【结 构 式】 |
【分子编号】53331 【品名】2-amino-4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phenylamine; 4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-1,2-benzenediamine 【CA登记号】n/a |
【 分 子 式 】C20H36N2O8 【 分 子 量 】432.51452 【元素组成】C 55.54% H 8.39% N 6.48% O 29.59% |
合成路线1
该中间体在本合成路线中的序号:(VI)The intermediate phenylenediamine derivative (VI) has been obtained as follows: The reaction of 2-[2-(2-methoxyethoxy)ethoxy]ethanol (I) with Ts-Cl and NaOH in THF/water gives the tosylate (II), which is condensed with pyrocatechol (III) by means of K2CO3 in methanol, yielding the aryl ether (IV). The nitration of (IV) with HNO3 in acetic acid affords the dinitro derivative (V), which is finally reduced to the target phenylenediamine intermediate (VI) with hydrazine in ethanol catalyzed by Pd/C.
【1】 Sessler, J.L.; Miller, R.A.; Harriman, A.M. (Pharmacyclics, Inc.; University of Texas System); Radiation sensitization using texaphyrins. US 5622946 . |
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) | 53327 | Methyl Triglycol | 112-35-6 | C7H16O4 | 详情 | 详情 |
(II) | 53328 | 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate | n/a | C14H22O6S | 详情 | 详情 |
(III) | 11599 | o-Dihydroxybenzene; Catechol; Pyrocatechol | 120-80-9 | C6H6O2 | 详情 | 详情 |
(IV) | 53329 | 1,2-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}benzene; 2-{2-[2-(2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phenoxy)ethoxy]ethoxy}ethyl methyl ether | n/a | C20H34O8 | 详情 | 详情 |
(V) | 53330 | 1,2-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-4,5-dinitrobenzene; 2-{2-[2-(2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-4,5-dinitrophenoxy)ethoxy]ethoxy}ethyl methyl ether | n/a | C20H32N2O12 | 详情 | 详情 |
(VI) | 53331 | 2-amino-4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phenylamine; 4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-1,2-benzenediamine | n/a | C20H36N2O8 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号:(VI)The condensation of 3-[2-(acetoxymethyl)-5-(benzyloxycarbonyl)-4-methyl-1H-pyrrol-3-yl]propionic acid methyl ester (VII) with 3,4-diethyl-1H-pyrrole (VIII) by means of Ts-OH in ethanol gives the bis adduct (IX). The reduction of both methoxycarbonyl groups of (IX) with borane/THF complex yields bis-propanol derivative (X), which is debenzylated by hydrogenation with H2 and TEA over Pd/C in THF to afford the dicarboxylic acid (XI). The reduction of (XI) with TFA, triethyl orthoformate and LiOH in methanol/water provides the dialdehyde (XII), which is cyclized with the intermediate phenylenediamine (VI) by means of HCl in methanol to give the pentacyclic compound (XIII).
【1】 Sessler, J.L.; et al.; Synthesis and structural characterization of lanthanide(III) texaphyrins. Inorg Chem 1993, 32, 14, 3175. |
【2】 Sessler, J.L.; Miller, R.A.; Harriman, A.M. (Pharmacyclics, Inc.; University of Texas System); Radiation sensitization using texaphyrins. US 5622946 . |
【3】 Sessler, J.L.; Hemmi, G.W.; Magda, D.; Miller, R.A.; Ross, K.L.; Wright, M.; Dow, W.C.; Smith, D.A.; Kral, V.A.; Iverson, B.; Mody, T. (University of Texas System); Texaphyrin metal complex mediated ester hydrolysis. WO 9429316 . |
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) | 53331 | 2-amino-4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phenylamine; 4,5-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-1,2-benzenediamine | n/a | C20H36N2O8 | 详情 | 详情 |
(VII) | 53332 | benzyl 5-[(acetyloxy)methyl]-4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylate | n/a | C20H23NO6 | 详情 | 详情 |
(VIII) | 53333 | 3,4-diethyl-1H-pyrrole | 16200-52-5 | C8H13N | 详情 | 详情 |
(IX) | 53334 | benzyl 5-[(5-{[5-[(benzyloxy)carbonyl]-3-(3-methoxy-3-oxopropyl)-4-methyl-1H-pyrrol-2-yl]methyl}-3,4-diethyl-1H-pyrrol-2-yl)methyl]-4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylate | n/a | C44H51N3O8 | 详情 | 详情 |
(X) | 53335 | benzyl 5-[(5-{[5-[(benzyloxy)carbonyl]-3-(3-hydroxypropyl)-4-methyl-1H-pyrrol-2-yl]methyl}-3,4-diethyl-1H-pyrrol-2-yl)methyl]-4-(3-hydroxypropyl)-3-methyl-1H-pyrrole-2-carboxylate | n/a | C42H51N3O6 | 详情 | 详情 |
(XI) | 53336 | 5-[(5-{[5-carboxy-3-(3-hydroxypropyl)-4-methyl-1H-pyrrol-2-yl]methyl}-3,4-diethyl-1H-pyrrol-2-yl)methyl]-4-(3-hydroxypropyl)-3-methyl-1H-pyrrole-2-carboxylic acid | n/a | C28H39N3O6 | 详情 | 详情 |
(XII) | 53337 | 5-[(3,4-diethyl-5-{[5-formyl-3-(3-hydroxypropyl)-4-methyl-1H-pyrrol-2-yl]methyl}-1H-pyrrol-2-yl)methyl]-4-(3-hydroxypropyl)-3-methyl-1H-pyrrole-2-carbaldehyde | n/a | C28H39N3O4 | 详情 | 详情 |
(XIII) | 53338 | 3-[4,5-diethyl-24-(3-hydroxypropyl)-16,17-bis{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-10,23-dimethyl-13,20,25,26,27-pentaazapentacyclo[20.2.1.1~3,6~.1~8,11~.0~14,19~]heptacosa-1(24),3,5,8,10,12,14,16,18,20,22-undecaen-9-yl]-1-propanol | n/a | C48H71N5O10 | 详情 | 详情 |