The method of receiving dihydromyrcene from the cis-pinane
(57) Abstract:The invention relates to organic chemistry, in particular to a method for dihydromyrcene - intermediate in the synthesis of aromatic substances. Dihydromyrcene produced by the catalytic isomerization of CIS-pinane at a temperature of 390-460oWith out using as catalyst the carbon material with a developed surface. It is preferable to use activated carbon Sibunit, filamentous carbon. Technical result - increase the selectivity of the process, simplifying the selection of the target product. 1 C.p. f-crystals, 1 table. The invention relates to organic chemistry, in particular to a method for production of CIS-pinane of dihydromyrcene - an intermediate in the synthesis of a number of aromatic substances.Dihydropyran is used as an intermediate in the synthesis of a number of aromatic substances [Lemee L, Ratier, M.; Duboudin J.-G. and Delmond Century Flash vacuum thermolysis of terpenic compounds in the pinane series. // Synth. Commun. 1995. V. 25. N 9. R. 1313]. One of the methods of its receipt - thermal isomerization of CIS-pinane [Lemee L. Ratier M, Duboudin J.-G. and Delmond Century . Flash vacuum thermolysis of terpenic compounds in the pinane series. // Synth. Commun. 1995. V. 25. N 9 R. 1313; J. Tanaka, T. Katagiri and K. Ozawa. thermal isomerization of pinane and its products. // Buil. Chem. Soc. Japan, 1971. V. 44. N 1. R. 130; Rienacker R., G. Ohloff Optisc products are Eridani, having very close with the target product boiling point, which complicates its release, and also TRANS-pinan and products of its isomerization.Closest to the proposed method is thermal isomerization of CIS-pinane at temperatures 385-500oWith quartz [J. Tanaka, T. Katagiri and K. Ozawa. thermal isomerization of pinane and its products. // Bull. Chem. Soc. Japan, 1971, V. 44. N 1. P. 130]. The reaction is carried out in a quartz reactor with a diameter of 20 and a length of 300 mm at a feed rate of Pinna 21 ml/hour. With increasing reaction temperature from 400 to 500oWith the conversion of Pinna increases from 27 to 97% and the selectivity for dihydromyrcene falls from 68 (425o(C) up to 26%.The invention solves the problem of increasing the selectivity of the process, reducing the amount of by-products, simplify the selection of the target product.The problem is solved by a method of catalytic isomerization of CIS-pinane, which is carried out at a temperature of 390-460oWith out using as catalyst the carbon material with a developed surface. As the carbon material used activated carbon Sibunit, filamentous carbon.The main by-products of ridenow the literature data are increasing the representation of ridenow.The hallmark of this method is the use as catalyst of carbon materials with a developed surface.The process of the proposed method allows to obtain dihydromyrcene with selectivity 88-95% conversion 24-35%. The invention is illustrated by the following examples.Example 1
In running the install through the layer of filamentary carbon (5 g) at a temperature of 390oWith miss a pair of CIS-pinane at a rate of 10 l/h as the carrier gas used argon. Dihydromyrcene from the reaction mass produce rectification. Conversion and product selectivity of the process is indicated in the table.Examples 2-9
The process was carried out as in example 1, varying the catalyst and the temperature. The data given in the table.Examples 10-12 illustrate the method on the prototype. The data given in the table.Data examples indicate the achievement of the objectives. 1. The method of receiving dihydromyrcene catalytic isomerization of CIS-pinane at a temperature of 380-460o, Characterized in that the catalyst used carbon material with a developed surface.2. The method according to p. 1, otlichalis the
< / BR>These compounds may find application in thin organic synthesis and in the synthesis of biologically active preparations containing substituents exclusively threo-configuration, special polymers
R = C4H9C6H13C9H19
FIELD: organic chemistry.
SUBSTANCE: alkyl(benzyl)allene of general formula (R-= =), wherein R is n-C2H11, n-C6H13,CH2Ph is reacts with EtMgBr, Mg, Cp2TiCl2, methyl iodide and CuCl in argon atmosphere in tetrahydrofuran medium for 18-22 hours. Total yield of target products is 69-86 %.
EFFECT: selective method for production of 3,6-dimethyl-4,7-dialkyl(phenyl)-2,6-octadiens.
1 tbl, 1 ex
FIELD: obtaining of unsaturated hydrocarbons.
SUBSTANCE: method involves obtaining a mixture, containing one or more cyclic unsaturated hydrocarbons and surplus from one or more non-cyclic unsaturated hydrocarbons, where the molar ratio of the non-cyclic unsaturated hydrocarbons to the cyclic unsaturated hydrocarbons ranges from 5:1 to 3:1. The indicated cyclic unsaturated hydrocarbons have ΔG less than 0 at 25°C and have a ring structure, containing "x" atoms of carbon. The method also involves reaction of a cross-metathesis mixture of one or more cyclic unsaturated hydrocarbons and one or more non-cyclic unsaturated hydrocarbons. The method is characterised by that, the cross-metathesis stage is carried out under effective conditions with formation of a mainly non-cyclic unsaturated hydrocarbon product, containing one molecule of the indicated cyclic unsaturated hydrocarbon and more than "x" carbon atoms. The indicated unsaturated hydrocarbon products contain 10-16 atoms of carbon.
EFFECT: cheap method, with high selectivity of obtaining non-cyclic unsaturated compounds, containing from ten to sixteen carbon atoms.
