4(Z-3-chloroallyl)benzyl alcohol → 4(Z-3-chloroallyl)benzyl(1R)cis-3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate

HRID 231671Notes

Reaction equation

HRID 231671 reaction equation
[Br:1][C:2]([Br:12])=[CH:3][C@H:4]1[C@@H:6]([C:7]([O-:9])=[O:8])[C:5]1([CH3:11])[CH3:10].[Cl:13]/[CH:14]=[CH:15]\[CH2:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21]O)=[CH:19][CH:18]=1>C(Cl)Cl.CN(C)C1C=CN=CC=1>[Br:1][C:2]([Br:12])=[CH:3][C@H:4]1[C@@H:6]([C:7]([O:9][CH2:21][C:20]2[CH:23]=[CH:24][C:17]([CH2:16]/[CH:15]=[CH:14]\[Cl:13])=[CH:18][CH:19]=2)=[O:8])[C:5]1([CH3:10])[CH3:11]

Participants

5

Reactant 2

HCID 132433484(Z-3-chloroallyl)benzyl alcoholHCID 22797648(1R)cis 3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate

Product 1

HCID 132433624(Z-3-chloroallyl)benzyl(1R)cis-3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent3×

Procedure

To a solution of (1R)cis 3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (0.11 g) in CH2Cl2 (3 ml) cooled to 0° is added successively 4(Z-3-chloroallyl) benzyl alcohol (0.070 g) in CH2Cl2 (2 ml), N,N1 dicyclohexylcarbodiimide (0.076 g) in CH2Cl2 (2 ml), and 4-dimethylamino pyridine (0.010 g). This mixture is stirred for 30 minutes at 0°, then for 16 hours at 20°. The resulting precipitate is filtered off, the filtrate evaporated under reduced pressure and the residue chromatographed on florisil. The fraction eluted by 7% diethyl ether in petroleum ether bp 60°-80° C. ether in petrol is evaporated to a residue of 4(-3-chloroallyl)benzyl (1R)-3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (0.15 g) 91% nD20 1.5684.

Workup

  1. waitfor 16 hours at 20°
  2. filtrationThe resulting precipitate is filtered off
  3. customthe filtrate evaporated under reduced pressure
  4. customthe residue chromatographed on florisil
  5. washThe fraction eluted by 7% diethyl ether in petroleum ether bp 60°-80° C. ether in petrol
  6. customis evaporated to a residue of 4(-3-chloroallyl)benzyl (1R)-3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (0.15 g) 91% nD20 1.5684

Sources & evidence

ORD record
ord-7c51e4fdd0154aedb8aa7109c8ababe2
Source dataset
uspto-grants-1989_07
Patent number
US04847438

Reaction notes

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