tert-Butanol → HCID 19891307, compound

HRID 893803Notes

Reaction equation

HRID 893803 reaction equation
CC(C)([O-])C.[K+].[Cl:7][CH:8](Cl)[C:9]1[CH:13]=[CH:12][S:11][CH:10]=1.[CH3:15][C:16](=[CH:18][CH3:19])[CH3:17].C(O)(C)(C)C>CCOCC>[Cl:7][C:8]1([C:9]2[CH:13]=[CH:12][S:11][CH:10]=2)[CH:18]([CH3:19])[C:16]1([CH3:17])[CH3:15]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 105532-Methyl-2-buteneHCID 19891317HCID 19891317, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 19891307HCID 19891307, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Potassium-t-butoxide (2.0 g, 18 mmol) was added over 5 min to a rapidly stirred solution of 3-dichloromethylthiophene produced as in a) (1.00 g 6.0 mmol) in dry ether (10-20 ml) at 0° C., containing 2-methylbut-2-ene (>8 equiv.). After 1 h at 20° C., the products were worked up as in Example 3a) to give oils which contained no starting material, although traces of t-butanol were present. The product was a mixture of geometrical isomers (anti/syn=1.31) (0.7 g, 59%). Kugelrohr distillation (oven temperature 80° C. at 0.1mmHg) afforded the product as a colourless oil (0.47 g, 40%) with no change in the isomer ratio (Found M+ 200.0431. C10H13SCl requires M, 200.0426). Chromatography on silica with petroleum as eluent resulted in decomposition of the minor (syn) isomer affording pure major anti-isomer (27%) (Found M+ 200.0437. C10H13SCl requires M, 200.0426) which showed νmax (film) 752s, 773s, 838s, 1453m, 2927s, 2950s and 2996 m cm-1 ; δH (200 MHz; CDCl3) 0.85 (3H, s), 1.22 (3H, s), 1.24 (4H, m), 7.11 (2H, m), 7.24 (1H, q, J 3, 5 Hz); m/z 200 (M+), 185 (M -CH3), 165 (M+ -Cl). From the 1H n.m.r. of the mixture, the minor (syn) isomer showed δH (200 Mz; CDCl3) 0.94 (3H, s), 1.05 (3H, d, J 6.5 Hz), 1.35 (1H, q, J 6.5 Hz), 1.48 (3H, s), 7.05 (1H, dd, J 1.5, 5.0 Hz) and 7.25 (2H,m); m/z 200 (M+), 185 (M+ -CH3), 165 (M+ -Cl).

Workup

  1. customto give oils which
  2. additiona mixture of geometrical isomers (anti/syn=1.31) (0.7 g, 59%)
  3. distillationKugelrohr distillation (oven temperature 80° C. at 0.1mmHg)

Sources & evidence

ORD record
ord-342bd4ab533f48f094fc760ab7a9ce7e
Source dataset
uspto-grants-1992_06
Patent number
US05126461

Reaction notes

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