The method of obtaining ala-4z-enes
The invention relates to the field of organic chemistry, namely, the method of production of Ala-4Z-ENES. Essence: Ala-4Z-ENES General formulawhere R = n-C6H13; n8H17; n9H19receive interaction of terminal allenes General formula R-CH= C= CH2where R is n-C6H13; n8H17; n9H19with triethylaluminium in the presence of a catalyst of zirconatetitanate in the amount of 2-6 mol.% with respect to the terminal Allen in an argon atmosphere at room temperature and atmospheric pressure in the environment of methylene chloride, for 8-12 h with subsequent acid hydrolysis of the reaction mass. The molar ratio of terminal allene: triethylaluminium is 10: (10-14). Effect: simplified method. table 1. The invention relates to the field of organic chemistry, specifically to a method for Ala-4Z-ENES General formula (1)where R= n-C6H13; n-C8H17the h9H19Z-Olefins and their derivatives can be used in thin organic synthesis, and also to obtain epoxides, alcohols, ketones, interest in production a method of obtaining the Z-olefin (Tolstikov, A., Dzhemilev, U. M., Vostrikova O. S. , Gimaev A. R., Uman L. I. a method of obtaining a Z-olefins. Auth. mon. 1657479 from 22.02.1991) gidrometeorologia disubstituted acetylenes (R--R) using triisobutylaluminum (VI3iAl) and isobutylamine (BuiMgBr), taken in a molar ratio BuiMgBr:Bu3iAl:R--R=l:(2.53.75): 2.5, in the presence of a catalyst Cp2TiCl2at room temperature (~20oS, 0.5 h) in sulphuric ether as solvent followed by acid hydrolysis of the reaction mass schemeThere is a method allows to obtain Ala-4Z-ENES with the condition of their involvement in the response of hard-Ala-4-ENES with a fixed position of the triple bond exclusively in the 4mposition.The known method (M. M. Bhagwat, D. Devaprabhakara. Selextive hydrogenation of allenes with chlorotris(tripnenylphosphine)rhodium catalyst. Tetrahedron Lett. , N 15, 1391-1392, 1972) receiving Ala-4Z-ENES by hydrogenation of 1,3-disubstituted 1,2-dienes (internal allenes) with hydrogen at atmospheric pressure in benzene at a temperature of 60oC for 24 h in the presence of 0.5 mol.% Tris(triphenylphosphine)radioid as a catalyst schemeOffers an improved method of obtaining Ala-4Z-ENES.The method consists in the interaction of terminal allenes General formula R-CH=C=CH2where R = n-C6H13; n8H17; n9H19with triethylaluminium (1t3), taken in a molar ratio of terminal allene: AlEt310:(1014), preferably 10:12, in the presence of a catalyst of zirconatetitanate (CpZrCl2) in an amount of 2 to 6 mol.% with respect to the terminal Allen, preferably 4 mol.%, in an argon atmosphere at room temperature (~ 20oC) and normal Dawley in methylene chloride (CH2CL2as the solvent for 8-12 hours, preferably 10 hours with subsequent acid (~ 10% model HC1) by hydrolysis of the reaction mass. The total yield of Ala-4Z-ENES (1) is 82-96%.The reaction proceeds according to the schemewhere R = n-C6H13; n-C8H17; n-C9H19
Ala-4Z-ENES (1) are formed only with the participation 1t3, terminal allenes and zirconium catalyst Cp2ZrCl2. In the presence of other aluminum compounds (e.g., Bu2iAlCl, VI3iA1,RA (for example, Zr(acac)4, ZrCl4Cp2TiCl2Pd(acac)2, Ni(acac)2, NiCl2, Fe(acac)2target products (1) are not formed.The conduct of a specified reaction in the presence of zirconium catalyst Cp2ZrCl2more than 6 mol.% does not lead to a significant increase in the yield of the target products (1). The use of the catalyst is less than 2 mol.% reduces the output of the Z-olefin (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. The reaction was carried out at a temperature of ~20oC. At a higher temperature (e.g., ~40o(C) has not been a significant increase in the yield of the target product, and at a lower temperature (for example, 0oC) decreases the reaction rate.Changing the ratio of initial reagents in the direction of increasing the content 1t3in relation to the original 1-substituted Allen does not lead to a significant increase in the yield of target products (1).The reaction was performed using methylene chloride as solvent. In other solvents (for example, aliphatic or aromatic) decreases the regiospecificity of the reaction and, along with Ala-4Z-s (1), we observed the formation of significant amounts of 1-atill-1-ENES.Su is on the more accessible terminal allene (R-==), triethylaluminium (1t3), which is produced in the country on an industrial scale, the reaction proceeds at room temperature (~20o(C) in methylene chloride (CH2CL2in the presence of a catalyst Cp2ZrCl2.In the known method are used less accessible 1,3-disubstituted 1,2-diene (the internal alleni), gaseous hydrogen, the reaction proceeds at elevated (60oC) temperature in benzene (C6H6in the presence of a rhodium catalyst (RhCl(PPh3)3).The proposed method has the following advantages.The method allows to obtain with high Regio - and stereoselectivity Ala-4Z-ENES (1), on the basis of available reagents (terminal allene and 1t3in mild conditions (~ 20o(C) in the presence of available catalyst Cp2ZrCl2.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 5 ml of methylene chloride (CH2Cl2), 10 mmol of 1,2-nonadiene, 0.4 mmol Cp2ZrCl2at a temperature of ~0oWith 12 mmol AlEt3, stirred for 10 hours at room temperature (~20oC) hydrolyzing -10% model HC1. And the 81-82o(20 Torr), IR spectrum (cm-1): 3080, 2920, 2850, 2300, 1640, 1460, 910, 720. An NMR spectrum1With (, M. D.): 0.77-0.92 (m, 6N, CH3), 1.06-1.55 (m, 10H, CH2), 1.76-1.99 (m, 4H, CH2-C=C), 5.26-5.36 (m, 2H, CH=CH). An NMR spectrum13With (CDCl3,, M. D.): 13.89 (K1), 23.00 (t2), 29.11 (t3), 129.71 (d4), 130.17 (With D.5), 27.35 (t6), 29.89 (t7), 29.43 (t8), 31.90 (t9), 22.74 (t10), 14.15 (K11). M+154.Other examples of the method shown in the table.The reaction was carried out at room temperature (~20o(C) in methylene chloride.
