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【结 构 式】

【分子编号】37848

【品名】1-(methoxymethoxy)-3-methylbenzene; methoxymethyl 3-methylphenyl ether

【CA登记号】

【 分 子 式 】C9H12O2

【 分 子 量 】152.19308

【元素组成】C 71.03% H 7.95% O 21.03%

与该中间体有关的原料药合成路线共 3 条

合成路线1

该中间体在本合成路线中的序号:(X)

The intermediate naphthaleneboronic acid (XIX) has been obtained as follows: The bromination of the 3-methylphenyl methoxymethyl ether (X) with NBS gives the dibromo compound (XI), which is treated with sodium phenylsulfinate to afford the sulfone (XII). The condensation of (XII) with methyl crotonate (XIII) by means of LDA and KOH gives the butyric acid (XIV), which is cyclized to the tetralone (XV) by means of trifluoroacetic anhydride (TFAA). The aromatization of (XV) by means of t-BuOK or NaOH yields the 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol (XVI), which is methylated with dimethyl sulfate to afford the methyl ether (XVII). The reaction of (XVII) with trimethyl borate and n-BuLi gives the boronic ester (XVIII), which is hydrolyzed with water and ammonium chloride yielding the desired naphthaleneboronic acid (XIX). Alternatively, the naphthaleneboronic acid (XIX) has been obtained as follows: The reaction of 2,4-dibromophenol methoxymethyl ether (XX) with n-BuLi and cyclohexyl(isopropyl)amine gives the benzyne intermediate (XXI), which, without isolation is cyclized with the lithium enolate of 3-methylcrotonic acid dimethylamide (XXII) to afford the previously described naphthol (XVI), which is purified by chromatography.

1 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(X) 37848 1-(methoxymethoxy)-3-methylbenzene; methoxymethyl 3-methylphenyl ether C9H12O2 详情 详情
(XI) 37849 [4-bromo-3-(bromomethyl)phenoxy]methyl methyl ether; 1-bromo-2-(bromomethyl)-4-(methoxymethoxy)benzene C9H10Br2O2 详情 详情
(XII) 37850 2-bromo-5-(methoxymethoxy)benzyl phenyl sulfone; [2-bromo-5-(methoxymethoxy)benzyl](dioxo)phenyl-lambda(6)-sulfane C15H15BrO4S 详情 详情
(XIII) 26361 methyl (E)-2-butenoate 623-43-8 C5H8O2 详情 详情
(XIV) 37851 4-[2-bromo-5-(methoxymethoxy)phenyl]-3-methyl-4-(phenylsulfonyl)butyric acid C19H21BrO6S 详情 详情
(XV) 37852 5-bromo-8-(methoxymethoxy)-3-methyl-4-(phenylsulfonyl)-3,4-dihydro-1(2H)-naphthalenone C19H19BrO5S 详情 详情
(XVI) 37853 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol C13H13BrO3 详情 详情
(XVII) 37854 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthyl methyl ether; 5-bromo-1-methoxy-8-(methoxymethoxy)-3-methylnaphthalene C14H15BrO3 详情 详情
(XVIII) 37855 dimethyl 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronate C16H21BO5 详情 详情
(XIX) 37856 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid C14H17BO5 详情 详情
(XX) 37857 (2,4-dibromophenoxy)methyl methyl ether; 2,4-dibromo-1-(methoxymethoxy)benzene C8H8Br2O2 详情 详情
(XXI) 37858 1-bromo-4-(methoxymethoxy)-1,3-cyclohexadien-5-yne; 4-bromo-1,3-cyclohexadien-5-yn-1-yl methoxymethyl ether C8H7BrO2 详情 详情
(XXII) 37859   C8H14LiNO 详情 详情

合成路线2

该中间体在本合成路线中的序号:(X)

The intermediate naphthaleneboronic acid (XIX) has been obtained as follows: The bromination of the 3-methylphenyl methoxymethyl ether (X) with NBS gives the dibromo compound (XI), which is treated with sodium phenylsulfinate to afford the sulfone (XII). The condensation of (XII) with methyl crotonate (XIII) by means of LDA and KOH gives the butyric acid (XIV), which is cyclized to the tetralone (XV) by means of trifluoroacetic anhydride (TFAA). The aromatization of (XV) by means of t-BuOK or NaOH yields the 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol (XVI), which is methylated with dimethylsulfate to afford the methyl ether (XVII). The reaction of (XVII) with trimethyl borate and n-BuLi gives the boronic ester (XVIII), which is hydrolyzed with water and ammonium chloride yielding the desired naphthaleneboronic acid (XIX). Alternatively, the naphthaleneboronic acid (XIX) has been obtained as follows: The reaction of 2,4-dibromophenol methoxymethyl ether (XX) with n-BuLi and cyclohexyl(isopropyl)amine gives the benzyne intermediate (XXI), which, without isolation is cyclized with the lithium enolate of 3-methylcrotonic acid dimethylamide (XXII) to afford the previously described naphthol (XVI), which is purified by chromatography.

