23743-26-2Relevant articles and documents
Burt et al.
, p. 203,205 (1979)
A synthetic double (bicyclic hexyl phosphine ) alkane method of the
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Paragraph 0006; 0016-0017, (2017/04/03)
The invention discloses a method for synthesizing bis(dicyclohexylphosphine)alkane, belonging to the field of organic synthesis. The method comprises the following steps: (1) under water-free oxygen-free conditions, carrying out amino protection on the initial raw material dicyclohexyl chlorophosphine to obtain dicyclohexyl diethylamino phosphine; and (2) reacting the dicyclohexyl diethylamino phosphine with diethyl cadmium to obtain an di(dicyclohexylphosphine)cadmium intermediate, and reacting with dichloroalkane to synthesize the bis(dicyclohexylphosphine)alkane compound. The method has the advantages of mild reaction conditions and high yield, is easy to operate, lowers the production cost, and is easier for industrial production.
Synthesis of 1,2-bis[(diorgano)phosphino]ethanes via Michaelis-Arbuzov type rearrangements
Baldwin, Lawrence C,Fink, Mark J
, p. 230 - 238 (2007/10/03)
A three-step process for the synthesis of the bis(diorganophosphino)ethanes R2PCH2CH2PR2 where R = Et, Ph, iPr, Cy and tBu was examined. In the first step, diorganochlorophosphines were allowed to react with ethylene glycol in the presence of triethylamine at room temperature in THF solution. For R = Ph, iPr and Cy, the bisphosphinites R2POCH2CH2OPR2 were obtained in high yield. For R = Et, the bisphosphinite could not be isolated but may be formed in 80% mixtures with tetraethyldiphosphine, Et2PPEt2, as a minor component. The reaction of di-t-butylchlorophosphine with ethylene glycol occurs at temperatures greater than 130 °C giving di-t-butyl phosphine oxide, tBu2PH(O), as the only phosphorus-containing product. Thermolysis of the bisphosphinites R2POCH2CH2OPR2 (R = Ph, iPr and Cy) at 190-260 °C for 24 h gave the bisphosphine oxides, R2P(O)CH2CH2(O)PR2 in 9% (Ph), 90% (iPr) and 93% (Cy) yields. A DSC study of the thermal rearrangement of Cy2POCH2CH2OPCy2 to Cy2P(O)CH2CH2(O)PCy2 yielded an enthalpy of isomerization of -40.4 ± 0.6 kcal mol-1. Reduction of the bisphosphine oxides, R2P(O)CH2CH2(O)PR2 (R = Ph, iPr and Cy) with trichlorosilane gave the bisphosphines, R2PCH2CH2PR2 in 80-85% yield. The overall yields of the bisphosphines R2PCH2CH2PR2 (R = iPr and Cy) in the three-step process were 61 and 75%, respectively, suggesting that this process should be an attractive synthetic pathway to these two bisphosphines.