Method of producing (2e,4e)-dodeca-2,4-dien-1-ylisovalerate

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and particularly to a method of producing (2E,4E)-dodeca-2,4-diene-1-ylisovalerate, involving hydroalumination-halogenation of 1-nonyne to obtain (1E)-1-halogennon-1-ene, cross-coupling (1E)-1-halogennon-1-ene with methyl acrylate to obtain methyl ether of (2E,4E)-dodeca-2,4-dienic acid, reducing methyl ether of (2E,4E)-dodeca-2,4-dienic acid with lithium aluminium hydride to obtain (2E,4E)-dodeca-2,4-diene-1-ol, acylating (2E,4E)-dodeca-2,4-dien-1-ol with an acyl chloride of isovaleric acid to obtain (2E,4E)-dodeca-2,4-dien-1-ylisovalerate, where synthesis of methyl ether of (2E,4E)-dodeca-2,4-dienic acid is carried out in by reacting (1E)-1-iodonon-1-ene, which is obtained by hydroalumination-iodination of 1-nonyne, with methyl acrylate in the presence of Pd(OAc)2, K2CO3, Bu4NCl in the medium of N-methyl pyrrolidone with the following molar ratio [(1E)-1-iodonon-1-ene] : [methyl acrylate] : [Pd(OAc)2] : [K2CO3] : [Bu4NCl] : [N-methyl pyrrolidone] = 1:2: 0.02 : 2.5 : 1 : 5.5 for 8 hours in the atmosphere of argon at 18-25°C.

EFFECT: method has the following advantages: higher output of (2E,4E)-dodeca-2,4-dien-1-ylisovalarate, and conducting the cross-coupling reaction without heating at 18-25°C prevents isomerisation of the (2E,4E)-diene system and increases stereochemical purity of the product.

4 ex

 

The invention relates to the field of organic chemistry, in particular to a method for (2E,4E)-dodeca-2,4-Dien-1-isovalerate.

(2E,4E)-Dodeca-2,4-Dien-1-isovalerate is the main component of the oil extracted from rhizomes purple angustifolia and Echinacea, which is widely used in pharmacological purposes.

The only known way to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate (1) (Auesbaeva, Rnewman, Tin, Synthesis of (2E,4E)-dodeca-2,4-Dien-1-isovalerate - the main component of the oil from the roots of Echinacea purpurea (Echinacea Purpurea) (Zhur.org.chem., 2010, Vol.46, Issue 2, .183-184), chosen for the prototype includes the following stages:

1. Hydroalumination-bromination of 1-Nonino (2) to give (1E)-1-Brannon-1-ene (3);

2. Cross-coupling of (1E)-1-Brannon-1-ene (3) with methyl acrylate to obtain methyl ester of (2E,4E)-dodeca-2,4-diene acid (4);

3. The recovery of the methyl ester of (2E,4E)-dodeca-2,4-diene acid (4) sociallyengaged to obtain (2E,4E)-dodeca-2,4-Dien-1-ol (5);

4. The acylation of (2E,4E)-dodeca-2,4-Dien-1-ol (5) the acid chloride isovalerianic acid to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate (1)

A. diisobutylaluminium, Br2b. MMA, Pd(OAc)2Bu4NCl, K2CO3; century LiAlH4;, the acid chloride isovalerianic acid, pyridine.

About the speaker output (2E,4E)-dodeca-2,4-Dien-1-isovalerate on the source (S)-1-bromo-1-nonen is 68%.

The method has significant drawbacks at the stage of cross-combinations (1E)-1-Brannon-1-ene (3) with methyl acrylate to obtain methyl ester of (2E,4E)-dodeca-2,4-diene acid (4).

1. Not a high yield of product.

2. Conducting the reaction at elevated temperature leads to isomerization of (2E,4E)-diene system and obtaining by-products.

Object of the invention is the creation of a more efficient way to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate with higher output.

