Potassium Carbonate → 3-Triphenylmethylthio-2-(t-butoxycarbonylaminoethylthiomethyl)pyridine

HRID 2085990

反応式

HRID 2085990 の反応式
[C:1]1([C:7]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:8][C:9]2[C:10]([CH2:15]O)=[N:11][CH:12]=[CH:13][CH:14]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.S(Cl)(Cl)=O.[C:33]([NH:40][CH2:41][CH2:42][SH:43])([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.C(OCC)(=O)C.CCCCCC>[C:23]1([C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[S:8][C:9]2[C:10]([CH2:15][S:43][CH2:42][CH2:41][NH:40][C:33]([O:35][C:36]([CH3:37])([CH3:38])[CH3:39])=[O:34])=[N:11][CH:12]=[CH:13][CH:14]=2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

参加物

7

反応物 4

HCID 11430Potassium CarbonateHCID 24386Thionyl ChlorideHCID 3017761N-(tert-butoxycarbonyl)-2-aminoethanethiolHCID 99080472-Hydroxymethyl-3-triphenylmethylthiopyridine

生成物 1

HCID 99372073-Triphenylmethylthio-2-(t-butoxycarbonylaminoethylthiomethyl)pyridine収率 95.7%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒2 回HCID 21226206Ethyl acetate hexane溶媒

反応条件

温度
0 °C

実験手順

Into a 3 L round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen purge was charged 3-triphenylmethylthio-2-hydroxymethylpyridine (40.0 g, 0.104 mol, 1 eq.) followed by DMF (1.2 L). The solution was cooled to 0° C. and a pre-formed solution of thionyl chloride (12.4 g, 0.104 mol, 1.0 eq.) in DMF (200 mL) was charged dropwise over approximately 5 minutes. To this orange coloured solution was charged BOC-cysteamine (18.4 g, 0.104 mol, 1 eq.) followed by finely powdered potassium carbonate (43.1 g, 0.104 mol, 1 eq) and the resulting suspension was vigorously stirred for two hours until TLC analysis showed reaction completion (1:1 EtOAc/hexanes). The solution was poured into a 3 L of a 4:1 mixture of ice water/4:1 ethyl acetate-hexane. The aqueous was separated and extracted with an additional 200 mL of 4:1 ethyl acetate-hexane. The organics were combined and washed with water (2×200 mL) then brine (2×200 mL). The organic layer was dried with sodium sulfate, filtered and the solvent was removed in vacuo to give 54 grams of a brown oil. This oil was purified by column chromatography on silica gel to give 41 grams of the title compound as a light yellow oil. 1H NMR (CDCl3) δ 1.41 (s, 9H); 2.77 (t, 2H); 3.42 (t, 3H); 4.11 (s, 2H); 7.05-7.45 (m, 16H); 8.22 (d, 1H); 8.65 (d, 1H).

後処理

  1. customInto a 3 L round bottom flask equipped with a mechanical stirrer
  2. customthermometer and nitrogen purge
  3. customThe aqueous was separated
  4. extractionextracted with an additional 200 mL of 4:1 ethyl acetate-hexane
  5. washwashed with water (2×200 mL)
  6. dry with materialThe organic layer was dried with sodium sulfate
  7. filtrationfiltered
  8. customthe solvent was removed in vacuo

出典と根拠

ORDレコード
ord-37a7aad56f4447518584c7138bfc2a1a
出典データセット
uspto-grants-2004_04
特許番号
US06723716B1

関連ノート

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