Benzo(B)Thiophene → 3-Methylbenzo[b]thiophene

HRID 846170Notes

Reaction equation

HRID 846170 reaction equation
S1C=CC2C=CC=CC1=2.Cl[C:11]1[S:15][C:14]2[CH:16]=[CH:17][CH:18]=[CH:19][C:13]=2[C:12]=1[CH3:20]>>[CH3:20][C:12]1[C:13]2[CH:19]=[CH:18][CH:17]=[CH:16][C:14]=2[S:15][CH:11]=1

Participants

3

Reactant 2

HCID 7221Benzo(B)ThiopheneHCID 123473452-Chloro-3-methyl-1-benzothiophene2×

Product 1

HCID 738173-Methylbenzo[b]thiophene

Procedure

from benzo[b]thiophene either by chloromethylation (R. Neidlen and E.P. Mrugowski: Arch. Pharm. [Weinheim, Ger.,] 308(7), 513-9, 1975): ##STR8## or by methylation and final bromination (D.A. Shirley and M.D. Cameron: JACS, 74, 664, 1952; U.S. Pat. No. 4,282,227): ##STR9## b) from 2- chloro-3-methylbenzo[b]thiophene by bromination (European Pat. No. 54,233): ##STR10## and 2- chloro-3-methylbenzo[b]thiophene is in turn obtained by chlorination of 3- methylbenzo[b]thiophene (V.I. Dronov et al, CA, 79, 115388f): ##STR11## c) from the corresponding thiophenol by total synthesis, for example, 2- chloro-2-propenyl-phenylthioether is formed by treating 2,3- dichloropropene, transposition in N,N-diethylaniline and cyclization with concentrated hydrochloric acid (W.K. Anderson and E.J. LaVoie, J. Chem. Soc., Chem. Commun., (5), 174, 1974; W.K. Anderson et al, J. Chem. Soc., Perkin Trans. 1, (1), 1-4, 1975): ##STR12## or by an alternative process also from the corresponding thiophenol by total synthesis, for example by forming respective 2- phenylthiopropionaldehyde acetal by treatment with 2-bromopropionaldehyde in sodium ethoxide and cyclization with an admixture of polyphosphoric acid and phosphorous pentoxide (Yasuo Matsuki and Fusaji Shoji, Nippon Kagaku Zasshi, 86,(10), 1067-72. 1965): ##STR13## d) in a similar manner the 3-position compounds are also obtained from the corresponding thiophenol by total synthesis and forming respective phenylthioacetone by treatment with chloroacetone and cyclization with polyphosphoric acid (N.B. Chapman, et al, J. Chem. Soc. C., (5), pp. 512-22, 1968; N.B. Chapman, et al, ibid, (5), 2747-51, 1968): ##STR14##

Sources & evidence

ORD record
ord-0b4c662d24a446ae9a88dbaece13dcd4
Source dataset
uspto-grants-1992_08
Patent number
US05135943

Reaction notes

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