111911-03-6Relevant articles and documents
ORGANISCHE PHOSPHORVERBINDUNGEN 80. HERSTELLUNG VON TRIAZOLYLMETHYL-PHOSPHONATEN UND VON TRIAZOLYL-METHYLPHOSPHONIUMSALZEN UND DEREN VERWENDUNG IN DER WITTIG-HORNER REAKTION
Maier, Ludwig,Kunz, Walter,Rist, Guenther
, p. 41 - 52 (2007/10/02)
Attemps to prepare 1H-1,2,4-triazol-1-ylmethylphosphonates (4 and 5) by a Mannichtype reaction or by transesterification of 1-hydroxylmethyl-1H 1,2,4-triazol 1 with teriary phosphites failed.On the other hand 4 and 5 are obtained by a Michaelis-Becker reaction from 1-chloromethyl-1H-1,2,4-triazol a and sodium phosphites in high yield.The Michaelis-Arbuzov reaction is less suited for the preparation of 4 and 5. 3 is obtained in good yield as a water clear liquid, b.p. 52-54 deg C/0.2 torr, from the interaction of 1 with thionyl chloride followed by treatment with a base.On standing at 0 deg or 20 deg C it decomposes within hours and yields the unsymmetrical methylen-bis(triazol) 3a in addition to other products.However an acetonitrile solution of 3 is stable for months.Heating this solution with tertiary phosphines gives triazolylsubstituted phosphoniumsalts 6 to 8.The Wittig-Horner reaction with 4 to 6 gives the olefinically substituted triazols 9-12 as a Z/E mixture in high yield.Alkylation of 4 with methyl and ethil iodide gives the corresponding alkylated diethyl-1H-1,2,4-triazol-1-yl-ethyl-1- and -propyl-1-phosphonates 14 and 15 which on hydrolysis with HCl yield 1H-1,2,4-triazo-1-yl-ethyl-1 and -propyl-1-phosphonic acids 17 and 18, respectively.Hydrolysis of 4 gives the unsubstituted 1H-1,2,4-triazol-1-ylmethyl-phosphonic acid 16.