The method of obtaining Ala-4Z-ENES General formula
where R is n-C6H13; n8H17; n9H19,
characterized in that the terminal allene General formula
R-CH= C= CH2,
where R is n-C6H13; n8H17; n9H19,
interact with triethylaluminium A1Et3in a molar ratio of terminal allene: AlEt310: (10-14), in the presence of a catalyst zircon-candalaria (Cf2SrCl2) in an amount of 2-6 mol. % the e methylene chloride as solvent followed by acid hydrolysis of the reaction mass.
FIELD: regeneration of heat and extraction of impurities.
SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.
EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.
19 cl, 3 tbl, 4 dwg, 5 ex
FIELD: petrochemical processes.
SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.
EFFECT: increased yield of desired product.
41 cl, 4 dwg, 5 ex
FIELD: petroleum chemistry.
SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.
EFFECT: method for production of target product of increased yield.
10 cl, 1 tbl, 3 dwg, 17 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.
EFFECT: improved performance characteristics of catalyst at low cost.
23 cl, 5 tbl, 22 ex
FIELD: petroleum chemistry.
SUBSTANCE: 1,3-butadiene is exposed to telomerization with telogene of general formula H-X-Y-H, wherein X represents oxygen, sulfur, nitrogen or phosphorus; Y represents carbon, nitrogen or silicium; and X and Y optionally may have substituents according to valence thereof to form telomer of general formula H2C=CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Said telomer is hydrolyzed to 1-substituted 2-octene of formula H3C-CH-CH2-CH2-CH2-CH=CH-CH2-X-Y-H. Substituted 2-octene is splitted to produce 1-octene.
EFFECT: improved method for production of 1-octene.
28 cl, 4 ex
FIELD: organic chemistry.
SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.
EFFECT: improved method for production of linear olefins.
12 cl, 3 tbl, 1 dwg, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: before olefin-containing raw material is brought into contact with isomerization catalyst, one or several components of the raw material are subjected to preliminary treatment coming into contact with preliminary treatment material containing zeolite with pore size at least 0.35 nm. Initial olefin is, in particular, vinylidene olefin of general formula CH2=C(R1)R2, wherein R1 and R2 independently represent alkyl groups having at least 2 carbon atoms so that molecular structure includes at least one allyl hydrogen atom.
EFFECT: increased selectivity.
10 cl, 1 tbl, 11 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: vinylidene olefin-containing starting material is brought into contact with isomerization catalyst consisting of molecule sieve in H form, which contains pore larger than 0.6 nm.
EFFECT: increased selectivity of catalyst.
12 cl, 1 tbl, 11 ex
FIELD: petrochemical processes.
SUBSTANCE: liquid olefin-containing feed stream is brought into contact with activated catalyst composed of basic metal oxides or essentially basic metal oxides under olefin isomerization conditions. Catalyst has original olefin isomerization activity and contains activity affecting admixture in amount not exceeding that which would lead to reduction in catalytic activity with a rate of about 0.075% of hourly conversion loss as measured under 1-butene-to-2-butene isomerization process conditions, said activity affecting admixture being on including sulfur, phosphorus, at least one transition metal, or combination thereof.
EFFECT: increased catalytic activity.
34 cl, 5 dwg, 3 tbl, 2 ex
FIELD: petrochemical processes.
SUBSTANCE: branched olefins from isomerization feedstock in the form of linear olefin/paraffin mixture containing 5 to 50% of linear olefins having 7 to 28 carbon atoms are obtained in the first isomerization stage, wherein carbon backbone of linear olefins in the isomerization feedstock is isomerized when in contact with isomerization catalyst, which is effective to isomerize carbon backbone in linear olefin blend to convert the latter into olefin blend, wherein average number of branches in molecule chain is at least 0.7, followed by second stage, wherein branched and linear molecules are separated, the former being essentially olefinic molecules and the latter olefinic and/or paraffin molecules. Resulting branched olefins are served as starting material for production of alcohols and alkylbenzenes.
EFFECT: enabled olefin branching control.
6 cl, 4 tbl, 3 ex