Triethylamine → (1R)-2-methyl-1-trichloromethyl-2-butenyl diazoacetate

HRID 127031Notes

Reaction equation

HRID 127031 reaction equation
[C:1]([O:7][C@@H:8]([C:13]([Cl:16])([Cl:15])[Cl:14])[CH:9]=[C:10]([CH3:12])C)(=[O:6])[CH2:2]C(C)=O.[CH2:17](N(CC)CC)C.S([N:34]=[N+:35]=[N-])(C1C=CC(C)=CC=1)(=O)=O.[OH-].[Na+]>C(#N)C>[N+:34](=[CH:2][C:1]([O:7][C@@H:8]([C:13]([Cl:14])([Cl:15])[Cl:16])[C:9]([CH3:17])=[CH:10][CH3:12])=[O:6])=[N-:35]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 13661p-Toluenesulfonyl azideHCID 14798Sodium HydroxideHCID 12525204(R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetate

Product 1

HCID 54365383(1R)-2-methyl-1-trichloromethyl-2-butenyl diazoacetateYield 62.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a solution of (1R)-3-methyl-1-trichloromethyl-2-butenyl acetoacetate (1.63 g, 5.68 mmole) from Example IA.2.(a) and triethylamine (0.57 g, 5.68 mmole) in 10 ml of acetonitrile was added dropwise in small portions at 7-10 minute intervals over a total period of 30 minutes a solution of tosyl azide (1.12 g, 5.68 mmole) in 2 ml of acetonitrile. After stirring at room temperature for 21/4 hours, the mixture was poured into 17 ml of aqueous 1 NaOH. After stirring an additional 45 minutes, the mixture was extracted three times with ether, and the combined ethereal extracts were dried over MgSO4. The dried solution was concentrated to give an orange oil. The oil was chromatographed on 8 (20×20 cm) preparative tlc plates (silica gel) with CH2Cl2 as eluent to afford (1R)-2-methyl-1-trichloromethyl-2-butenyl diazoacetate (0.96 g, 62% isolated yield) as a yellow oil; [α]D31 =+59° (hexane).

Workup

  1. customwas added dropwise in small portions at 7-10 minute
  2. customof 30 minutes
  3. stirringAfter stirring an additional 45 minutes
  4. extractionthe mixture was extracted three times with ether
  5. dry with materialthe combined ethereal extracts were dried over MgSO4
  6. concentrationThe dried solution was concentrated
  7. customto give an orange oil
  8. customThe oil was chromatographed on 8 (20×20 cm) preparative tlc plates (silica gel) with CH2Cl2 as eluent

Sources & evidence

ORD record
ord-dac562aaa8b04ebcb8c1d365a8d56277
Source dataset
uspto-grants-1981_03
Patent number
US04254282

Reaction notes

Loading…