Method of producing (4e)-tridec-4-en-1-ylacetate

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and particularly to a method of producing (4E)-tridec-4-en-1-ylacetate. (4E)-tridec-4-en-1-ylacetate is a sex pheromone for tomato moth (Keiferia lycopersicella), which is a dangerous pest for solanaceae. Results of the invention can be useful in chemistry and agriculture. The method of producing (4E)-tridec-4-en-1-ylacetate includes alkylating malonic ester with (E)-1,3-dichloropropene to obtain diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate, decarbalkoxylating diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate to obtain ethyl(4E)-5-chloropent-4-enoate, Fe-catalysed cross-coupling of the ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate, reducing the ethyl(4E)-tridec-4-enoate to obtain (4E)-tridec-4-en-1-ol, acetylation of the (4E)-tridec-4-en-1-ol to obtain (4E)-tridec-4-en-1-ylacetate. According to the invention, Fe-catalysed cross-coupling of ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate is carried out in the presence of a Fe(acac)2Cl catalyst in a mixture of tetrahydrofuran and N-methylpyrrolidone, wit the following molar ratio of reactants [(ethyl(4E)-5-chloropent-4-enoate]:[octylmagnesium bromide]:[Fe(acac)2Cl]:[tetrahydrofuran ]:[N-methylpyrrolidone]=1:1.15:0.01:12:7 for 30 min at 0-5°C.

EFFECT: advantage of the disclosed method is higher output of (4E)-tridec-4-en-1-ylacetate.

3 ex

 

The invention relates to the field of organic chemistry, in particular to a method for producing (4E)-tridec-4-EN-1-racette.

(4E)-Tridec-4-EN-1-ylacetic is the sex pheromone of tomato moth (Keiferia lycopersicella), a dangerous pest of solanaceous crops.

The results of the invention can be used in chemistry and agriculture.

A method of obtaining (4E)-tridec-4-EN-1-ilaclama (Melikyan, G., Aslanian, H., Atanesyan K. A., Mkrtchyan D. A., Badinan W. O. // Chemistry of natural. Conn. 1990. So 1. S. 102-106) based on the reduction of migration (5Z)-tridec-EN-4-olide. The method is based on the difficult raw materials and characterized by a low overall yield of the desired product (13%).

A method of obtaining (4E)-tridec-4-EN-1-ilaclama (Odinokov C. N., Vahidov P. P., Shamaev R. N., Gilmanova N. In. // Chemistry of natural. Conn. 1995. So 3. S. 490-493), based on the rearrangement of Clausena with low overall yield of the desired product (10%).

A method of obtaining (4E)-tridec-4-EN-1-ilaclama (Bikulov L. M., willow,,, Abduvahabov A. A. // Chemistry of natural. Conn. 1991. So 3. S. 444), based on the condensation of Coverages. The method is based on hard-to-raw ((3E)-1-bromides-3-ene) and is characterized by insufficient high overall yield of the desired product (27%).

A method of obtaining (4E)-tridec-4-EN-1-ol is the immediate precursor of (4E)-tridec-4-EN-1-ilaclama (Seufert W., Buschamann E., BeckerR., Seppelt W., Mackenroth W., patent DE 4006919, 1991), based on the isomerization of (4Z)-tridecen-1-ol in the desired transisomer. The method is based on hard-to-raw ((4Z)-tridecen-1-Ola) and are extremely low stereoselectivity (isomeric composition of the product (E/Z=80/20). Because of 1-2%, the content of (Z)-isomer inhibits attractive properties (4E)-tridec-4-EN-1-racette, the method is unsuitable for practical use.

Selected by the authors as a prototype method for producing (4E)-tridec-4-EN-1-ilaclama (I) (Shamaev R. N., Sunagatullin A. W., Zorin centuries Fe-catalyzed synthesis of [(4E)-tridec-4-EN-1-ilaclama - sex pheromone of tomato moth (Keiferia lycopersicella) // the Journal of organic chemistry. 2013. So 49. No. 5. S. 687) based on available and cheap raw materials (E)-1,3-dichloropropene (obtained by distillation of a mixture of isomers of 1,3-dichloropropene - tonnage industrial waste chlorination of propylene), high stereoselectivity and includes the following stages:

1. alkylation of malonic ether (II) (E)-1,3-dichloropropanol (III) in the presence of K2CO3and of catalytic amounts of 18-crown-6 with getting diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate (IV);

