SU1747452A1 - Method of 1-phenyl-3-alkylphospholanes synthesis - Google Patents

Abstract

Usage: as intermediates of organophosphorus synthesis. The essence of the invention: the product 1-phenyl-3-butylphospholane with 6Н5-рО CH2 CjH-y And BF С14Н21Р, yield 78%, bp. 105-108 ° C / 1 mmHg; 1-phenyl-3-hexylphospholane CeHs-PQ. and BF CieHasP, yield 76%, bk. 128-130 ° C / 1 mmHg; bp 162-165 ° C / 1 mm Hg Reagent 1: (С2Н5) ЗА1. Reagent 2: CH2 CH-CH2R, where R is n-CsNu, n-CsHn, n-SvNts. Conditions: reaction: in the environment of an aliphatic hydrocarbon in the presence of a catalyst-dicyclopentadiene zirconium dichloride at room temperature under an inert gas atmosphere for 8 hours, followed by treatment of the resulting reaction mixture with phenyldichlorophosphine in ether at 0 ° C and stirring at room temperature 6- 8 h (С2Нб) ЗА1, catalyst a-olefin and CeHsPCte are taken in a molar ratio of (1-1.2) :( 0.01-0.03): 1; (1.2-1.3). J

Description

This invention relates to organic chemistry, in particular, to methods for producing 1-phenyl-3-alkylphospholanes of the general formula

ph-paCH2-R where KK-C3H, CsHu, SvNp which are used as initial reagents in organic synthesis, as plasticizers, flame retardant impregnations for nitrates and cellulose acetates, flotation reagents for the release of some rare metals, in the production of insecticides,

when producing high-molecular compounds, they are used as additives to improve the quality of gasolines and lubricating oils; they are used as surfactants in the textile industry.

The purpose of the invention is to develop a new method for producing 1-phenyl-3-alkylphospholans.

The goal is achieved by the fact that the mixture contains triethyl aluminum (EtaAl). dicyclopentadienyl zirconium dichloride (Cp2ZrCI 2) and α-olefin of the formula R — CH2 – CH – CH2, where R is CzH7, CsHn, C8Hi7, taken in the Molar C oof of the corresponding

Xj

4 SL Yu

Venous (1-1,2) :( 0.01-0.03): 1, preferably 1.1: 0.02: 1, stirred in an environment of an aliphatic solvent at room temperature (23-25 ° C) for 8 hours, followed by the addition of an ethereal phenyldichlorophosphine (PhPCte) solution at OOC, taken in a molar ratio of R - CH2-CH CH2: PhPCl2 1: (1.2-1.3), preferably 1: 1.25, and stirring the reaction mass at room temperature (23-25 ° C) 6-8 hours

Under these conditions, the yield of 1-phenyl-3-alkylphospholanes is 71-82%. The reaction proceeds according to the scheme

R - CH2 - CH CH2 + Ets A

cngv

where R is SzNu, C5Hn, CaHi7.

The use of a catalyst (Cp2ZrCl2) in an amount of more than 3 mol.% With respect to a-olefin does not lead to a significant increase in the yield of the target product. The use of CpaZrCte in an amount of less than 1 mol.% Reduces the yield of 1-phenyl-3-alkylphosphates, which is associated with a decrease in catalytically active sites in the reaction mixture. Carrying out the reaction at a higher temperature does not contribute to an increase in the yield of the target products; at a lower temperature, the reaction rate decreases. An excess of PhPCte does not lead to a significant increase in the yield of phospholans, a lack of PhPCte reduces the yield of target products.

Example. In a 50 ml glass reactor, mounted on a magnetic stirrer, under an atmosphere of argon, 11 mmol of EtaAl are placed in 3 ml of hexanes, 0.2 mmol of Cp2ZrCl2 and 10 mmol of 1-hexene, stirred for 8 hours at room temperature (23-25 ° C) , cooled to 0 ° C, 12.5 mmol of PhPCte in 5 ml of ether are added dropwise, the temperature is raised to room temperature (23-25 ° C), kept under stirring for 7 hours. The reaction mass is treated with a saturated solution, extracted with chloroform, the mixture 1.72 g (78%) of 1-phenyl-3-butylphospholane.

Other examples confirming this method are shown in the table.

To reduce the fire hazardous process of the EgzA process (must be used in aliphatic solvents. Diluted EtaA solution is not fire-hazardous. Hexane, heptane, octane, cyclohexane can be used as aliphatic solvents. In examples 1-11 EtaAl was diluted with hexane, added dropwise as an ethereal solution at 0 ° to avoid a sudden warming of the reaction mass. After adding all of PhPCl2, the temperature was slowly (30 min) brought to room temperature (23-25 ° C). For example, in the conditions of Example 1 at 35 ° C, the yield of 1-phenyl-3-butylphospholane is 70%. At a lower temperature, for example, 0 ° C , in the conditions of example 1, the yield of the target product is 52%. It is not economically feasible to use a larger amount of PhPCte,

since in this case the yield of the target product does not increase significantly. With smaller amounts, for example with the ratio RCH2CH CH2: PhPCl2 1: 1 under the conditions of example 1, the yield of the target product is 59%.

Thus, a new method of obtaining individual 1-phenyl-3-alkylphospholans with high yield and selectivity has been developed.

Claims (1)

Invention Formula The method of obtaining 1-phenyl-3-alkylphospholans of the general formula sbN5- Cx CH2R where R is n-C3H, n-CsHn, n-C3H, which implies that triethyl aluminum is reacted with a-olefin of formula CH2CH-CH2-R. where R has the indicated values, in the presence of a catalyst, dicyclopentadienyl zirconium dichloride in an aliphatic hydrocarbon medium at room temperature under an inert gas atmosphere for 8 hours, followed by treatment of the reaction mixture with phenyldichlorophosphine in ether medium at 0 ° C and stirring the reaction mixture at room temperature for 6 -8 h, and triethylaluminum, the catalyst, a-olefin and phenyldichlorophosphine are used in the molar ratio is (1-1.2) :( 0.01-0.03): 1: (1.2-1.3).