BEITRäGE ZUR CHEMIE DER ACYLPHOSPHINE: üBER 1-ADAMANTYLACYL-, DI-1-ADAMANTYLACYL- UND 1-ADAMANTOYLPHOSPHINE. DARSTELLUNG UND EINIGE REAKTIONEN

Abstract

Acylphosphines of the type (1-Ad)_nP[C(:O)R]_3-n, (n=1,2; Bu=1-Ad, Ph) were synthesized via the reaction of 1-AdPH₂ or (1-Ad)₂PH with the corresponding carboxylic acid chlorides/NEt₃. The reaction of 1-AdPHz with phtaloyl dichloride/NEt₃, led to the five-membered heterocycle 4. In the case of n=1, R=1-Ad the monosubstitution product 1-AdP(H)C(:O)(1-Ad) lb was also observed. 1-AdP(H)C(:O)Ph le was selectively formed when 1-AdPHz was allowed to react with PhC(O)CI/K,CO₃ whereas the remaining PH-proton in le could be substituted by C(:O)′Bu in its reaction with ′BuC(:O)Cl/ NEt, to give 2d. The action of trifluoroacetic acid anhydride on 1-AdPHz or (I-Ad)₂PH led to the trifluoroacetyl phosphines 2c and 3c. The reaction of 1-AdP[C(:O)′Bu]₂ 2a with aqueous H₂O₂ or elemental sulfur furnished the corresponding chalcogenides 5 and 6, with a large excess of methyl iodide [1-AdPMe₁]1 7 was formed. The carbonyl complexes (L)M(CO), (L=2a; M=Ni, n=3: 8; M=Fe, n=4: 9) were obtained upon reaction of 2a with Ni(CO), and Fe₂(CO)₉, respectively. Tris-1-adamantoylphosphine 10 was formed as a by-product in the reaction of P(SiMe₃)₃ with 1-AdC(:O)Cl and was converted to the chalcogenides [(1-AdC(:O)],P(:X) (X=0: 13; X=S: 14).

Key Words:

• Acyl phosphines
• 1-adamantyl phosphorus compounds
• NMR.