2. carbamaxepine diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate (IV) to obtain ethyl(4E)-5-chlorphen-4-enoate (V);

3. cross-coupling of ethyl(4E)-5-chlorphen-4-enoate (V) octylacrylamide in the presence of 1.5 mol% Fe(acac) 3in a mixture of tetrahydrofuran and N-methylpyrrolidone at room temperature to obtain ethyl(4E)-tridec-4-enoate (VI);

4. recovery of ethyl(4E)-tridec-4-enoate (VI) sociallyengaged obtaining (4E)-tridec-4-EN-1-ol (VII);

5. acetylation of (4E)-tridec-4-EN-1-ol (VII) acetylchloride in the presence of pyridine to obtain (4E)-tridec-4-EN-1-ilaclama (I).

The total yield of (4E)-tridec-4-EN-1-ilaclama (I) source (E)-1,3-dichloropropene is 31%.

The disadvantage of this method is the low yield ethyl(4E)-tridec-4-enoate (VI) at the stage of Fe-catalyzed cross-combination of ethyl(4E)-5-chlorphen-4-enoate (V) octylacrylamide.

Object of the invention is the creation of a more efficient way to obtain (4E)-tridec-4-EN-1-ilaclama (I) with a higher output.

This task is solved in that in the production method of (4E)-tridec-4-EN-1-ilaclama (I), comprising the alkylation of malonic ether (II) (E)-1,3-dichloropropanol (III) to give diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate (IV), carbamaxepine diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate (IV) to obtain ethyl(4E)-5-chlorphen-4-enoate (V), Fe-catalyzed cross-coupling of ethyl(4E)-5-chlorphen-4-enoate (V) octylacrylamide to obtain ethyl(4E)-tridec-4-enoate (VI), the recovery of ethyl(4E)-rides-4-enoate (VI) to give (4E)-tridec-4-EN-1-ol (VII), acetylation of (4E)-tridec-4-EN-1-ol (VII) to give (4E)-tridec-4-EN-1-ilaclama (I), according to the invention Fe-catalyzed cross-coupling of ethyl(4E)-5-chlorphen-4-enoate (V) octylacrylamide to obtain ethyl(4E)-tridec-4-enoate (VI) is carried out in the presence of a catalyst of Fe(acac)2Cl in a mixture of tetrahydrofuran and N-methylpyrrolidone in the following molar ratio of the reagents [(ethyl(4E)-5-chlorphen-4-INOUT]:[octylacrylamide]:[Fe(acac)2Cl]:[tetrahydrofuran]:[N-organic]=1:1.15:0.01:12:7 for 30 min at 0-5°C.

The method is as follows. To a solution of ethyl(4E)-5-chlorphen-4-enoate (V), Fe(acac)2Cl in a mixture of tetrahydrofuran and N-methylpyrrolidone in argon atmosphere was added dropwise at 0°C solution of octylacrylamide in THF and stirred for 30 minutes (0-5°C) in the following molar ratio of the reactants [ethyl(4E)-5-chlorphen-4-INOUT]:[octylacrylamide]:[Fe(acac)2Cl]:[tetrahydrofuran]:[N-organic]=1:1.15:0.01:12:7. Further operations for separation and purification of ethyl(4E)-tridec-4-enoate (VI) do not differ from the prototype.

In the invention, the output ethyl(4E)-tridec-4-enoate (VI) increased to 83% (prototype 72%). The total yield of (4E)-tridec-4-EN-1-ilaclama (I) source (E)-1,3-dichloropropene (III) increases to 36% (the prototype of 31%). The content of (Z)-isomer in the product is less than 0.7%.