This task is solved in that in the production method of (2E,4E)-dodeca-2,4-Dien-1-isovalerate, including hydroalumination-halogenoalkane 1-Nonino obtaining (1E)-1-halogen-1-ene, cross-coupling of (1E)-1-halogen-1-ene with methyl acrylate to obtain methyl ester of (2E,4E)-dodeca-2,4-diene acid, recovery of the methyl ester of (2E,4E)-dodeca-2,4-diene acid sociallyengaged to obtain (2E,4E)-dodeca-2,4-Dien-1-ol, acylation (2E,4E)-dodeca-2,4-Dien-1-ol the acid chloride isovalerianic acid to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate, according to the invention the synthesis of the methyl ester of (2E,4E)-dodeca-2,4-diene acid is carried out by the interaction of (1E)-1-itnon-1-ene (obtained by hydroalumination-moderowaniem 1-Nonino) with methyl acrylate in the presence of Pd(OAc)2, K2CO3Bu4NCl in the rede N-methylpyrrolidone in the following molar ratio: [(1E)-1-itnon-1-ene]:[MMA]:[Pd(OAc) 2]:[K2CO3]:[Bu4NCl]:[N-organic]=1:2:0,02:2,5:1:5,5 within 8 h in an argon atmosphere at 18-25°C.

The method is as follows. A mixture of (1E)-1-itnon-1-ene, methyl acrylate, Pd(OAc)2, K2CO3and Bu4NCl in the environment of N-methylpyrrolidone is stirred in an argon atmosphere at room temperature for 8 h with the following molar ratio of the reagents [(1E)-1-itnon-1-ene]:[MMA]:[Pd(OAc)2]:[K2CO3]:[Bu4NCl]:[N-organic]=1:2:0,02:2,5:1:5,5 within 8 h in an argon atmosphere at 18-25°C. a Further operation on the separation and purification of the methyl ester of (2E,4E)-dodeca-2,4-diene acids do not differ from the prototype.

In the invention, the yield of methyl ester of (2E,4E)-dodeca-2,4-diene acid is increased to 98% (prototype - 92%). The total yield of (2E,4E)-dodeca-2,4-Dien-1-isovalerate on the source (1E)-1-itnon-1-ene is 72% (prototype - 68% at baseline (1E)-1-Brannon-1-ene).

Example 1. Receiving (1E)-1-itnon-1-ene. To a solution of 12.4 g (0.1 mol) 1-Nonino in 120 ml of absolute hexane was added 150 ml of a 1M solution of diisobutylaluminium (DIBAH) in hexane and stirred 6 h at 55°C in argon atmosphere. The reaction mixture was cooled to -50°C was added a solution of 27.9 g (0.11 mol) of iodine in 150 ml of anhydrous tetrahydrofuran for 1 h Then the reaction mixture was heated for 1 h to room temperature is, was stirred at this temperature for another 12 h and was added with ice cooling, 250 ml of 10% solution of sulfuric acid. The organic layer was separated, the aqueous was extracted with hexane (3×150 ml). The combined organic layers were washed with saturated NaCl solution, dried Na2So4and concentrated. The product was isolated by the method of column chromatography (SiO2, hexane-chloroform, 6:1). The output of 22.5 g (89%). IR spectrum, ν, cm-1: 2955, 2926, 2855, 1607, 1456, 1211, 1198, 945. An NMR spectrum1N, δ, ppm: 0.88 t (3H, CH3), 1.21-1.42 m (10H, SN2), 2.04 (2H, WITHN2CH=, J 7.0 Hz), 5.97 (1H, C1H=, J 14.3 Hz), 6.45-6.55 m (1H, C2H=). An NMR spectrum13S, δ, ppm: 14.00 (CH3), 22.58 (C8), 28.30 (CH2), 28.82 (CH2), 28.96 (CH2), 31.68 (7), 35.98 (3), 74.23 (1), 146.59 (2). Mass spectrum, m/z (IRel, %): 252 (34) [M]+, 167 (40), 154 (35), 83 (70), 70 (16), 69 (100), 57 (12), 56 (11), 55 (39), 43 (28), 41 (25), 39 (12).

Example 2. Obtaining methyl ester (2E,4E)-dodeca-2,4-diene acid.

