Water → HCID 69666761, compound

HRID 1791027Notes

Reaction equation

HRID 1791027 reaction equation
C([Li])CCC.[Cl-].[Cl:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O=[C:29]1[CH2:35][CH2:34][C:33]2[CH:36]=[C:37]([C:40]([O:42][CH3:43])=[O:41])[CH:38]=[CH:39][C:32]=2[O:31][CH2:30]1.O>CCCCCC.O1CCCC1>[Cl:7][CH:8]=[C:29]1[CH2:35][CH2:34][C:33]2[CH:36]=[C:37]([C:40]([O:42][CH3:43])=[O:41])[CH:38]=[CH:39][C:32]=2[O:31][CH2:30]1

Participants

7

Reactant 4

HCID 962WaterHCID 197823(Chloromethyl)triphenylphosphonium chlorideHCID 11401737HCID 11401737, compoundHCID 178418339Butyllithium

Product 1

HCID 69666761HCID 69666761, compoundYield 24.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

0.08 ml (0.2 mmol) of a 1.9M solution of n-butyllithium in hexane is added dropwise to a suspension of 76 mg (0.22 mmol) of chloromethyltriphenylphosphonium chloride in 1.7 ml of tetrahydrofuran cooled to 0° C. The solution is stirred for one hour and then 40 mg (0.18 mmol) of methyl 3-oxo-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate, prepared according to example 4, in 2.5 ml of tetrahydrofuran are added at 0° C. via a hollow tube. The solution is stirred at ambient temperature for 1 h 30 and then water is added. After concentrating the solution, dichloromethane is added. The phases are separated and then the aqueous phase is extracted with dichloromethane. The combined organic phases are then washed using brine, are then dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 10/90) to provide 11 mg (24%) of methyl 3-(chloromethylene)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of a mixture of two isomers in a Z/E ratio (70/30); 1H NMR (300 MHz, CDCl3): 2.6 (m, 2H), 2.99 (m, 2H), 3.9 (s, 3H), 4.79 (s, 2H), 6.07 (s, 1H), 7.04 (d, J=8.3 Hz, 1H), 7.84 (m, 2H).

Workup

  1. additionare added at 0° C. via a hollow tube
  2. stirringThe solution is stirred at ambient temperature for 1 h 30
  3. concentrationAfter concentrating the solution, dichloromethane
  4. additionis added
  5. customThe phases are separated
  6. extractionthe aqueous phase is extracted with dichloromethane
  7. washThe combined organic phases are then washed
  8. customare then dried
  9. concentrationare finally concentrated under vacuum
  10. customThe crude reaction product
  11. customis then purified by chromatography on silica gel (ethyl acetate/heptane 10/90)

Sources & evidence

ORD record
ord-d43c41bede90405fa3fc743006c413f3
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

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