The way to obtain (z)-1,2-dialkyl-1,2-diethylethylene
(57) Abstract:The invention relates to a method for producing (Z)-1,2-dialkylanilines General formula 1, where R=n-C3H7n-C4H9. These hydrocarbons can be used as monomers in the process of oligomerization, polymerization and intermediates used in paint industry. The proposed method lies in the interaction dialkylamides acetylenes of the formula R-CC-R triethylaluminium (Et3A1) in the presence of zirconatetitanate (Cp2ZrC12) as a catalyst in their molar ratio, respectively, 10: (10:20): (0,1-0,5). The interaction is carried out at normal conditions in the environment of hexane with stirring for 8 hours Then to the reaction mass at 0oTo add atylosia (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60) and the reaction mass is stirred for 16-20 h at room temperature with subsequent hydrolysis of the reaction mixture with hydrochloric acid. Effect: increase of the compounds of formula 1 of disubstituted acetylenes with high Regio - and stereoselectivity. 1 PL.The present invention relates to the field of organic chemistry, specifically to the way the
Unsaturated hydrocarbons and their derivatives can be used as starting monomers in the processes of oligomerization, polymerization, as well as intermediates used in paint industry.The known method (R. D. Gardner, M. Narayana, J. Org. Chem., 1961, V. 26, P. 3518) obtain Tetra-substituted olefins interaction getdialogwindow with metallic magnesium in ether scheme
< / BR>The known method does not allow to obtain (Z)-1,2-dialkyl-1,2-diethylethylene.The known method (E. Negishi, N. Okukado, A. O. King, D. E. Van Horn, C. J. Spiegel, J. Am. Chem. Soc., 1978, V. 100, p. 2254) obtain Tetra-substituted olefins interaction disubstituted acetylenes with equimolar number of trimethylaluminum (Me3Al) in the presence of catalytic amounts of zirconatetitanate (Cp2ZrCl2) at room temperature and then adding to the reaction mass of alkenyl-, aryl - or alkylhalogenide, equimolar amount of zinc chloride (ZnCl2), catalytic amounts of palladium acetylacetonate or Nickel (Pd(acac)2or Ni(acac)2) and triphenylphosphine (PH3P) using the pattern
< / BR>The known method does not allow to obtain (Z)-1,2-dialkyl-1,2-diethylethylene.We propose a new way to obtain (Z)-1,2-dia is ENES RCCR (octene-4, decina-5) with triethylaluminium (Et3Al) in the presence of catalytic amounts of zirconatetitanate (Cp2ZrCl2), taken in a molar ratio 10:(10-20):(0,1-0,5) accordingly, predominantly 10:15:0,3, at room temperature (23-25oC) and atmospheric pressure in hexane with stirring for 8 hours, followed by adding to the reaction mass at a temperature of ~ 0oWith tiltability (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60), mostly 10:50, with stirring the reaction mass for 16-20 hours, preferably 18 hours, at room temperature (23-25o(C) with subsequent hydrolysis of the reaction mixture model HC1 solution. Get (Z)-1,2-dialkyl-1,2-diethylethylene 1 output 45-66%.< / BR>Use the specified reaction smaller quantities of E3Al and tiltability (EtTs) reduces the yield of the target product 1. Use in the reaction of large quantities of tiltability (EtTs) does not lead to a significant increase in the yield of the target product 1. At a higher temperature (for example, 60oC) the yield of the target products is not increased, and at a lower temperature (for example, 0oC) decreases the reaction rate.Without triethylaluminum and tiltability (EtTs) Southsea.Significant differences of the proposed method:
1. In the known method used by alkenyl-, aryl - or alkylhalogenide, while the proposed use atylosia (EtTs).2. In the known method as catalysts zirconatetitanate (Cp2ZrCl2), acetylacetonate, palladium or Nickel (Pd(acac)2or Ni(acac)2in the presence of socializaton of zinc chloride, while the proposed uses only the catalyst zirconatetitanate (Cp2ZrCl2).4. The proposed method allows to obtain (Z)-1,2-dialkyl-1,2-diethylethylene, whereas according to the method are formed 1,2,2-trialkyl-1 alkenyl(aryl, quinil)ethylene.The advantages of the proposed method:
1. In contrast to known methods proposed allows to obtain (Z)-1,2-dialkyl-1,2-diethylethylene 1 of disubstituted acetylenes with high Regio - and stereoselectivity.The method is illustrated by examples:
EXAMPLE 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, inert gas load 10 ml of hexane, 10 mmol decina-5, 15 mmol Et3Al and 0.3 mmol Cp2ZrCl2, stirred for 8 hours at room temperature) and stirred the reaction mass for 18 hours at room temperature (23-25oC). The reaction mass hydrolyzing model HC1 solution, the organic layer is separated from the water. From the organic layer emit (Z)-1,2-di(n-butyl)-1,2-diethylethylene with yield 59%.The spectral characteristics of the (Z)-1,2-dialkyl-1,2-diethylethylene
< / BR>An NMR spectrum13With (, m D.): 14,15 (Cl), 24,43 (C2), 31,06 (C3), 31,64 (C4), 134,46 (C5), 23,19 (C6), 13,89 (C7). M+196.Other examples of the method shown in the table.All experiments were performed at room temperature (23-25oC). As a solvent used hexane at 10 ml The way to obtain (Z)-1,2-dialkyl-1,2-diethylethylene General formula
< / BR>where R=n-C3H7n-C4H9,
characterized in that dialkylamino acetylene formula RCCR interact with triethylaluminium (Et3Al) in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in a molar ratio RCCR:Et3Al:Cp2ZrCl2= 10:(10:20):(0,1-0,5) under normal conditions in the environment of hexane with stirring for 8 h and then adding to the reaction mass at a temperature of 0oWith tiltability (EtTs), taken in a molar ratio RCCR:EtTs = 10:(40-60) with stirring the reaction mass for 16-20 h at room those who
< / 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
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