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【结 构 式】

【分子编号】39937

【品名】7-(allyloxy)-5-methoxy-4-methyl-2-benzofuran-1(3H)-one

【CA登记号】

【 分 子 式 】C13H14O4

【 分 子 量 】234.25176

【元素组成】C 66.66% H 6.02% O 27.32%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(VIII)

The metal-ammonia reduction of 4,6-dimethoxy-m-xylene (I) gives 1,5-dimethyl-2,4-dimethoxy-1,4-cyclohexadiene (II), which by treatment with potassium tert-butoxide in DMSO is converted into the conjugated diene (III). The Dies-Alder reaction of (III) with dimethyl acetylenedicarboxylate (A), and subsequent elimination of the bridge affords dimethyl 3-methyl-4,6-dimethoxyphthalate (IV), which is selectively monodemethylated with BCl3 yielding the o-hydroxyphthalic ester (V). The hydrolysis and anhydrization of (V) gives 3-hydroxy-5-methoxy-6-methylphthalic anhydride (VI), which is reduced with Zn and HCl in acetic acid affording 4-methyl-5-methoxy-7-hydroxyphthalide (VII). The reaction of (VII) with allyl bromide (B) by means of K2CO3 in ether gives the allylic ether (VIII), which undergoes thermal rearrangement into 4-methyl-5-methoxy-7-hydroxy-6-allyl-phthalide (IX). The ozonolysis of (IX) affords the aldehyde (X), which by a Wittig condensation with 1-formylethylydenetriphenylphosphorane (XI) is converted into the new aldehyde (XII). A new Wittig reaction of (XII) with the phosphorane (XIII) gives the ethyl ester (XIV), which is finally hydrolyzed and partially reduced with diimide.

1 Castaner, J.; Hillier, K.; Mycophenolic acid. Drugs Fut 1978, 3, 8, 594.
2 Wright, J.J.; Birch, A.J.; A total synthesis of mycophenolic acid. J Chem Soc 1969, 14, 788-789.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(B) 11463 3-Bromo-1-propene; 3-Bromopropene;allyl bromide 106-95-6 C3H5Br 详情 详情
(A) 24551 Dimethyl acetylenedicarboxylate; Dimethyl 2-butynedioate;Acetylenedicarboxylic acid dimethyl ester 762-42-5 C6H6O4 详情 详情
(I) 39930 1,5-dimethoxy-2,4-dimethylbenzene; 5-methoxy-2,4-dimethylphenyl methyl ether C10H14O2 详情 详情
(II) 39931 1,5-dimethoxy-2,4-dimethyl-1,4-cyclohexadiene; 5-methoxy-2,4-dimethyl-1,4-cyclohexadien-1-yl methyl ether C10H16O2 详情 详情
(III) 39932 3-methoxy-4,6-dimethyl-1,3-cyclohexadien-1-yl methyl ether; 2,4-dimethoxy-1,5-dimethyl-1,3-cyclohexadiene C10H16O2 详情 详情
(IV) 39933 dimethyl 4,6-dimethoxy-3-methylphthalate C13H16O6 详情 详情
(V) 39934 dimethyl 6-hydroxy-4-methoxy-3-methylphthalate C12H14O6 详情 详情
(VI) 39935 7-hydroxy-5-methoxy-4-methyl-2-benzofuran-1,3-dione C10H8O5 详情 详情
(VII) 39936 7-hydroxy-5-methoxy-4-methyl-2-benzofuran-1(3H)-one C10H10O4 详情 详情
(VIII) 39937 7-(allyloxy)-5-methoxy-4-methyl-2-benzofuran-1(3H)-one C13H14O4 详情 详情
(IX) 39938 6-allyl-7-hydroxy-5-methoxy-4-methyl-2-benzofuran-1(3H)-one C13H14O4 详情 详情
(X) 39939 2-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-2-benzofuran-5-yl)acetaldehyde C12H12O5 详情 详情
(XI) 39940 2-(triphenylphosphoranylidene)propanal C21H19OP 详情 详情
(XII) 39941 (E)-4-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-2-benzofuran-5-yl)-2-methyl-2-butenal C15H16O5 详情 详情
(XIII) 39942 ethyl 2-(triethylphosphoranylidene)acetate C10H21O2P 详情 详情
(XIV) 39943 ethyl (2E,4E)-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-2-benzofuran-5-yl)-4-methyl-2,4-hexadienoate C19H22O6 详情 详情
Extended Information