The method of obtaining trans-3,4-tetrahydrothiophene
The invention relates to a method for producing TRANS-3,4-dialkylacrylamide. TRANS-3,4-dialkylacrylamide produced by interaction of 1-ethyl-TRANS-3,4-dialkylaminomethyl (ADC) with thionyl chloride (SOCl2) in a molar ratio ADC: SOCl2=10:(1014) in hexane solution at -40oC for 6-8 hours the Invention allows the reaction at a low temperature using thionyl chloride instead of toxic benzene. table 1. The invention relates to the field of organic chemistry, in particular to a method for producing TRANS-3,4-dialkylacrylamide General formula (1)where R=n-C4H9the h5H11the h7H15.These compounds can be used as accelerators in the vulcanization of rubber, additives for lubricating oils and fuels.The known method ( . Dzhemilev, U. M., A. Ibragimov,, Ergaliev M. N., Muslumov P. P. Synthesis and transformations of metallocycles. Message 16. Synthesis of a new class of acyclic alyuminiiorganicheskikh connections - threo-2,3-disubstituted 1,4-volumebutton using zirconium catalysts. WPI. An. Ser. chem., 1995, 8, S. 1561-15 the butane with a threefold excess of elemental sulfur (S8) in boiling benzene (~ 80o(C) in argon atmosphere for 8 hours. The target products are formed from the outputs 62-78% schemewhere R=alkyl.The disadvantage of this method is the increased fire hazards of the process, because the reaction takes place in boiling benzene. In addition, benzene is a toxic solvent with mutagenic properties.The known method (. Dzhemilev, U. M., A. Ibragimov,, Ergaliev M. N., Muslumov P. P. Synthesis and transformations of metallocycles. Message 14. Stereoselective synthesis of TRANS-3,4-disubstituted dialkylacrylamide Izv. An. The series of chem. , 1994, 2, S. 276-278) to obtain TRANS-3,4-disubstituted dialkylacrylamide (1) the interaction of 1-ethyl-TRANS-3,4 - dialkylaminomethyl with a threefold excess of elemental sulfur (S8) in solution in dry benzene in an argon atmosphere at a temperature of ~80oC for 6-8 hours with outputs 65-80% schemewhere R=alkyl.The disadvantages of this method: 1. Increased fire hazards of the process, because the reaction is carried out in boiling benzene.2. Carrying out the reaction using toxic benzene, which has mutagenic properties.3. Increased consumption of one of the C-3,4-dialkylanilines.We propose a new method for production of TRANS-3,4-dialkylacrylamide.The method consists in the interaction of 1-ethyl-TRANS-3,4-dialkylaminomethyl (ADC) with thionyl chloride (SOCl2), taken in a molar ratio ADC:SOCl2=10:(1014), preferably 10:12, in hexane solution at -40oC for 6-8 hours, preferably 7 hours. The output of TRANS-3,4-dialkylacrylamide is 73-82%. The reaction takes place according to the schemewhere R=n-C4H9the h5H11n-C7H15.Conducting the process at a higher temperature (for example, 0oC) reduces the selectivity of the reaction. Carrying out the process at lower temperatures (e.g. -50oC) reduces the reaction rate. Changing the ratio of initial reagents in the direction of increasing the content of SOCl2with respect to the ADC does not lead to a significant increase in the yield of target products (1).Significant differences of the proposed method.If in the known method for the sulfonation used a three-fold excess of elemental sulfur (S8), the reaction proceeds at elevated temperatures (~80o(C) in boiling benzene. In the proposed spooney temperature (-40o(C) in hexane.The method is illustrated by the following examples.EXAMPLE 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, an argon atmosphere was placed 10 mmol 1-ethyl-TRANS-3,4-di(n-butyl)aromaticity in 10 ml of hexane at a temperature of -40oWith added 12 mmol of thionyl chloride (SOCl2) and stirred for 7 hours at this temperature. Upon completion of the reaction the reaction mass is treated with 5% Hcl, allocate TRANS-3,4-di(n-butyl)tetrahydrothiophene with the release of 78%.Spectral characteristics of TRANS-3,4-di(n-butyl)-tetrahydrothiophene (1):
An NMR spectrum1N (, M. D.): 0,92 (t, 6N, CH3), 1,12-at 1.91 (m, 14N, CH, CH2), 2,33-2,64, 2,86-3,06 (m, 4H, CH2S).An NMR spectrum13With (, M. D.): 36,51 t (1), 48,77 d (2), 32,73 t (3), 30,21 t (4), 22,94 t (5), 14,06 to (5). M+200.Other examples of the method shown in the table.Add thionyl chloride and subsequent reaction of sulfonation was carried out at -40oWith in hexane.