Example 1. Obtain ethyl(4E)-tridec-4-enoate (VI). To a solution of 0.507 is (3.12 mmol) of ethyl(4E)-5-chlorphen-4-enoate (V), 9 mg (1 mol %) Fe(acac)2Cl in a mixture of 3 ml of tetrahydrofuran and 2.1 ml of N-methylpyrrolidone in argon atmosphere was added dropwise at 0°C 1 M solution of octylacrylamide in tetrahydrofuran (3.6 ml, 3.6 mmol). Was stirred for 30 minutes at 0-5°C. Then was added 10 ml of 5% HCl solution and 10 ml of hexane, the organic layer was separated and the aqueous was extracted with hexane (2×10 ml). The combined organic layers were washed with saturated solution of NaHCO3, dried Na2SO4and concentrated. The product was isolated by the method of column chromatography. Output 0.624 g (83%), oily substance. IR spectrum, ν, cm-1: 2924, 2853, 1735, 1470, 1371, 1344, 1300, 1248, 1177, 1161, 1040, 968. An NMR spectrum1N, δ, M. D.: 0.88 t (3H; C13H3, J 7 Hz), 1.23-1.36 m (15 NM,CH_3CH2O, 6 CH2), 1.96 (2H, C3H2, J 6.7 Hz), 2.27-2.39 m (4H, C2H2C6H2), 4.13 (2H, CH2O, J7 Hz), 5.34-5.51 m (2H,=C4H,=C5H). An NMR spectrum13C, δWith, M. D.: 14.03 (13), 14.18(CH_3CH2O), 22.63 (12), 27.90 (3), 29.10 (CH2/sub> ), 29.25 (CH2), 29.43 (CH2), 29.67 (CH2), 31.85 (C11), 32.45 (C6), 34.47 (C2), 60.13 (CH2O), 127.87 (C5), 131.79 (C4), 173.22 (C1). Mass spectrum, m/z (IRel, %): 152 (44), 110 (41), 109 (21), 101 (29), 98 (28), 97 (46), 95 (38), 88 (83), 84 (46), 83 (38), 82 (32), 81 (47), 71 (38), 70 (46), 69 (51), 68 (36), 67 (69), 61 (25), 60 (20), 57 (30), 55 (85), 54 (35), 43 (73), 41 (100).

Example 2. Receipt of (4E)-tridec-4-EN-1-ol (VII). To a solution of 0.54 g (2.2 mmol) of ethyl(4E)-tridec-4-enoate (VI) in 20 ml of absolute ether was added 0.08 g (1.5 mmol) of LiAlH4at 0°C in an argon atmosphere. Was stirred at room temperature for 3 h until complete conversion of the ester (V) (control according to GC). Then was added 10 ml of 5% HCl solution and 10 ml of hexane, the organic layer was separated and the aqueous was extracted with hexane (2×10 ml). The combined organic layers were washed with saturated solution of NaHCO3, dried Na2SO4and concentrated. The product was isolated by the method of column chromatography. Output 0.385 g (88%), oily substance. IR spectrum, ν, cm-1: 3339 ush. (OH), 2955, 2926, 2853, 1466, 1454, 1059, 966, 909. An NMR spectrum1H, δ, M. D.: 0.88 t (3H; C13H3, J7 Hz), 1.23-1.34 (m N, 6CH2), 1.62 sq (2N, C2H2, J6.9 Hz), 1.90 ush. (1H,CH2OH_), 1.97 (2H, WITH3H2, J 6.8 Hz), 2.07 (2H, C6H2, J7 Hz), 3.63 t (2H, C1H2 , J6.7 Hz), 5.37-5.48 m (2H, =C4N =C5N). An NMR spectrum13S, δWith, M. D.: 14.03 (13), 22.60 (12), 28.83 (3), 29.13 (CH2), 29.25 (CH2), 29.43 (CH2), 29.52 (CH2), 31.83 (C11), 32.40 (CH2), 32.52 (C6), 62.38 (1), 129.30 (C5), 131.16 (C4). Mass spectrum, m/z (IRel, %): 97 (16), 96 (31), 95 (30), 83 (23), 82 (63), 81 (73), 79 (30), 71 (23), 69 (34), 68 (84), 67 (81), 57 (36), 56 (18), 44 (14), 43 (57), 42 (15), 41 (100).

