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【结 构 式】 
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【分子编号】38373 【品名】methyl 4-[(3,3,7,7,10,10-hexamethyl-1,2,5,8-dithiadiazecan-5-yl)methyl]benzoate 【CA登记号】 |
【 分 子 式 】C21H34N2O2S2 【 分 子 量 】410.64524 【元素组成】C 61.42% H 8.35% N 6.82% O 7.79% S 15.62% |
合成路线1
该中间体在本合成路线中的序号：(VI)The cyclization of 2,2,5,5-tetramethyl-3,4-dithiahexane-1,6-dial (I) with 2-methylpropane-1,2-diamine (II) in hoot ethanol gives 3,3,6,6,10,10-hexamethyl-1,2-dithia-5,8-diazacyclodeca-4,8-diene (III), which is reduced with NaBH3CN in ethanol to afford the corresponding cyclodecane compound (IV). The condensation of (IV) with 4-(bromomethyl)benzoic acid methyl ester (V) by means of K2CO3 in refluxing acetonitrile yields the adduct (VI), which is condensed with 2-(diethylamino)ethylamine (VII) by means of Al(CH3)3 in refluxing dichloromethane to provide the corresponding amide (VIII). Ring opening of (VIII) at the S-S bond by means of dithiothreitol (DTT) and TEA in MeOH gives the dithiol (IX), which is finally treated with TcO4Na, SnCl2 and NaOH in ethanol/water.
| 【1】 Auzeloux, P.; et al.; Technetium-99m radiolabelling of an N-amino-alkyl-benzamide nitrido- and oxo-technetium bis(aminoethanethiol) derivative synthesis and biological results. Potential melanoma tracer agents. J Label Compd Radiopharm 1999, 42, 6, 567. |
| 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) | 38370 | 2-[(1,1-dimethyl-2-oxoethyl)disulfanyl]-2-methylpropanal | C8H14O2S2 | 详情 | 详情 | |
| (II) | 29645 | 2-amino-1,1-dimethylethylamine; 2-methyl-1,2-propanediamine | 811-93-8 | C4H12N2 | 详情 | 详情 |
| (III) | 38371 | 3,3,6,6,10,10-hexamethyl-3,6,7,10-tetrahydro-1,2,5,8-dithiadiazecine | C12H22N2S2 | 详情 | 详情 | |
| (IV) | 38372 | 3,3,6,6,10,10-hexamethyl-1,2,5,8-dithiadiazecane | C12H26N2S2 | 详情 | 详情 | |
| (V) | 14565 | methyl 4-(bromomethyl)benzoate | 2417-72-3 | C9H9BrO2 | 详情 | 详情 |
| (VI) | 38373 | methyl 4-[(3,3,7,7,10,10-hexamethyl-1,2,5,8-dithiadiazecan-5-yl)methyl]benzoate | C21H34N2O2S2 | 详情 | 详情 | |
| (VII) | 12420 | N-(2-Aminoethyl)-N,N-diethylamine; N,N-Diethylethylene-diamine; N(1),N(1)-Diethyl-1,2-ethanediamine | 100-36-7 | C6H16N2 | 详情 | 详情 |
| (VIII) | 38374 | N-[2-(diethylamino)ethyl]-4-[(3,3,7,7,10,10-hexamethyl-1,2,5,8-dithiadiazecan-5-yl)methyl]benzamide | C26H46N4OS2 | 详情 | 详情 | |
| (IX) | 38375 | N-[2-(diethylamino)ethyl]-4-[[[2-methyl-2-[(2-methyl-2-sulfanylpropyl)amino]propyl](2-methyl-2-sulfanylpropyl)amino]methyl]benzamide | C26H48N4OS2 | 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 cyclization of 2,2,5,5-tetramethyl-3,4-dithiahexane-1,6-dial (I) with 2-methylpropane-1,2-diamine (II) in hot ethanol gives 3,3,6,6,10,10-hexamethyl-1,2-dithia-5,8-diazacyclodeca-4,8-diene (III), which is reduced with NaBH3CN in ethanol to afford the corresponding cyclodecane compound (IV). The condensation of (IV) with 4-(bromomethyl)benzoic acid methyl ester (V) by means of K2CO3 in refluxing acetonitrile yields the adduct (VI), which is condensed with 2-(diethylamino)ethylamine (VII) by means of Al(CH3)3 in refluxing dichloromethane to provide the corresponding amide (VIII). Ring opening of (VIII) at the S-S bond by means of dithiothreitol (DTT) and TEA in methanol gives the dithiol (IX), which is finally treated with TcO4Na, PPh3 and N,S-dimethyldithiocarbazate (MDTCZ) in ethanol / 1M HCl.
| 【1】 Auzeloux, P.; et al.; Technetium-99m radiolabelling of an N-amino-alkyl-benzamide nitrido- and oxo-technetium bis(aminoethanethiol) derivative synthesis and biological results. Potential melanoma tracer agents. J Label Compd Radiopharm 1999, 42, 6, 567. |
| 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) | 38370 | 2-[(1,1-dimethyl-2-oxoethyl)disulfanyl]-2-methylpropanal | C8H14O2S2 | 详情 | 详情 | |
| (II) | 29645 | 2-amino-1,1-dimethylethylamine; 2-methyl-1,2-propanediamine | 811-93-8 | C4H12N2 | 详情 | 详情 |
| (III) | 38371 | 3,3,6,6,10,10-hexamethyl-3,6,7,10-tetrahydro-1,2,5,8-dithiadiazecine | C12H22N2S2 | 详情 | 详情 | |
| (IV) | 38372 | 3,3,6,6,10,10-hexamethyl-1,2,5,8-dithiadiazecane | C12H26N2S2 | 详情 | 详情 | |
| (V) | 14565 | methyl 4-(bromomethyl)benzoate | 2417-72-3 | C9H9BrO2 | 详情 | 详情 |
| (VI) | 38373 | methyl 4-[(3,3,7,7,10,10-hexamethyl-1,2,5,8-dithiadiazecan-5-yl)methyl]benzoate | C21H34N2O2S2 | 详情 | 详情 | |
| (VII) | 12420 | N-(2-Aminoethyl)-N,N-diethylamine; N,N-Diethylethylene-diamine; N(1),N(1)-Diethyl-1,2-ethanediamine | 100-36-7 | C6H16N2 | 详情 | 详情 |
| (VIII) | 38374 | N-[2-(diethylamino)ethyl]-4-[(3,3,7,7,10,10-hexamethyl-1,2,5,8-dithiadiazecan-5-yl)methyl]benzamide | C26H46N4OS2 | 详情 | 详情 | |
| (IX) | 38375 | N-[2-(diethylamino)ethyl]-4-[[[2-methyl-2-[(2-methyl-2-sulfanylpropyl)amino]propyl](2-methyl-2-sulfanylpropyl)amino]methyl]benzamide | C26H48N4OS2 | 详情 | 详情 |