Dimethyl Sulfide → (Z)-(3S,5S)-1-(2-chloroethylidene)-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylenecyclohexane

HRID 581622Notes

Reaction equation

HRID 581622 reaction equation
ClN1C(=O)CCC1=O.CSC.[C:12]([Si:16]([C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1)([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[O:17][C@H:18]1[CH2:23][C@@H:22]([O:24][Si:25]([C:38]([CH3:41])([CH3:40])[CH3:39])([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:21]/[C:20](=[CH:42]/CO)/[C:19]1=[CH2:45])([CH3:15])([CH3:14])[CH3:13].[CH2:58]([Cl:60])Cl>>[Cl:60][CH2:58]/[CH:42]=[C:20]1\[C:19](=[CH2:45])[C@@H:18]([O:17][Si:16]([C:12]([CH3:15])([CH3:14])[CH3:13])([C:52]2[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=2)[C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[CH2:23][C@@H:22]([O:24][Si:25]([C:38]([CH3:41])([CH3:40])[CH3:39])([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH2:21]\1

Participants

5

Reactant 4

HCID 1068Dimethyl SulfideHCID 6344Dichloromethane2×HCID 31398ChlorosuccinimideHCID 86754184(Z)-(3S,5S)-2-[3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylene-cyclohexylidene]-ethanol

Product 1

HCID 86754183(Z)-(3S,5S)-1-(2-chloroethylidene)-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylenecyclohexane

Procedure

1.31 g (9.81 mmol) of N-chloro-succinimide in 34 ml of abs. CH2Cl2 was treated at -10° with 749 μl (10.2 mmol) of dimethyl sulfide. 15 Minutes later, 2.95 g (4.559 mmol) of (Z)-(3S,5S)-2-[3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylene-cyclohexylidene]-ethanol, dissolved in 10 ml of CH2Cl2, was slowly added to the resultant white suspension at the same temperature and then stirred for additional 30 minutes at RT. The reaction mixture was then poured onto crushed ice, extracted with ether, washed with water, dried over sodium sulfate and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=97.5/2.5) yielded 2.76 g of (Z)-(3S,5S)-1-(2-chloro-ethylidene)-3,5-bis-(tert-butyl-diphenyl-silanyloxy)-2-methylene-cyclohexane as yellowish foam.

Workup

  1. additionwas slowly added to the resultant white suspension at the same temperature
  2. additionThe reaction mixture was then poured
  3. customonto crushed ice
  4. extractionextracted with ether
  5. washwashed with water
  6. dry with materialdried over sodium sulfate
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-b3f33cfb10244b928558bfeec5d6d31e
Source dataset
uspto-grants-1999_07
Patent number
US05919986

Reaction notes

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