Thiomorpholine → 4-[1-(Diphenylmethyl)azetidin-3-yl]thiomorpholine

HRID 749418ノート

反応式

HRID 749418 の反応式
CS(O[CH:6]1[CH2:9][N:8]([CH:10]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:7]1)(=O)=O.[NH:23]1[CH2:28][CH2:27][S:26][CH2:25][CH2:24]1.CCN(C(C)C)C(C)C>>[C:11]1([CH:10]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[N:8]2[CH2:7][CH:6]([N:23]3[CH2:28][CH2:27][S:26][CH2:25][CH2:24]3)[CH2:9]2)[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

参加物

4

反応物 3

HCID 67164ThiomorpholineHCID 81531DiisopropylethylamineHCID 27587161-(Diphenylmethyl)azetidin-3-yl methanesulfonate

生成物 1

HCID 689772644-[1-(Diphenylmethyl)azetidin-3-yl]thiomorpholine収率 91%

実験手順

A mixture of 1-(Diphenylmethyl)azetidin-3-yl methanesulfonate (see J. Org. Chem.; 56; 1991; 6729; 10 g, 31.5 mmol), thiomorpholine (3.9 g, 38 mmol) and DIPEA (4.9 g, 38 mmol) was refluxed overnight. The volatiles were removed by evaporation and the residue was partitioned between CH2Cl2 and NaHCO3 aq. The organic layer was washed twice with NaHCO3 aq. and then extracted with an aqueous solution of citric acid (3×70 mL of 1M). The aqueous layer was cooled and then pH adjusted with aqueous NaHCO3 and then 2M NaOH aq. The mixture was extracted with a mixture of CH2Cl2-EtOAc-ethanol and the organic solution was dried over MgSO4 and then removed by evaporation. There was obtained 9.3 g (91%) of 4-[1-(diphenylmethyl)azetidin-3-yl]thiomorpholine as a pale yellow solid. 1H NMR (400 MHz, CDCl3): 2.5 (m, 4H), 2.7 (m, 4H), 2.8 (t, 2H), 3.0 (qn 1H), 3.4 (m, 2H), 4.4 (s, 1H), 7.1-7.4 (m, 1OH); LCMS: m/z 325 (M+1)+.

後処理

  1. temperaturewas refluxed overnight
  2. customThe volatiles were removed by evaporation
  3. customthe residue was partitioned between CH2Cl2 and NaHCO3 aq. The organic layer
  4. washwas washed twice with NaHCO3 aq.
  5. extractionextracted with an aqueous solution of citric acid (3×70 mL of 1M)
  6. temperatureThe aqueous layer was cooled
  7. extraction2M NaOH aq. The mixture was extracted with a mixture of CH2Cl2-EtOAc-ethanol
  8. dry with materialthe organic solution was dried over MgSO4
  9. customremoved by evaporation

出典と根拠

ORDレコード
ord-c125e8e9281f42d4b0a13f9d1ff04c33
出典データセット
uspto-grants-2008_07
特許番号
US07402581B2

反応ノート

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