Example 3. Receipt of (4E)-tridec-4-EN-1-ilaclama (I). To a solution of 0.24 g (1.21 mmol) of (4E)tridec-4-EN-1-ol (VII) in 3 ml of absolute diethyl ether was added 0.115 g (1.45 mmol) of pyridine, 0.114 g (1.45 mmol) of acetylchloride at 0°C. was Stirred for one hour at room temperature. Then was added 5 ml of water and 10 ml of hexane, the organic layer was separated and the aqueous was extracted with hexane (2×10 ml). The combined organic layers were washed with saturated solution of NaHCO3, dried Na2SO4. The solvent was evaporated. The product was isolated by the method of column chromatography. Output 0.270 g (93%), oily substance. IR spectrum, ν, cm-1: 3020, 2924, 2850, 1743, 1450, 1375, 1240, 1051, 965. An NMR spectrum1H, δ, M. D.: 0.88 t (3H; C13H3, J7 Hz), 1.24-1.34 m (12H, 6CH2), 1.68 kV (2H, C2H2, J7 Hz), 1.97 (2H, C6H2, J 6.9 Hz), 2.03-2.07 m (5H, C3H2CH3C=O), 4.06 t (2H, C1H2, J 6.7 Hz), 5.34-5.47 m (2H, =C4N =C5H). An NMR spectrum13S, δWith, M. D.: 14.05 (C13(C_H3C=O), 22.62 (12), 28.44 (C2), 28.79 (C3), 29.12 (CH2), 29.24 (CH2), 29.42 (CH2), 29.48 (CH2), 31.85 (C11), 32.51 (C6), 63.97 (C1), 128.56 (C5), 131.59 (C4), 171.16(C_H3C=O). Mass spectrum, m/z (IRel, %): 96 (20), 95 (17), 82 (39), 81 (48), 79 (16), 69 (19), 68 (87), 67 (63), 55 (37), 54 (32), 43 (100), 41 (49).

The advantage of the proposed method is higher output (4E)-tridec-4-EN-1-ilaclama (I).

The method of obtaining (4E)-tridec-4-EN-1-racette, including alkylation of malonic ester (E)-1,3-dichloropropanol to obtain diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate, carbamaxepine diethyl[(2E)-3-chlorpro-2-EN-1-yl]propanoate to obtain ethyl(4E)-5-chlorphen-4-enoate, Fe-catalyzed cross-coupling of ethyl(4E)-5-chlorphen-4-enoate with octylacrylamide to obtain ethyl(4E)-tridec-4-enoate, restoration of ethyl(4E)-tridec-4-enoate obtaining (4E)-tridec-4-EN-1-ol, acetylation (4E)-tridec-4-EN-1-ol with the receipt of (4E)-tridec-4-EN-1-racette, characterized in that the Fe-catalyzed cross-CIT the food ethyl(4E)-5-chlorphen-4-enoate with octylacrylamide to obtain ethyl(4E)-tridec-4-enoate carried out in the presence of a catalyst of Fe(acac) 2Cl in a mixture of tetrahydrofuran and N-methylpyrrolidone in the following molar ratio of the reagents [(ethyl(4E)-5-chlorphen-4-INOUT]:[octylacrylamide]:Fe(ASAS)2CL]:[tetrahydrofuran]:[N-organic]=1:1.15:0.01:12:7 for 30 min at a temperature of 0-5°C.



 

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7 ex

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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.

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11 cl, 7 ex

FIELD: industrial organic synthesis.

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FIELD: chemistry.

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: chemistry.

SUBSTANCE: invention relates to an improved method of producing low-molecular substituted phenylbenzoates of general formula: , where R1=C3H7O-, C7H15O-, C8H17O-, C7H|5-, R2=-CHO, -CN, -C3H7, X=H-, HO-, through condensation of an acyl chloride of benzoic acid and substituted phenol in a solvent and subsequent separation of the end product, the acyl chloride of benzoic acid used being a compound of formula: , where R1=C3H7O-, C7H15O-, C8H17O-, C7H15-, the substituted phenol used is a compound of formula: , where R2=-CHO, -CN, -C3H7, X=H-, HO-, the solvent used is methylene chloride; condensation is carried out in the presence of triethylamie while exposing the reaction solution to ultrasound at frequency of 25-30 kHz for 1-1.5 hours at room temperature. The end product is obtained with such high purity that it can be used to modify polymer materials without purification. Recrystallisation from ethanol is sufficient to purify the end product when used as a component of liquid crystal compositions.

EFFECT: invention has the following advantages: 3-5 times shorter duration of the condensation process; 1,6 times increase in output of the product; avoiding preparatory operations associated with absolutisation of pyridine; considerably shorter duration and labour input in purification.

1 tbl, 13 ex

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

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to application of ester compounds of benzoic acid, taken from group, which includes 1-phenylvinyl 4-methoxybenzoate; 1-(4-methoxyphenyl)-vinyl 4-tert-butyl benzoate, 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate, 1-phenylvinyl 4-tert-butyl benzoate, 4-benzoyloxy-2-methoxybenzolsulphonic acid, 3-diethylaminophenyl benzoate and 3-(1-pyrrolidinyl) phenyl benzoate and 3-methoxy salicylate, as component for preparing composition for protection of human organism or animal or material from ultraviolet radiation, containing effective quantity at least one of claimed compounds, as component for preparing composition, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, as component for preparing composition for individual hygiene, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, as component for preparing industrial composition, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, and as component for preparing composition, which at photo-regrouping shows quantity of obtained UV-B radiation.

