【结 构 式】 |
【分子编号】31871 【品名】bromo(pentyl)magnesium 【CA登记号】693-25-4 |
【 分 子 式 】C5H11BrMg 【 分 子 量 】175.35134 【元素组成】C 34.25% H 6.32% Br 45.57% Mg 13.86% |
合成路线1
该中间体在本合成路线中的序号:(III)The protection of the OH group of 2-hydroxyacetonitrile (I) with TBDMS-Cl and imidazole in THF gives the silyl ether (II), which is treated with pentylmagnesium bromide (III) in ethyl ether yielding the protected 1-hydroxyoctan-3-one (IV), which is deprotected with HCl in methanol/water affording the corresponding hydroxyketone (V). Finally, this compound is treated with hydroxylamine-O-sulfonic acid in liquid ammonia.
【1】 Forman, S.A.; Miller, K.W.; Olsen, R.W.; Kloczewiak, M.A.; Addona, G.H.; Husain, S.S.; Cohen, J.B.; Pratt, M.B.; Synthesis and properties of 3-(2-hydroxyethyl)-3-N-pentyldiazirine, a photoactivable general anesthetic. J Med Chem 1999, 42, 17, 3300. |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
40596 | (aminooxy)(hydroxy)dioxo-lambda(6)-sulfane | 2950-43-8 | H3NO4S | 详情 | 详情 | |
(I) | 14029 | Ethylene cyanohydrin; ECN; 3-Hydroxypropanenitrile | 109-78-4 | C3H5NO | 详情 | 详情 |
(II) | 31870 | 3-[[tert-butyl(dimethyl)silyl]oxy]propanenitrile | C9H19NOSi | 详情 | 详情 | |
(III) | 31871 | bromo(pentyl)magnesium | 693-25-4 | C5H11BrMg | 详情 | 详情 |
(IV) | 31872 | 1-[[tert-butyl(dimethyl)silyl]oxy]-3-octanone | C14H30O2Si | 详情 | 详情 | |
(V) | 31873 | 1-hydroxy-3-octanone | C8H16O2 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号:(III)Dimethylaluminium chloride-catalyzed ring opening of butyrolactone (I) with N,O-dimethylhydroxylamine furnishes the N-methoxy amide (II). Subsequent condensation of the Weinreb amide (II) with pentylmagnesium bromide (III) gives rise to the hydroxy ketone (IV). Further oxidation of the primary alcohol function of (IV) under Swern conditions leads to keto aldehyde (V). Then, Wittig condensation of aldehyde (V) with (methoxycarbonylmethylene) triphenylphosphorane (VI) affords the unsaturated ester (VII). Treatment of (VII) with urea-hydrogen peroxide in the presence of scandium triflate generates the hydroperoxide compound (VIII), which undergoes further intramolecular ring closure in the presence of triethylamine, leading to the 1,2-dioxane (IX). Enzymatic hydrolysis of ester (IX) employing pig liver esterase gives acid (X). After activation of (X) as the corresponding pentafluorophenyl ester (XI), condensation with propylamine in pyridine provides the title N-propyl amide
【1】 Murakami, N.; Kawanishi, M.; Mostaqul, H.M.; Tsuruta, K.; Itagaki, S.; Horii, T.; Kobayashi, M.; Exploitation for new antimalarials using spongean peroxides as scaffolds. 22nd Symp Med Chem (Nov 27 2002, Shizuoka) 2002, Abst 1P-12. |
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) | 20576 | dihydro-2(3H)-furanone | 96-48-0 | C4H6O2 | 详情 | 详情 |
(II) | 59681 | 4-hydroxy-N-methoxy-N-methylbutanamide | C6H13NO3 | 详情 | 详情 | |
(III) | 31871 | bromo(pentyl)magnesium | 693-25-4 | C5H11BrMg | 详情 | 详情 |
(IV) | 59682 | 1-hydroxy-4-nonanone | C9H18O2 | 详情 | 详情 | |
(V) | 59683 | 4-oxononanal | C9H16O2 | 详情 | 详情 | |
(VI) | 14689 | Methyl (triphenylphosphoranylidene)acetate; (methoxycarbonylmethylene)triphenylphosphorane;Methyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate | 2605-67-6 | C21H19O2P | 详情 | 详情 |
(VII) | 59684 | methyl (E)-6-oxo-2-undecenoate | C12H20O3 | 详情 | 详情 | |
(VIII) | 59685 | methyl (E)-6-hydroperoxy-6-methoxy-2-undecenoate | C13H24O5 | 详情 | 详情 | |
(IX) | 60083 | methyl 2-(6-methoxy-6-pentyl-1,2-dioxan-3-yl)acetate | C13H24O5 | 详情 | 详情 | |
(X) | 60084 | 2-(6-methoxy-6-pentyl-1,2-dioxan-3-yl)acetic acid | C12H22O5 | 详情 | 详情 | |
(XI) | 60085 | 2,3,4,5,6-pentafluorophenyl 2-(6-methoxy-6-pentyl-1,2-dioxan-3-yl)acetate | C18H21F5O5 | 详情 | 详情 |