24 cl, 10 ex, 9 tbl, 4 dwg
SUBSTANCE: invention relates to a method for synthesis of 1-aminomethyl-α,ω-alkadiines of general formula (1): , where R2N = piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC≡C-(CH2)n-C≡CH, where n=4, 6, 8, react with gem-diamines R2NCH2NR2, where R2N is as defined above, in the presence of a copper (I) chloride catalyst (CuCl), taken in molar ratio α,ω-diacetylene: gem-diamine: CuCl=10:10: (0.3-0.7),preferably 10:10:0.5 mmol without a solvent at temperature of 80°C and atmospheric pressure for 4-5 hours. 1-aminomethyl-α,ω-alkadiines can be used in fine organic synthesis and particularly in synthesis of scarce polycyclic compounds, as well as in synthesis of biologically active substances.
EFFECT: method increases output of the desired products.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method of separating isopentane-isoamylene-isoprene-containing hydrocarbon fractions or butane-butylene-divinyl hydrocarbon fractions obtained at the first step of two-step dehydrogenation of corresponding paraffin hydrocarbons, involving separation of paraffin-olefin-diene fraction obtained at the first dehydrogenation step through extraction rectification, and is characterised by that a vapour stream is extracted from a desorber via lateral collection, where the said vapour stream contains large amount of diene, and after condensation, said stream is taken for extraction of the diene end product at the second extraction rectification step, and an olefin fraction which does not contain diene is collected from the top of the desorber and taken to the second dehydrogenation step.
EFFECT: use of said method increases output of the end product.
1 cl, 2 ex, 1 dwg
SUBSTANCE: invention relates to a method for synthesis of asymmetric α,ω-di(aminomethyl)alkadiines of general formula (1): where R2N = piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC=C-(CH2)n-C=CH, where n=4, 6, 8, react with an equimolar amount of N,N,N1N1-tetramethyldiaminomethane (bisamine) in the presence of a catalyst 6-hydrate samaric nitrate (Sm(NO3)2*6H2O), taken in molar ratio of α,ω-diacetylene: bisamine: (Sm(NO3)2*6H2O) =10:10:(0.3-0.7), preferably 10:10:0.5 moles, without a solvent at temperature 80°C and atmospheric pressure for 3 hours, with subsequent addition to the reaction mass of gem-diamine R2NCH2NR2, where R2N is as defined above, in amount which is equimolar to bisamine and stirring the reaction mass for 3-5 hours. The asymmetric α,ω-di(aminomethyl)alkadiines can be used in fine organic synthesis, particularly for synthesis of scarce polycyclic compounds.
EFFECT: improved synthesis of said derivatives.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing substituted or unsubstituted 1,7-diolefins of formula (9) in which R7-R12 independently denote hydrogen, an alkyl with 1-4 carbon atoms or halogen, through hydrodimerisation of non-cyclic olefins with at least two conjugated double bonds in the presence of a reducing agent and a catalyst, characterised by that the reducing agent used is formic acid and/or formate, and the catalyst used is a carbene metal complex which contains group VIII-X metals and at least one carbene ligand of formula (1) or (2): in which R1 R2 denote -(CH2)n-B, B denotes a monocyclic or polycyclic aryl group with 6-14 carbon atoms or a monocyclic or polycyclic heterocycle with 5-14 carbon atoms and heteroatoms, which contains 1-3 heteroatoms, selected from a group comprising nitrogen, oxygen or sulphur, n is a number ranging from 0 to 4, R3, R4, R5 and R6 denote hydrogen, alkyl, heteroaryl, aryl, -CN, -COOH, -COO-alkyl, -COO-aryl, -OCO-alkyl, -OCO-aryl, -OCOO-alkyl, -OCOO-aryl, -CHO, -CO-alkyl, -CO-aryl, -NH2, -NH(alkyl), -N(alkyl)2, -NH(aryl), -N(aryl)2, fluoro, chloro, bromo, iodo, -OH, -CF3, -NO2, - ferrocenyl, -SO3H or -PO3H2, wherein alkyl denotes an alkyl group with 1-12 carbon atoms, aryl denotes an aryl with 5-14 carbon atoms, and substitutes R3 and R4 may also be part an aliphatic or aromatic ring bound by a bridge, where substitutes R1 and R2 may be identical or different, substituted or unsubstituted, and substitutes R3, R4 R5 and R6 may also be identical or different, substituted or unsubstituted.
EFFECT: besides easy handling of the catalyst, the invention is also characterised by high efficiency.
16 cl, 12 tbl, 14 ex
SUBSTANCE: invention relates to a method of producing α,ω-di(aminomethyl)alkadiines of general formula (1) , where R2N=piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC=C-(CH2)n-C≡CH, where n=4, 6, 8 react with gem-diamines R2NCH2NR2, where R2N is as described above, in the presence of a copper (I) chloride (CuCl) catalyst, taken in molar ratio α,ω-diacetylene: bisamine: CuCl=10:20:(0.3-0.7), preferably 10:20:0.5 mmol, at temperature 80°C and atmospheric pressure for 4-6 hours. α,ω-aminomethylated diacetylenes can be used in fine organic synthesis, particularly for producing hard-to-get polycyclic compounds.
EFFECT: method increases output of the desired products.
1 cl, 1 ex, 1 tbl