Hydrochloric Acid → HCID 20313162, compound

HRID 2420139Notes

Reaction equation

HRID 2420139 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([CH:20]2[CH2:23][CH:22]([C:24](OC)=[O:25])[CH2:21]2)=[CH:16][CH:15]=1.Cl>CCCCCC.O1CCCC1>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([CH:20]2[CH2:21][CH:22]([C:24](=[O:25])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9])[CH2:23]2)=[CH:18][CH:19]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 12958Dimethyl methylphosphonateHCID 20313159HCID 20313159, compoundHCID 178418339Butyllithium

Product 1

HCID 20313162HCID 20313162, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyl lithium (16.2ml. of a 1.23M solution in hexane) was added dropwise to a stirred solution of dimethyl methylphosphonate (2.48g.) in dry tetrahydrofuran (25ml.) at -78° C. in an atmosphere of argon. After 10 minutes, a solution of methyl 3-(4-chlorophenyl)cyclobutanecarboxylate mixed isomers (2.24g.) in dry tetrahydrofuran (25ml.) was added dropwise, and stirred at -78° C. for 2 hours. The reaction mixture was warmed to room temperature and neutralised by the addition of 1N hydrochloric acid (20ml.) to the stirred solution. The tetrahydrofuran was evaporated, and the residue was partitioned between ethyl acetate and water. The ethyl acetate extract was dried over sodium sulphate and the solvent was evaporated. The crude product was purified by dry column chromatography on "Kieselgel 60" (100g.) eluting with ethyl acetate, to give dimethyl 2-[3-(4-chlorophenyl)cyclobutyl]-2-oxoethylphosphonate, as a mixture of cis and trans isomers, RF = 0.35 and 0.40 (ethyl acetate). The n.m.r. spectrum in deuteriochloroform showed the following characteristic signals (δ values):

Workup

  1. temperatureThe reaction mixture was warmed to room temperature
  2. customThe tetrahydrofuran was evaporated
  3. customthe residue was partitioned between ethyl acetate and water
  4. extractionThe ethyl acetate extract
  5. dry with materialwas dried over sodium sulphate
  6. customthe solvent was evaporated
  7. customThe crude product was purified
  8. dry with materialby dry column chromatography on "Kieselgel 60" (100g.)
  9. washeluting with ethyl acetate

Sources & evidence

ORD record
ord-e9d9a819d7994cb98269cfcc82a8b9f8
Source dataset
uspto-grants-1978_08
Patent number
US04109015

Reaction notes

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