Pyridine → HCID 67793288, compound

HRID 981443Notes

Reaction equation

HRID 981443 reaction equation
Cl[C:2]([O:4][CH2:5][CH3:6])=[O:3].[CH3:7][C:8]1[C:13](=[O:14])[CH2:12][CH2:11][C:10]([CH3:16])([CH3:15])[C:9]=1/[CH:17]=[CH:18]/[CH:19]([OH:21])[CH3:20].N1C=CC=CC=1>ClCCl>[CH2:5]([O:4][C:2](=[O:14])[OH:3])[CH3:6].[OH:21][CH:19]([CH3:20])[CH:18]=[CH:17][C:9]1[C:10]([CH3:15])([CH3:16])[CH2:11][CH2:12][C:13](=[O:14])[C:8]=1[CH3:7]

Participants

5

Reactant 3

HCID 1049PyridineHCID 10928Ethyl chloroformateHCID 6430464HCID 6430464, compound

Product 1

HCID 67793288HCID 67793288, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
7.5 °C

Procedure

A solution of ethyl chloroformate (1.74g, 0.016 mol in dichloromethane (10mL) was added dropwise over a 1 hour period to a cold (5° C.) solution of 4-oxo-β-ionol (3.33g, 0.016 mol, which may be prepared as described by R. Kaiser and D. Lamparsky, Helv. Chim. Acta, 1978, 61, 2328-2335), pyridine (1.28g, 0.016 mol) and dichloromethane (30mL). After stirring the mixture at 5-10° C. for 2 hours it was added to ice water (20mL). The organic layer was washed with 5% phosphoric acid solution until neutral and dried over sodium sulfate. The solvent was removed and the residue chromatographed. Kugelrohr distillation (bath temp. 150° C., 0.5 mm) gave 2.0g (GLC purity; 85%) of 3-(3-hydroxy-1-butenyl)-2,4,4-trimethyl-2-cyclohexen-1-one ethyl carbonate. 1H-NMR (CDCl3) δ 1.12 (6H,s), 1.35 (3H,d,J=7Hz), 1.40 (3H,t,J=7Hz), 1.77 (3H,s), 1.7-2.7 (4H,m), 4.20 (2H,q,J=7Hz), 4.8-5.4 (1H,m), 5.53 (1H,dd,J=16 and 6Hz), 6.31 (1H,d,J=16Hz); IR (film)v max 2960, 1745, 1665, 1460, 1440, 1365, 1250 cm-1 ; MS m/e 280, 265, 236, 207, 191, 134.

Workup

  1. washThe organic layer was washed with 5% phosphoric acid solution until neutral and
  2. dry with materialdried over sodium sulfate
  3. customThe solvent was removed
  4. customthe residue chromatographed
  5. distillationKugelrohr distillation (bath temp. 150° C., 0.5 mm)

Sources & evidence

ORD record
ord-54d525d802794ace929e59b18a635a3c
Source dataset
uspto-grants-1991_02
Patent number
US04992106

Reaction notes

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