EFFECT: invention also relates to composition for protecting human or animal organism or protection of material from ultraviolet radiation, contains effective quantity of at least one above mentioned ester compound of benzoic acid.

40 cl, 6 dwg, 33 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and particularly to a method of producing (4E)-tridec-4-en-1-ylacetate. (4E)-tridec-4-en-1-ylacetate is a sex pheromone for tomato moth (Keiferia lycopersicella), which is a dangerous pest for solanaceae. Results of the invention can be useful in chemistry and agriculture. The method of producing (4E)-tridec-4-en-1-ylacetate includes alkylating malonic ester with (E)-1,3-dichloropropene to obtain diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate, decarbalkoxylating diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate to obtain ethyl(4E)-5-chloropent-4-enoate, Fe-catalysed cross-coupling of the ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate, reducing the ethyl(4E)-tridec-4-enoate to obtain (4E)-tridec-4-en-1-ol, acetylation of the (4E)-tridec-4-en-1-ol to obtain (4E)-tridec-4-en-1-ylacetate. According to the invention, Fe-catalysed cross-coupling of ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate is carried out in the presence of a Fe(acac)2Cl catalyst in a mixture of tetrahydrofuran and N-methylpyrrolidone, wit the following molar ratio of reactants [(ethyl(4E)-5-chloropent-4-enoate]:[octylmagnesium bromide]:[Fe(acac)2Cl]:[tetrahydrofuran ]:[N-methylpyrrolidone]=1:1.15:0.01:12:7 for 30 min at 0-5°C.

EFFECT: advantage of the disclosed method is higher output of (4E)-tridec-4-en-1-ylacetate.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for the production of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate, comprising an interaction under reaction conditions between 5-tert-butyl-3-methylcatechol (BMC) and triethylamine and a member selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid derivative, where the derivative of the aromatic carboxylic acid is an aromatic acyl halide, an aromatic anhydride, an aromatic carboxylate salt or any combination thereof; and where the aromatic carboxylic acid is benzoic acid; and forming a composition comprising 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD). Synthesis pathways for a precursor to 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate are provided. The precursor is 5-tert-butyl-3-methylcatechol.

EFFECT: simple and cost-effective method with high yield.

10 cl, 2 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to substituted aromatic phenylenediether of structure

,

in which groups R1-R14 are similar or different , group R1 does not represent isopropyl or tertiary alkyl group, and each of groups R1 and R3 is selected from the group, consisting of non-substituted alkyl group, containing from 1 to 20 carbon atoms, non-substituted alkenyl group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations; and each of groups R2, R4 and R5-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon groups, consisting from 1 to 20 carbon atoms, halogen atom and their combinations, on condition that R2 and R4 do not represent bromine simultaneously. Invention also relates to substituted aromatic phenylenediether of structure (II), in which groups R1-R14 are similar or different, group R2 represents alkyl group, containing from 2 to 20 carbon atoms, and each of groups R5-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations; and all groups R2, R7 and R12 do not represent tert-butyl groups simultaneously. Invention also relates to substituted aromatic phenylenediether of structure (II), in which groups R1-R14 are similar or different, each of groups R1, R3, R4 represents hydrogen atom, group R2 represents hydrocarbon group, containing from 1 to 20 carbon atoms, at least, one of groups R7 and R12 is selected from the group, consisting of halogen atom, primary hydrocarbon group, containing from 1 to 20 carbon atoms, which can optionally contain halogen or silicon atoms or alkoxygroup as substituents, and secondary hydrocarbon group, containing from 1 to 20 carbon atoms, which can optionally contain halogen atoms, silicon atoms or alkoxygroup as substituents; and each of groups R5-R6, R8-R11 and R13-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations.

EFFECT: said compounds are prospective components of improved catalytic systems for production of polymers, based on olefins, which have improved properties.

7 cl, 1 tbl

FIELD: pharmacology.

SUBSTANCE: ophthalmic composition contains a formula compound, where the values for R1 and R2 groups are given in the claims, and an ophthalmologically acceptable carrier. The invention also relates to a method for dry eye treatment, comprising local administration of a therapeutically effective amount of the ophthalmic composition to the eye of the subject in need.

EFFECT: increased efficiency.

20 cl, 6 dwg, 6 ex

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