An NMR spectrum1N: 0.8, 1.12, 1.34, 2.13, 2.46, 2.79, 6.99, 12.1.

Itermittent:

C12H18O2

IR-spectrum: 2988, 1718,1632, 1376, 1256, 1076, 756.

An NMR spectrum13From: KZT 166.2, 140.3, 135.3, 60.1, 41.1, 40.3, 37.6, 32.1, 31.2, 26.3, 20.8, 14.3.

An NMR spectrum1H: 1.25, 1.75, 1.79, 2.58, 2.82, 2.88, 2.95, 3.25, 4.62, 7.27.

1. The method of obtaining Martinovi acid or Martinovi acid and its complex ether, kiuchumi oxidation of the substrate by chlorine dioxide in the environment of an organic solvent, characterized in that the substrate is selected from Mertens or myrtenol and the oxidation is carried out at a temperature of 40-500In the environment of an organic solvent selected from the group of: acetone, benzene, alcohol, in a molar ratio myrtenol or Mertens to chlorine dioxide of 1:(0.5 to÷3,5), with subsequent transfer to the water-soluble salt and allocation Martinovi acid, and, in the case of use as a solvent of the alcohol - ether complex Martinovi acid.

2. The method according to claim 1, characterized in that the oxidation exercise control over the course of the reaction by TLC until the disappearance of the spot of the original substrate.

3. The method according to claim 1, characterized in that the raw montenovo acid optionally purified by chromatography or by crystallization from light hydrocarbons type of hexane, pentane.



 

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