【结 构 式】 |
【分子编号】12991 【品名】1-[(3-Methyl-2-butenyl)sulfanyl]benzene; 3-Methyl-2-butenyl phenyl sulfide 【CA登记号】 |
【 分 子 式 】C11H14S 【 分 子 量 】178.29816 【元素组成】C 74.1% H 7.91% S 17.98% |
合成路线1
该中间体在本合成路线中的序号:(III)The condensation of thiophenol (II) with 3-methyl-2-butenyl bromide (I) by means of NaOH in refluxing acetone gives 3-methyl-2-butenyl(phenyl)sulfide (III), which is cyclized by means of P2O5 and H3PO4 in refluxing benzene to yield 4,4-dimethyl-3,4-dihydro-1H-1-benzothiopyran (IV). The acylation of (IV) with acetyl chloride catalyzed by SnCl4 in benzene affords the corresponding 6-acetyl derivative (V), which by dehydration with lithium diisopropylamide and diethyl chlorophosphate in THF is converted into 6-ethynyl-4,4-dimethyl-3,4-dihydro-2H-1-benzothiopyran (VI). Finally, this compound is condensed with ethyl 6-chloropyridine-3-carboxylate (VII) by means of butyllithium in THF. The ester (VII) is obtained by esterification of the corresponding acid (VIII) with ethanol by means of dicyclohexylcarbodiimide (DCC) and dimethylaminopyridine (DMAP).
【1】 Ngo, J.; Leeson, P.A.; Castaner, J.; Tazarotene. Drugs Fut 1997, 22, 3, 249. |
【2】 Chandraratna, R.A.S. (Allergan, Inc.); Disubstd. acetylenes bearing heteroaromatic and heterobicyclic groups having retinoid like activity. EP 0284288; JP 88255277; JP 95324085 . |
【3】 Chandraratna, R.A.S. (Allergan, Inc.); Disubstd. acetylenes bearing heteroaromatic and heterobicyclic groups having retinoid like activity. US 5089509 . |
【4】 Chandraratna, R.A. (Allergan, Inc.); Disubstd. acetylenes bearing heteroaromatic and heterobicyclic groups having retinoid like activity. WO 9611686 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(I) | 12989 | 4-Bromo-2-methyl-2-butene; 1-Bromo-3-methyl-2-butene | 870-63-3 | C5H9Br | 详情 | 详情 |
(II) | 12951 | Benzenethiol; Phenylmercaptan; Phenylhydrosulfide | 108-98-5 | C6H6S | 详情 | 详情 |
(III) | 12991 | 1-[(3-Methyl-2-butenyl)sulfanyl]benzene; 3-Methyl-2-butenyl phenyl sulfide | C11H14S | 详情 | 详情 | |
(IV) | 12992 | 4,4-Dimethylthiochromane | C11H14S | 详情 | 详情 | |
(V) | 12993 | 1-(4,4-Dimethyl-3,4-dihydro-2H-thiochromen-6-yl)-1-ethanone | C13H16OS | 详情 | 详情 | |
(VI) | 12994 | 6-Ethynyl-4,4-dimethylthiochromane | C13H14S | 详情 | 详情 | |
(VII) | 12995 | ethyl 6-chloronicotinate | 49608-01-7 | C8H8ClNO2 | 详情 | 详情 |
(VIII) | 12996 | 6-Chloronicotinic acid | 5326-23-8 | C6H4ClNO2 | 详情 | 详情 |