_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

Organic derivatives of Group V
R"CL
-R'CL
1
R'OHI o RP(O)(OR'J
om1ne 7 2
RPlOR'J2 s
~ RP(S){OR'J2
Fig. 4. 9 Some reactions of alkyldichlorophosphines.
Table 4.5. Reactions of R"PCI 0_"
+ + +
Reagent RPCl,.Cr R 2 PCJ,.Cr R,PCI.Cr
S0 2 RP(O)Cl 2 R 2 P(O)Cl R,PO
H 2 S RP(S)Cl 2 R 2 P(S)Cl R,PS
R'OH RP(O)(OR') 2 R 2 P(0)(0R') R,PO
H 2 0 RP(O)(OH) 2 R 2 P(0)(0H) R,PO
Other prodllct(s)
SOCI 2
HCI
R'Cl + HCI
HCI
arsenic(V) to arsenic(III). Hydrolysis and alcoholysis of the halides R"PX,_"
proceeds as shown in Table 4.5, and leads to the acids RPO(OH) 2 or R 2 P0(0H) or
their esters. Hydrolysis takes place very readily. As the free chlorides are not very
stable, their complexes with AICI, or PCl 5 are often used instead.
4.9.4 Organo-arsenic and -antimony compounds
Reactions of organoarsenic compounds are summarized in Fig. 4.1 O. Alkylarsonic
and dialkylarsinic acids can be prepared by the Meyer reaction. An alkyl
halide or sulphate is treated with an alkali metal arsenite in aqueous solution.
- 11\0-r
As(ONa), + RX----. NaX + RAs0(0Na) 2 ---> RAs0(0H) 2
This reaction also is apparently driven by the formation of the As=O bond; this
involves formal oxidation of arsenic from the + 3 to the + 5 state. Arylarsonic
acids are often obtained from aryldiazonium salts by the Bart reaction ( p. 2 h) or
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