New phosphide(s) phosphine(s) and di:phosphine(s) - used in catalyst for co-polymerisation of carbon mono:oxide and olefinically unsatd. cpds.

摘要

(i) Phosphides of formula R9PMY (I) are prepd. by reacting an alkali metal (M) with a phosphine of formula R7R8R9P, in liq. NH3. (ii) Diphosphines of formula R9HP-R-PR9H (II) are prepd. by (a) reacting (I) with a proton donor to give the corresp. monophosphine R9PH2 (III), (b) converting (III) to the corresp. Li phosphide, R9PLiH (IV) by reaction with an alkyl-Li cpd., and (c) reacting (IV) with a di-halo cpd. of formula X-R-X. (iii) Diphosphines of formula R9R10P-RPR9R10 (V) are prepd. by (a) converting (II) to the corresp. Li diphosphide of formula R9LiP-R-PR9Li (VI) by reaction with an alkyl-Li cpd., and (b) reacting (VI) with a monohalo cpd. of formula X-R10, or by (c) reacting (IV) with a monohalo cpd. of formula X-R10, to give a monophosphine of formula R9R10PH (VII), (d) converting (VII) to the corresp. Li phosphide of formula R9R10PLi (VIII) by reaction with an alkyl-Li cpd., and (e) reacting (VIII) with a dihalo cpd. X-R-X. (iv) New phosphides of formula (I), and new phosphines of formula (VII) and R9R10R11P, and phosphines obtd. by reacting the specifically claimed phosphides with a proton donor are claimed. In the formulae, M = alkali metal; Y = H or Me; R9 = aryl gp., opt. with polar substit.; in the new cpds., R9 is polar-substd.; R7, R8 = aryl gps. with polar substit(s). in the o- or m-position w.r.t. P, and at least 1 substit. in the o-position; hydrocarbon gps. opt. polar-substd., with a C=C gp. linked to P through an aliphatic C; or H, but are not both H; X = halogen; R = divalent organic bridging gp. with at least 2C; R10, R11 = aliphatic hydrocarbon gp., opt. polar-substd.