To a solution of 12.6 g (0.05 mol) of (1E)-1-itnon-1-ene in 30 ml of N-methylpyrrolidone was added 8.6 g (0.1 mol) of methyl acrylate, 17.3 g (0.125 mol) K2CO3, 13.9 g (0.05 mol) Bu4NCl and 0.224 g (1 mmol) of Pd(OAc)2. The reaction mixture was stirred under argon at 18-25°C for 8 h, then was added 100 ml of hexane and 100 ml of water. The organic layer was separated, the aqueous was extracted with hexane (3×100 ml). The combined organic is layers were washed with saturated solution of NaCl, dried Na2SO4and concentrated. The product was isolated by the method of column chromatography (hexane - Et2O 9:1). Yield 10.3 g (98%). IR spectrum, ν, cm-1: 2953, 2926, 2855, 1719 (C=O), 1645 (C=C), 1616 (C=C), 1435, 1261, 1140, 999. An NMR spectrum1N, δ, ppm: 0.89 t (3H, CH3), 1.21-1.48 m (10H, SN2), 2.16 (2H, WITHN2CH=, J 7 Hz), 3.74 (3H, CH3O), 5.80 (1H, C2H=, J 15.3 Hz), 6.08-6.22 m (2H, 2CH=), 7.23-7.31 m (1H, CH=). An NMR spectrum13S, δ, ppm: 14.04 (12), 22.61 (11), At 28.67 (CH2), 29.06 (CH2), 29.11 (CH2), 31.74 (10), 32.92 (C6), Is at 51.36 (CH3O), 118.62 (2), 128.27 (4), 144.96 (5or3), 145.37 (3or5), 167.72 (1). Mass spectrum, m/z (IRel, %): 210 (2) [M]+, 113 (36), 111 (100), 82 (30), 81 (53), 79 (38), 67 (34), 66 (28), 55 (31), 43 (43), 41 (53), 28 (34).

Example 3. Obtain (2E,4E)-dodeca-2,4-Dien-1-ol. To a solution of 0.76 g (0.02 mol) LiAlH4in 100 ml of absolute diethyl ether under stirring and cooling (0°C) in argon atmosphere for 1 h was added 6.93 g (0.033 mol) of methyl ester of (2E,4E)-dodeca-2,4-diene acid. The reaction mixture was heated to room temperature, stirred for 2 hours, again cooled to 0°C and carefully was added 30 ml of water. The organic layer was separated, washed with saturated solution of NaCl, dried Na2SO4and concentrated. The product was isolated by the method of column chromatography (hexane - Et2O, 7:3). The output of 5.33 g (88%). Expect, ν, cm-1: 3335 (HE), 3019, 2955, 2924, 2855, 1458, 1437, 1090, 1049, 988. An NMR spectrum1H, δ, ppm: 0.88 t (3H, CH3, J 6.7 Hz), 1.21-1.44 m (10H, 5CH2), 2.08 (2H, CH2CH=, J 6.7 Hz), 3.62 (1H, HE), 4.16 (2H, CH2OH, J 5.7 Hz), 5.66-5.77 m (2H, 2CH=), 6.00-6.26 (2H, 2CH=). An NMR spectrum13S, δ, ppm: 14.04 (CH3), 22.61 (C11), 29.11 (2CH2), 29.17 (CH2), 31.77 (10), 32.58 (6), At 63.47 (C1), 129.28 (2CH=), 132.08 (CH=), 135.80 (CH=). Mass spectrum, m/z (IRel, %): 182 (7) [M]+, 91 (42), 84 (79), 83 (74), 81 (42), 80 (66), 79 (100), 77 (41), 67 (48), 55 (62), 43 (42), 41 (78).

Example 4. Obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate. To a mixture of 3.79 g (20.8 mmol) of (2E,4E)-dodeca-2,4-Dien-1-ol and 2.47 g (31.2 mmol) of absolute pyridine in 80 ml of absolute ether at 0°C in an atmosphere of argon was added 3.01 g (25 mmol) of acid chloride of isovalerianic acid. The reaction mixture was stirred 1 h at 0°C and 2 h at room temperature, was added 30 ml of water, the organic layer was separated, dried Na2SO4and concentrated. The product was isolated by the method of column chromatography (hexane - Et2O, 93:7). The output of 4.67 g (84%). IR spectrum, ν, cm-1: 2957, 2926, 2872, 2857, 1736 (C=O), 1458, 1294, 1254, 1184, 1166, 1121, 1098, 988. An NMR spectrum1N, δ, M. D.: 0.88 t (3H, CH3, J 6.7 Hz), 0.95 d (6N, 2CH3, J 6.4), 1.21-1.44 m (10H, SN2), 2.02-2.24 m (5H,N2SN=,N(CH3)2WithN2Soo), 4.58 (2H, CH2O, J 6.4 Hz), 5.59-5.78 m (2H, 2CH=), 5.95-6.07 m (1H, CH=), 6.21-6.30 m (1H, CH=). Spec is p NMR 13S, δ, ppm: 14.04 (12), 22.35 (2CH3), 22.61 (11), 25.65 (WithN(CH3)2), 29.09 (2CH2), 29.52 (CH2), 31.77 (10), 32.58 (6), 43.38 (WithH2MEO)64.65 (1), 123.98 (CH=), 129.01 (CH=), 134.73 (CH=), 136.78 (CH=), 172.86 (C=O). Mass spectrum, m/z (IRel, %): 266 (2) [M]+, 85 (100), 80 (27), 79 (35), 67 (16), 57 (52), 41 (20).

