Pyridine → HCID 67794398, compound

HRID 981442Notes

Reaction equation

HRID 981442 reaction equation
Cl[C:2]([O:4][CH2:5][CH3:6])=[O:3].[CH3:7][C:8]1[CH:14](/[CH:15]=[CH:16]/[CH:17]([OH:19])[CH3:18])[C:13]([CH3:21])([CH3:20])[CH2:12][C:10](=[O:11])[CH:9]=1.N1C=CC=CC=1>ClCCl>[CH2:5]([O:4][C:2](=[O:11])[OH:3])[CH3:6].[OH:19][CH:17]([CH3:18])[CH:16]=[CH:15][CH:14]1[C:13]([CH3:20])([CH3:21])[CH2:12][C:10](=[O:11])[CH:9]=[C:8]1[CH3:7]

Participants

5

Reactant 3

HCID 1049PyridineHCID 10928Ethyl chloroformateHCID 5370052HCID 5370052, compound

Product 1

HCID 67794398HCID 67794398, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
25 °C

Procedure

A solution of ethyl chloroformate (5.42g, 0.05 mol) in dichloromethane (10mL) was added dropwise over a 30 minute period to a cold (10° C.) solution of 3-oxo-α-ionol (5.20g, 0.025 mol, which may be prepared as described by A. J. Aasen, B. Kimland and C. R. Enzell in Acta Chem. Scand., 1973, 27, 2107-2114) and pyridine (3.96g, 0.05 mol) in dichloromethane (80mL). The mixture was stirred at 25° C. for 18 hours. Dichloromethane (100mL) was then added and the mixture washed with 5% phosphoric acid solution (3×100mL), saturated sodium bicarbonate solution until neutral and dried (sodium sulfate). Evaporation of solvent and chromatography of the residue followed by kugelrohr distillation (150° C. both temp. 0.5 mm) provided 4-(3-hydroxy-1-butenyl)-3,5,5,-trimethyl-2-cyclohexen-1-one ethyl carbonate (2.15g, GLC purity; 87%) 1H-NMR(CDCl3) δ 0.97 (3H,s), 1.05 (3H, s), 1.31 (3H, t, J=7Hz), 1.41 (3H, d, J=7Hz), 1.92 (3H,s) 2.1-2.3 (2H,dd), 2.4-2.7 (1H,m), 4.25 (2H,q, J=7Hz), 5.0-5.4 (1H,m), 5.5-5.8 (2H,m), 5.95 (1H,s); OR (film) Vmax 2960, 1750, 1670, 1630, 1470, 1450, 1370, 1260 cm-1 ; MS m/e 280, 224, 190,175, 134, 108.

Workup

  1. custommay be prepared
  2. washthe mixture washed with 5% phosphoric acid solution (3×100mL), saturated sodium bicarbonate solution until neutral and
  3. dry with materialdried (sodium sulfate)
  4. customEvaporation of solvent and chromatography of the residue
  5. distillationfollowed by kugelrohr distillation (150° C. both temp

Sources & evidence

ORD record
ord-6f449dcd5f764b3999750fe3cc79585f
Source dataset
uspto-grants-1991_02
Patent number
US04992106

Reaction notes

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