Diketene → HCID 13718272, compound

HRID 851454Notes

Reaction equation

HRID 851454 reaction equation
[CH2:1]=[C:2]1[O:6][C:4](=[O:5])[CH2:3]1.[C:7]1([P:13]([O-:19])[S:14]CCCC)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>>[CH2:1]([O:19][P:13]([CH2:1][CH:2]1[O:6][C:4](=[O:5])[CH2:3]1)([C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1)=[S:14])[CH2:2][CH2:3][CH3:4]

Participants

3

Reactant 2

HCID 12661DiketeneHCID 131712989HCID 131712989, compound

Product 1

HCID 13718272HCID 13718272, compound

Conditions

Temperature
85 °C

Procedure

A mixture of 7.4 parts of diketene and 1.2 parts of bis-(t-butylcyclohexyl)-perdicarbonate was added dropwise over 1 hour to 65.4 parts of vigorously stirred n-butyl phenylthiophosphonite which was heated at 85° C. in a nitrogen atmosphere. The mixture was then passed down a wiped wall still at 70° C. and a pressure of 0.013 mb to remove unreacted starting materials. The residue was distilled on the wiped wall still at 115° C. and a pressure of 0.013 mb and gave crude n-butyl(2-oxo-4-oxetanylmethyl)phenylthiophosphinate as a colourless oil which contained a more volatile impurity. The crude product was passed down a wiped wall still at 85° C. and a pressure of 0.013 mb and the involatile fraction was found to be pure n-butyl(2-oxo-4-oxetanylmethyl)phenylthiophosphinate which 31P NMR showed to be a mixture of diastereoisomers having chemical shifts at δ-83.7 and δ-83.2 and which had the following elemental analysis by weight.

Workup

  1. customstill at 70° C.
  2. customa pressure of 0.013 mb to remove unreacted
  3. distillationThe residue was distilled on the wiped wall still at 115° C.

Sources & evidence

ORD record
ord-ba08713ef52347f2a0742db66b0c7649
Source dataset
uspto-grants-1983_05
Patent number
US04384966

Reaction notes

Loading…