Chloroiodomethane → HCID 23387571, compound

HRID 990019Notes

Reaction equation

HRID 990019 reaction equation
[C:1]([NH:11][C@H:12]([C:16]([O:18][CH2:19][CH:20]([O:28][C:29](=[O:47])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])[CH2:21][C:22]([CH3:27])([CH3:26])[C:23]([OH:25])=[O:24])=[O:17])[CH:13]([CH3:15])[CH3:14])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].[OH-].C([N+](CCCC)(CCCC)CCCC)CCC.[Cl:66][CH2:67]I>O1CCOCC1>[C:1]([NH:11][C@H:12]([C:16]([O:18][CH2:19][CH:20]([O:28][C:29](=[O:47])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])[CH2:21][C:22]([CH3:26])([CH3:27])[C:23]([O:25][CH2:67][Cl:66])=[O:24])=[O:17])[CH:13]([CH3:15])[CH3:14])([O:3][CH2:4][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1)=[O:2]

Participants

5

Reactant 3

HCID 11644ChloroiodomethaneHCID 2723671Tetrabutylammonium HydroxideHCID 23387556HCID 23387556, compound

Product 1

HCID 23387571HCID 23387571, compoundYield 64.5%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 5-(N-CBz-L-valyloxy)-4-stearoyloxy-2,2-dimethylvaleric acid (16.0 g, 24 mmol) in dioxane (500 mL), was added dropwise a 40% aqueous solution of tetrabutylammonium hydroxide (14.3 mL). After stirring for 5 min, the solution was evaporated to dryness through co-evaporation with dioxane and toluene. The residue was dissolved in dichloromethane (500 mL) and then chloroiodomethane (17.5 mL, 240 mmol) was added and the solution was stirred for 6 h at room temperature. The solution was concentrated under reduced pressure and the residue was shaken with hexane/ethyl acetate (1:1 v/v, 400 mL). The yellow crystalline solid was filtered off and the filtrate was washed with aqueous solution of sodium thiosulfate (0.1 M) and the filtered through anhydrous sodium sulfate and evaporated to dryness. The residue was column chromatographed (silica gel, 1%MeOH in CH2Cl2), to give 11.0 g of chloromethyl 5-(N-CBz-L-valyloxy)-4-stearoyloxy-2,2-dimethylvalerate.

Workup

  1. customthe solution was evaporated to dryness through co-evaporation with dioxane and toluene
  2. dissolutionThe residue was dissolved in dichloromethane (500 mL)
  3. stirringthe solution was stirred for 6 h at room temperature
  4. concentrationThe solution was concentrated under reduced pressure
  5. stirringthe residue was shaken with hexane/ethyl acetate (1:1 v/v, 400 mL)
  6. filtrationThe yellow crystalline solid was filtered off
  7. washthe filtrate was washed with aqueous solution of sodium thiosulfate (0.1 M)
  8. filtrationthe filtered through anhydrous sodium sulfate
  9. customevaporated to dryness
  10. customchromatographed (silica gel, 1%MeOH in CH2Cl2)

Sources & evidence

ORD record
ord-9de632814d9a4316a2ef4db5cd75dd21
Source dataset
uspto-grants-2002_10
Patent number
US06458772B1

Reaction notes

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