The proposed method has the following advantages:

1. Higher output (2E,4E)-dodeca-2,4-Dien-1-isovalerate.

2. Carrying out the reaction cross-combination without heating at 18-25°C prevents isomerization (2E,4E)-diene system and increases the stereochemical purity of the product.

The way to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate, including hydroalumination-halogenoalkane 1-Nonino obtaining (1E)-1-halogeno-1-ene, cross-coupling of (1E)-1-halogen-1-ene with methyl acrylate to obtain methyl ester of (2E,4E)-dodeca-2,4-diene acid, recovery of the methyl ester of (2E,4E)-dodeca-2,4-diene acid sociallyengaged to obtain (2E,4E)-dodeca-2,4-Dien-1-ol, acylation (2E,4E)-dodeca-2,4-Dien-1-ol the acid chloride isovalerianic acid to obtain (2E,4E)-dodeca-2,4-Dien-1-isovalerate, characterized in that the synthesis of the methyl ester of (2E,4E)-dodeca-2,4-diene acid is carried out by the interaction of (1E)-1-itnon-1-ene, obtained by hydroalumination-moderowaniem 1-Nonino, with methyl acrylate in risotti Pd(OAc) 2, K2CO3Bu4NCl in the environment of N-methylpyrrolidone in the following molar ratio [(1E)-1-itnon-1-ene]:[MMA]: [Pd(OAc)2]:[K2CO3]:[Bu4NCl]:[N-organic]=1:2:0,02:2,5:1:5,5 within 8 h in an argon atmosphere at 18-25°C.



 

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SUBSTANCE: invention relates to synthesis of 1,3-dicarboxylic compounds, specifically to a method for synthesis of ethyl ethers of 2-alkyl-4-aryl-3-oxobutanoic acids of general formula:

,

where for R=3,5-Me2C6H3, R1=Me, Et, i-Pr; for R=2,6-Cl2C6H3, R1=Me; for R=2- CI-6-FC6H3, R1=Me, involving acylation of di(bromine-magnesium)salt of ethyl ether of 2-alkyl-3,3-dihydroxyacrylic acid, selected from a group comprising di(bromine-magnesium)salt of ethyl ether of 2-methyl-3,3-dihydroxyacrylic acid, di(bromine-magnesium) salt of ethyl ether of 2-ethyl-3,3-dihydroxyacrylic acid and di(bromine-magnesium) salt of ethyl ether of 2-isopropyl-3,3-dihydroxyacrylic acid, obtained in situ from isopropyl magnesium bromide and the corresponding 2-(carbethoxy)alkanoic acid, arylacetyl chloride, selected from 3,5-dimethylphenylacetyl chloride, 2,6-dichlorophenylacetyl chloride and 2-fluoro-6-chlorophenylacetyl chloride, in molar ratio of arylacetyl chloride: di(bromine-magnesium) salt of ethyl ether of 2-alkyl-3,3-dihydroxyacrylic acid equal to 1: 1.6-2.2, in a medium of anhydrous tetrahydrofuran with subsequent treatment of the reaction mass with aqueous solution of citric acid and extraction of the end product.

EFFECT: high output and purity of disclosed compounds.

7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

The invention relates to a method for producing (nitroxymethyl)phenyl esters of derivatives of salicylic acid of the formula (I)

where R1means OCOR3group, where R3means methyl, ethyl or a linear or branched C3-C5alkyl;R2means hydrogen

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