Triethylamine → Brassitin

HRID 645940

反応式

HRID 645940 の反応式
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]([CH2:10][NH2:11])=[CH:2]1.[CH3:12]CN(CC)CC.Cl[C:20]([O:22]C)=[S:21]>CO.O>[CH3:12][S:22][C:20]([NH:11][CH2:10][C:3]1[C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][C:9]=2[NH:1][CH:2]=1)=[O:21]

参加物

6

反応物 3

HCID 8471TriethylamineHCID 4721071H-Indol-3-YlmethanamineHCID 554404Methyl chloromethanethioate

生成物 1

HCID 10036413Brassitin収率 94.3%

試薬・触媒・溶媒 2

HCID 962Water触媒HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

Freshly made 25 (190 mg, 1.3 mmol) and Et3N (271 μL, 1.95 mmol) was dissolved in anhydrous MeOH (10 mL). The flask was cooled to 0° C. and methyl chlorothioformate (116 μL, 1.36 mmol) was added dropwise followed by stirring at room temperature for 6 hours. A few drops of H2O were added to quench excess reagent and the volatiles were evaporated. The residue was dissolved in EtOAc (35 mL) and washed with 0.5 M HCl (2×20 mL), sat. NaHCO3 (20 mL), and brine (15 mL). The organic solution was dried with Na2SO4, filtered and concentrated to afford a crude brownish-orange solid (270 mg). After recrystallization from CH2Cl2/hexanes, beige crystals: 125 mg, 44% yd. mp 110-111° C. 1H NMR (CDCl3) δ 8.15 (br s, 1H, NH), 7.64 (d, 1H, ArH J=7.9), 7.39 (d, 1H, ArH J=7.1), 7.23 (m, 1H, ArH), 7.18 (m, 1H, ArH), 7.13 (m, 1H, ArH), 5.52 (br s, 1H, CH2NHC), 4.67 (d, 2H, ArCH2, J=5.1), 2.38 (s, 3H, SCH3). 13C NMR (CDCl3) δ 167.6, 136.3, 126.3, 123.3, 122.5, 119.9, 118.7, 112.1, 111.3, 36.9, 12.4. EI-MS m/z (%) 220 (37, M+), 205 (9), 172 (12, M+-SCH3), 130 (100). NP-HPLC r.t.=9.827 min. RP-HPLC (1/1 CH3CN/H2O+0.1% TFA) r.t.=9.512 min.

後処理

  1. customto quench excess reagent
  2. customthe volatiles were evaporated
  3. dissolutionThe residue was dissolved in EtOAc (35 mL)
  4. washwashed with 0.5 M HCl (2×20 mL), sat. NaHCO3 (20 mL), and brine (15 mL)
  5. dry with materialThe organic solution was dried with Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-42aff33a833c45ca80461d7255418b67
出典データセット
uspto-grants-2010_04
特許番号
US07705022B2

関連ノート

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