SU1754705A1 - Method of n-octa-2,7-dienylamines synthesis - Google Patents

Abstract

The invention relates to amines, in particular to methods for the preparation of M-octa-2,7-dienylamines, used for the synthesis of surfactants, biologically active compounds. The goal is to increase the yield of the target product. Synthesis is carried out by reaction of butadiene with a secondary amine in an organic solvent, such as benzene, toluene, alcohol, acetonitrile, methanol, in the presence of a Pd (OCOR) 2 catalyst, where R is CH3, (CH2) CHS3, (CH2) i4CH3, (CH2 ) 1bCH3, C6H5, boron trifluoride etherate and tertiary phosphoins PR g, where phenyl, n-butyl, cyclohexyl. at a molar ratio of reagents 1 (7-20) :( 1-3), respectively, at 60-70 ° C. These conditions allow an increase in the yield of 1700 to 1715-3233 g / g of Pd. At the same time, the process temperature decreases from 100 to 60-70 ° C. 2 tab.

Description

The invention relates to an improved process for the preparation of linear tertiary amines - M-octa-2,7-dienylamines, used to synthesize surfactants, biologically active compounds, by catalytic telomerization of butadiene (BD) with aliphatic and aromatic secondary amines.

Known methods for the preparation of octadiene amines by telomerization of butadiene with 6 amines in the presence of divalent nickel compounds with cocatalysts of the type Nl (Acac) 2 / PhP) OR) 2 / NaBH4, Nl (ROCO) 2 / PhP (OR) 2 / NaBH4, R Alk Ph. with the yield of the target products at 90-100 ° C for 4-1 ERP, not more than 300 g per 1 g of nickel and a high content of by-products — P2MC4H butenylamines (35-95%).

The closest to the proposed method is the method of producing M-octa-2,7-dienylamines by telomerizing butadiene with

aliphatic amines in the presence of bis- (acetylacetonate) palladium and triphenylphosphine in methanol at 100 ° C.

The disadvantages of this method include the relatively low yields of the target products (1700 g / g Pd) under relatively hard, (100 ° C) conditions for metal complex catalysis.

The aim of the invention is to increase the yield of the target products.

The goal is achieved by the fact that according to the method, M-octa-2,7-dedylamines are obtained by telomerizing butadiene with secondary amines in an organic solvent, such as benzene, toluene, kolume, methanol, acetonitrile, in the Presence of a catalyst, palladium carboxylate of the general formula: Pd (OCOR) 2, where R СНз, (СН2) зСН3, (CH2) i4CH3, (СН2) 1bСНз, СБН5, and also boron trifluoride ether and tertiary phosphine of the general formula PP h. where R Ph,

but

four

3

cl

nVi, Su in molar ratio, equals 1: (7-20): (), respectively, at 60-70 ° С.

PRI me R 1. A solution of 0.076 is sequentially charged into a 300 ml stainless steel autoclave in an argon atmosphere at -5 ° C. g (0.3 mmol) of bis- (acetate) palladium and 0.079 g (0.3 mmol) of triphenylphosphine in 30 ml of absolute benzene, 85 ml (1 mol) of the recondensed liquefied butadiene, 52 ml (0.5 mol) of dry diethylamine and 0.24 ml (b mmol) of trifluoride boron etherate, distillate and desiccant in argon. The autoclave is closed and thermostatic at 70 ° C for 7 hours. After cooling the autoclave to room temperature and unloading, the spent catalyst is separated, passing the reaction mass through an aluminum oxide layer (Act I, 50 g), followed by washing the layer with benzene. The filtrates are combined, the solvent is distilled off in a water bath, the product is distilled in vacuum, after determining the composition of the reaction mixture by GLC (Chromium-5, column 1.2 m, 0.4 cm, SE-30 on media Inerton-Super, 5 %, the detector - ionization-flame, the carrier gas - helium). 89.6 g of M-octa-2,7-dienyl diethylamine are isolated. The selectivity of 100%, the yield of the target product 2808 g per 1 g of Pd (99%).

N, M-Diethyl-M-octa-2,7-diene-1-ethyl n, b.p. 81-82 ° C / 3 mm Hg., At 1.4535, M + 181.

The data of elemental analysis and NMR1H spectroscopy correspond to the literature.

Analogously to example 1, other experiments were carried out, the conditions of the experiments and the obtained data are given in Tables 1 and 2.

Thus, the proposed method allows to increase the yield of target products from 1700 to 1715-3233 r / r Pd. At the same time, the process temperature

decreases from 100 to 60-70 ° C.

Claims (1)

Invention Formula The method of obtaining M-octa-2,7-dienylamines by telomerizing butadiene with secondary amines in organic solvents when heated in the presence of a catalyst based on compounds of palladium and tertiary phosphine, characterized in that, in order to increase the yield of the target product, As a catalyst, a catalyst system is used that includes palladium carboxylate of the general formula Pd (OCOR) 2, where. (CH2) CCHN, (CHAHChN, (CH2) 1BCH3, CeHs, boron trifluoride etherate, and tertiary phosphine of the formula RNA, where R is phenyl, n-buti or cyclohexyl, in a molar ratio 1: (7-20): {1-3), respectively, the process is carried out at 60-70 ° C, and benzene, trluolg cumene, methanol, acetonitrile are used as the solvent. Telomerization of butadiene with diethylamine in the presence of the catalytic system carxoxylate palladium - trifluoride ethorate - tertiary phosphine Table Reduced the amount of bis- (acetate) palladium (0.056 g, 0.25 mmel) Telomerizine b / thiene e secondary amines and the presence of an organic system 6is- (acetT) p8ll & rma-ether etreftrafluoristoga 6orz-tripheny1fo: fin (1 1-20), Conditions of frost 1 Table 1