1 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(X) 37848 1-(methoxymethoxy)-3-methylbenzene; methoxymethyl 3-methylphenyl ether C9H12O2 详情 详情
(XI) 37849 [4-bromo-3-(bromomethyl)phenoxy]methyl methyl ether; 1-bromo-2-(bromomethyl)-4-(methoxymethoxy)benzene C9H10Br2O2 详情 详情
(XII) 37850 2-bromo-5-(methoxymethoxy)benzyl phenyl sulfone; [2-bromo-5-(methoxymethoxy)benzyl](dioxo)phenyl-lambda(6)-sulfane C15H15BrO4S 详情 详情
(XIII) 26361 methyl (E)-2-butenoate 623-43-8 C5H8O2 详情 详情
(XIV) 37851 4-[2-bromo-5-(methoxymethoxy)phenyl]-3-methyl-4-(phenylsulfonyl)butyric acid C19H21BrO6S 详情 详情
(XV) 37852 5-bromo-8-(methoxymethoxy)-3-methyl-4-(phenylsulfonyl)-3,4-dihydro-1(2H)-naphthalenone C19H19BrO5S 详情 详情
(XVI) 37853 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol C13H13BrO3 详情 详情
(XVII) 37854 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthyl methyl ether; 5-bromo-1-methoxy-8-(methoxymethoxy)-3-methylnaphthalene C14H15BrO3 详情 详情
(XVIII) 37855 dimethyl 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronate C16H21BO5 详情 详情
(XIX) 37856 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid C14H17BO5 详情 详情
(XX) 37857 (2,4-dibromophenoxy)methyl methyl ether; 2,4-dibromo-1-(methoxymethoxy)benzene C8H8Br2O2 详情 详情
(XXI) 37858 1-bromo-4-(methoxymethoxy)-1,3-cyclohexadien-5-yne; 4-bromo-1,3-cyclohexadien-5-yn-1-yl methoxymethyl ether C8H7BrO2 详情 详情
(XXII) 37859   C8H14LiNO 详情 详情

合成路线3

该中间体在本合成路线中的序号:(X)

The intermediate naphthaleneboronic acid (XIX) has been obtained as follows: The bromination of the 3-methylphenyl methoxymethyl ether (X) with NBS gives the dibromo compound (XI), which is treated with sodium phenylsulfinate to afford the sulfone (XII). The condensation of (XII) with methyl crotonate (XIII) by means of LDA and KOH gives the butyric acid (XIV), which is cyclized to the tetralone (XV) by means of trifluoroacetic anhydride (TFAA). The aromatization of (XV) by means of t-BuOK or NaOH yields the 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol (XVI), which is methylated with dimethylsulfate to afford the methyl ether (XVII). The reaction of (XVII) with trimethyl borate and n-BuLi gives the boronic ester (XVIII), which is hydrolyzed with water and ammonium chloride yielding the desired naphthaleneboronic acid (XIX). Alternatively, the naphthaleneboronic acid (XIX) has been obtained as follows: The reaction of 2,4-dibromophenol methoxymethyl ether (XX) with n-BuLi and cyclohexyl(isopropyl)amine gives the benzyne intermediate (XXI), which, without isolation is cyclized with the lithium enolate of 3-methylcrotonic acid dimethylamide (XXII) to afford the previously described naphthol (XVI), which is purified by chromatography.

1 Hoye, T.R.; et al.; Total synthesis of michellamines A-C, korupensamines A-D, and ancistrobrevine B. J Org Chem 1999, 64, 19, 7184.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(X) 37848 1-(methoxymethoxy)-3-methylbenzene; methoxymethyl 3-methylphenyl ether C9H12O2 详情 详情
(XI) 37849 [4-bromo-3-(bromomethyl)phenoxy]methyl methyl ether; 1-bromo-2-(bromomethyl)-4-(methoxymethoxy)benzene C9H10Br2O2 详情 详情
(XII) 37850 2-bromo-5-(methoxymethoxy)benzyl phenyl sulfone; [2-bromo-5-(methoxymethoxy)benzyl](dioxo)phenyl-lambda(6)-sulfane C15H15BrO4S 详情 详情
(XIII) 26361 methyl (E)-2-butenoate 623-43-8 C5H8O2 详情 详情
(XIV) 37851 4-[2-bromo-5-(methoxymethoxy)phenyl]-3-methyl-4-(phenylsulfonyl)butyric acid C19H21BrO6S 详情 详情
(XV) 37852 5-bromo-8-(methoxymethoxy)-3-methyl-4-(phenylsulfonyl)-3,4-dihydro-1(2H)-naphthalenone C19H19BrO5S 详情 详情
(XVI) 37853 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthol C13H13BrO3 详情 详情
(XVII) 37854 5-bromo-8-(methoxymethoxy)-3-methyl-1-naphthyl methyl ether; 5-bromo-1-methoxy-8-(methoxymethoxy)-3-methylnaphthalene C14H15BrO3 详情 详情
(XVIII) 37855 dimethyl 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronate C16H21BO5 详情 详情
(XIX) 37856 5-methoxy-4-(methoxymethoxy)-7-methyl-1-naphthylboronic acid C14H17BO5 详情 详情
(XX) 37857 (2,4-dibromophenoxy)methyl methyl ether; 2,4-dibromo-1-(methoxymethoxy)benzene C8H8Br2O2 详情 详情
(XXI) 37858 1-bromo-4-(methoxymethoxy)-1,3-cyclohexadien-5-yne; 4-bromo-1,3-cyclohexadien-5-yn-1-yl methoxymethyl ether C8H7BrO2 详情 详情
(XXII) 37859   C8H14LiNO 详情 详情
Extended Information