【结 构 式】 |
【分子编号】30329 【品名】3,6,9-Tris(tert-butoxycarbonylmethyl)-4(R)-[4,4-diphenylcyclohexyloxy(hydroxy)phosphoryloxymethyl]-3,6,9-triazaundecanedioic acid di-tert-butyl ester 【CA登记号】 |
【 分 子 式 】C53H84N3O14P 【 分 子 量 】1018.235542 【元素组成】C 62.52% H 8.32% N 4.13% O 22% P 3.04% |
合成路线1
该中间体在本合成路线中的序号:(XXII)The reduction of benzoin (XIII) with NaBH4 in ethanol/water gives the diol (XIV), which by a pinacol rearrangement by means of H2SO4 in hot acetic acid yields the diphenylacetaldehyde (XXV). The cyclization of (XV) with methyl vinyl ketone (XVI) by means of KOH in ethanol affords the cyclohexenone (XVII), which is reduced first with H2 over Pd/C in THF and then with NaBH4 in ethanol/water giving the 4,4-diphenylcyclohexanol (IX). The reaction of (IX) with PCl3 in THF yields the dichlorophosphite (XVIII), which is treated with imidazole (XIX) in THF affording the bis imidophosphite (XX). The condensation of (XX) with the previously obtained penta tert-butyl acetate compound (VI) in THF/heptane gives the imidophosphite (XXI), which is oxidized with sodium periodate yielding the phosphoric acid diester (XXII). Finally, the hydrolysis of (XXII) with HCl in ether/water eliminates the tert-butyl groups affording the desired chelating ligand (XII).
【1】 Amedio, J.C. Jr.; et al.; A practical preparation of 4,4-diphenylcyclohexanol: A key intermediate in the synthesis of MS-325. Synth Commun 1998, 28, 20, 3895. |
【2】 Dunham, S.O.; Lauffer, R.B. (Epix Medical, Inc.); Contrast-enhanced diagnostic imaging method for monitoring interventional therapies. WO 9917809 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(VI) | 30317 | 3,6,9-Tris(tert-butoxycarbonylmethyl)-4(R)-(hydroxymethyl)-3,6,9-triazaundecanedioic acid di-tert-butyl ester | C35H65N3O11 | 详情 | 详情 | |
(IX) | 30319 | 4,4-diphenylcyclohexanol | C18H20O | 详情 | 详情 | |
(XII) | 30322 | 3,6,9-Tris(carboxymethyl)-4(R)-[4,4-diphenylcyclohexyloxy(hydroxy)phosphoryloxymethyl]-3,6,9-triazaundecanedioic acid | C33H44N3O14P | 详情 | 详情 | |
(XIII) | 24135 | 2-hydroxy-1,2-diphenyl-1-ethanone; benzoin | 579-44-2 | C14H12O2 | 详情 | 详情 |
(XIV) | 30331 | Hydrobenzoin; 1,2-diphenyl-1,2-ethanediol | 655-48-1 | C14H14O2 | 详情 | 详情 |
(XV) | 30323 | 2,2-diphenylacetaldehyde | 947-91-1 | C14H12O | 详情 | 详情 |
(XVI) | 30324 | 3-buten-2-one; methyl vinyl ketone | 78-94-4 | C4H6O | 详情 | 详情 |
(XVII) | 30325 | 4,4-diphenyl-2-cyclohexen-1-one | C18H16O | 详情 | 详情 | |
(XVIII) | 30326 | Dichlorophosphorous acid 4,4-diphenylcyclohexyl ester | C18H19Cl2OP | 详情 | 详情 | |
(XIX) | 10255 | Imidazole; 1H-Imidazole | 288-32-4 | C3H4N2 | 详情 | 详情 |
(XX) | 30327 | 4,4-diphenylcyclohexyl di(1H-imidazol-1-yl)phosphinite | C24H25N4OP | 详情 | 详情 | |
(XXI) | 30328 | 3,6,9-Tris(tert-butoxycarbonylmethyl)-4(R)-[4,4-diphenylcyclohexyloxy(1-imidazolyl)phosphoryloxymethyl]-3,6,9-triazaundecanedioic acid di-tert-butyl ester | C56H86N5O12P | 详情 | 详情 | |
(XXII) | 30329 | 3,6,9-Tris(tert-butoxycarbonylmethyl)-4(R)-[4,4-diphenylcyclohexyloxy(hydroxy)phosphoryloxymethyl]-3,6,9-triazaundecanedioic acid di-tert-butyl ester | C53H84N3O14P | 详情 | 详情 |