SYNTHESIS OF POLYOLS BEARING PHOSPHONATE GROUPS. PART II: EPOXIDES USED AS STARTING MATERIALS

Abstract

Three epoxyphosphonates were prepared. These compounds have the following general formula: CH₂(O)C(R)-Z-PO(OCH₂CH₃)₂ with (II): R[dbnd]H, Z[dbnd]H₂; (V): R[dbnd]H, Z[dbnd]H₂O(CH₂)₃S(CH₂)₃; (VI): R[dbnd] CH₃. (II) is obtained by epoxidation of diethyl allylphosphonate by hydrogen peroxide in the presence of benzonitrile with a yield superior to 60%. (V) is obtained by photoaddition of HS(CH₂)₃PO(OCH₂CH₃)₂ to ally1 glycidyl ether CH₂(O)CH CH₂-O- CH₂CH[dbnd]CH₂ with a high yield. (VI) is obtained by addition of diethyl hydrogenophosphonate HPO(OCH₂CH₃)₂ to I-chloropropan-Zone CH₃C(O) CH₂Cl with a yield of 80%.

These epoxides then lead to polyols bearing a phosphonate group by ring opening with diethanolamine (HOCH₂CH₂)₂NH:(HOCH₂CH₂)₂NCH₂C(OH)(R)-Z-PO(OCH₂CH₃)₂ with (VII): R[dbnd]H, Z[dbnd]H₂; (VIII): R[dbnd]H, Z[dbnd]H₂O(CH₂)₃S(CH₂)₃; (IX):R[dbnd] CH₃.

This reaction appears to be an easy method without any need for solvent or catalyst, and could be of industrial interest.

Key Words:

• Epoxides
• diethanolamine
• polyols
• phosphonates
• amino -methylphosphonic