Triphenylphosphine → 2-Cyclopropyl-2-(4-chlorophenyl)ethyl thiolacetate

HRID 1383217Notes

Reaction equation

HRID 1383217 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.[CH:34]1([CH:37]([C:40]2[CH:45]=[CH:44][C:43]([Cl:46])=[CH:42][CH:41]=2)[CH2:38][OH:39])[CH2:36][CH2:35]1.[S:47]1[CH:51]=[CH:50][CH:49]=[C:48]1[CH2:52][C:53](O)=[O:54]>O1CCCC1>[S:47]1[CH:51]=[CH:50][CH:49]=[C:48]1[CH2:52][C:53]([O:39][CH2:38][CH:37]([CH:34]1[CH2:36][CH2:35]1)[C:40]1[CH:45]=[CH:44][C:43]([Cl:46])=[CH:42][CH:41]=1)=[O:54]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 159702-Thiopheneacetic acidHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 156167072-Cyclopropyl-2-(4-chlorophenyl)ethanol

Product 1

HCID 571968882-Cyclopropyl-2-(4-chlorophenyl)ethyl thiolacetateYield 65.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A stirred solution of 11.7 grams (0.045 mole) of triphenylphosphine in 75 mL of dry tetrahydrofuran was cooled to 0° C., and 9.0 grams (0.045 mole) of diisopropyl azodicarboxylate was added dropwise. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 30 minutes. Successively, 4.4 grams (0.022 mole) of 2-cyclopropyl-2-(4-chlorophenyl)ethanol (prepared in Example 1, Step B) and 3.4 grams (0.045 mole) of thiolacetic acid were then added. The exothermic reaction caused the reaction mixture temperature to rise to 39° C. After cooling to ambient temperature the reaction mixture was stirred for 16 hours. The reaction mixture was then concentrated under reduced pressure to a residual oil. The oil was subjected to chromatography on silica gel using methylene chloride:heptane (1:4) as eluant. The appropriate fractions were combined and concentrated under reduced pressure, yielding 4.6 grams of 2-cyclopropyl-2-(4-chlorophenyl)ethyl thiolacetate as an oil. The nmr and the ir spectra were consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. customThe exothermic reaction
  3. customto rise to 39° C
  4. temperatureAfter cooling to ambient temperature the reaction mixture
  5. stirringwas stirred for 16 hours
  6. concentrationThe reaction mixture was then concentrated under reduced pressure to a residual oil
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-31058f644bae4061b33a481df66f9b84
Source dataset
uspto-grants-1989_02
Patent number
US04808762

Reaction notes

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