The method of obtaining TRANS-3,4-dialkylacrylamide General formula
14) in hexane solution at -40oC for 6-8 hours
FIELD: organic chemistry.
SUBSTANCE: claimed method includes interaction of disubstituted acetylenes with n-BuMgCl and thionyl chloride SOCl2 in presence of zircon acetyl dichloride in argon atmosphere at room temperature in diethyl ether for 6-10 hours. Yield of target product is 48-58 %. Compounds of present invention are useful in food processing industry, as biologically active compounds, colorants, additives for oils and hydraulic liquids.
EFFECT: simplified method with increased yield; accessible and non-toxic raw materials.
1 tbl, 9 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 2,3,4,5-tetraalkylthiophenols. Method involves interaction of disubstituted acelylenes with n-BuMgCl and sulfur monochloride (S2Cl2) in the presence of zirconacene dichloride as a catalyst, in argon atmosphere, at room temperature in diethyl ether medium for 6-10 h. Proposed method provides preparing the end product with the yield 40-54% by simplified technology and with using easily available and nontoxic raw. Synthesized compounds can be used in food processing industry, as biologically active compounds, dyes, addition agents to oils and hydraulic liquids.
EFFECT: improved method of synthesis.
1 tbl, 9 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 2,3,4,5-tetraalkylthiophenes. Method involves interaction of disubstituted acetylenes with R'-AlCl2 and SOCl2 in the presence of metallic Mg and zirconacene dichloride as a catalyst in argon atmosphere in tetrahydrofuran medium for 11-15 h. Proposed method shows the simplified technology and uses easily available and nontoxic raw and provides preparing the end product with the yield about 47-54%. Synthesized compounds can be used in food industry, as biologically active compounds, dyes, addition agents to oils and hydraulic liquids.
EFFECT: improved method of synthesis, valuable properties of compounds.
1 tbl, 10 ex
SUBSTANCE: invention relates to organic chemistry, specifically to a method of producing 2,3,4,5-tetraalkylthiophenes, which can be used as an intermediate product during synthesis of dyes, biologically active compounds, as well as components of flavour boosters in food, additives to oil and hydraulic fluids. A method is described for producing 2,3,4,5-tetraalkylthiophenes, involving reaction of disubstituted acetylenes with n-BuMgCl in the presence of a zirconocene dichloride catalyst in an argon atmosphere at room temperature in diethyl ether for 2-4 hours with subsequent addition of elemental sulphur S8 in equimolar amount with respect to BuMgCl and boiling in benzene for 5 hours.
EFFECT: obtaining end product with high selectivity using simple technique due to exclusion of difficult to access 1,4-butadiene diiodide, highly pyrophoric n-butylithium and highly toxic carbon disulphide.
1 cl, 1 tbl, 9 ex
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention refers to new 2-phenylethylaminosubstituted derivatives of carboxamides of formula (I) where J, J, W, R, R0, R1, R2, R3 and R4 have values, such as specified in cl. 1 of the patent claim, and to their pharmaceutically acceptable salts, pharmaceutical compositions containing them as sodium and/or calcium channel modulators for prevention, relief and treatment of a broad range of pathologies including neurological, mental, cardiovascular, inflammatory, ophthalmologic, urological and gastrointestinal diseases.
EFFECT: preparation of new 2-phenylethylaminosubstituted derivatives of carboxamides.
22 cl, 1 dwg, 10 tbl, 117 ex
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention relates to amide of δ-amino-γ-hydroxy-ω-arylalcane acid of formula and its pharmaceutically acceptable salts. Also described are pharmaceutical compositions, which include said compounds, and application of said compounds for preparation of medication, intended for treatment of pathological states, associated with renin activity, in particular for treatment of hypertension.
EFFECT: obtaining pharmaceutically acceptable salts, which possess rennin-inhibiting ability.
21 cl, 161 ex
SUBSTANCE: invention relates to a method of obtaining 2-dodecyl-5-(2,3,7,8-bis-(9H, 10H-anthracene-9,10-diyl)pyren-1-yl)thiophene, which consists in the interaction of 1-bromopyrene with 2-dodecyl-5-tributylstannylthiophene by the Stille reaction with obtaining the first half-product 5-(pyren-1-yl)-2-dodecylthiophene, with the following bromination of the latter with obtaining the second half-product 2-dodecyl-5-(3,6,8-tribromopyren-1-yl)thiophene, its following heating with anthracene and sodium amine in the argon atmosphere.
EFFECT: developed is the novel method of synthesising a derivative of pentasubstituted pyrene with the application of a cross-combination by Stille and highly reactive arine intermediates, which in a result leads to the synthetic availability of pentasubstituted pyrene derivatives, which can be applied for distant detection of nitroaromatic compounds present on surfaces, in solutions of nonpolar solvents, water and in air.
2 dwg, 1 tbl