Tricyclohexylphosphine → 3-benzenesulfonyl-3H-indene-1-carboxylic acid ethyl ester

HRID 10081

반응식

HRID 10081 반응식
C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.CC(C)([O-])C.[Na+].[CH2:26]([O:28][C:29](=[O:35])[CH:30]=[CH:31]OCC)[CH3:27].[C:36]1([S:42]([CH2:45][C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][C:47]=2Br)(=[O:44])=[O:43])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.P([O-])(O)(O)=O.[K+]>O1CCCC1.C(OC)(C)(C)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:26]([O:28][C:29]([C:30]1[C:47]2[C:46](=[CH:51][CH:50]=[CH:49][CH:48]=2)[CH:45]([S:42]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)(=[O:44])=[O:43])[CH:31]=1)=[O:35])[CH3:27]

참가 물질

9

반응물 5

HCID 75806TricyclohexylphosphineHCID 221780Ethyl 3-ethoxy-2-propenoateHCID 516951Monobasic potassium phosphateHCID 113359052-Bromobenzyl Phenyl SulfoneHCID 23676156Sodium t-butoxide

생성물 1

HCID 99234833-benzenesulfonyl-3H-indene-1-carboxylic acid ethyl ester수율 85%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 8028Tetrahydrofuran용매2회HCID 15413tert-Butyl methyl ether용매

반응 조건

온도
0 °C

실험 절차

A solution of tricyclohexylphophine (46 mg, 0.164 mmol) in tetrahydrofuran (2.5 mL) under nitrogen was charged with palladium (II) acetate (24.5mg, 0.109 mmol). The reaction mixture was stirred for 45 minutes, then cooled to 0° C. and charged with sodium tert-butoxide (270 mg, 2.73 mmol). After 5 minutes a solution of β-ethoxyacrylic acid ethyl ester (158 μL, 1.09 mmol) and 2-bromobenzyl phenyl sulfone (340 mg, 1.09 mmol) in tetrahydrofuran (2.5 mL) was added dropwise over 2 minutes. Upon complete addition the reaction was warmed to room temperature and then heated to 60° C. for 2 hours. The reaction was cooled to room temperature, then diluted with methyl tert-butyl ether (25 mL) and poured into aqueous potassium dihydrogen phosphate (0.25 M, 25 mL), pH=7. The aqueous layer was separated and saturated by addition of solid sodium chloride and extracted with ethyl acetate (2×50 mL). The organic layer was separated and washed twice with aqueous saturated sodium chloride (2×30 mL), dried over sodium sulfate, filtered and concentrated in vacuo affording 3-benzenesulfonyl-3H-indene-1-carboxylic acid ethyl ester as a light orange oil (304 mg, 0.925 mmol, 85%). 1H NMR (400 MHz, CDCl3) δ 7.88–7.86 (m, 1H), 7.75–7.72 (m, 1H), 7.49–7.43 (m, 3H), 7.36–7.32 (m, 2H), 7.27–7.25 (m, 3H), 5.15 (d, 1H, J=2.1), 4.27 (q, 2H, J=7.1), 1.34 (t, 3H, J=7.1); IR (ATR, neat) 1709, 1649, 1463, 1444, 1314, 1271, 1247, 1188, 1133, 1081, 1044, 773, 752, 722, 686, 575, 528.

후처리

  1. additionUpon complete addition the reaction
  2. temperaturewas warmed to room temperature
  3. temperatureheated to 60° C. for 2 hours
  4. temperatureThe reaction was cooled to room temperature
  5. customThe aqueous layer was separated and saturated by addition of solid sodium chloride
  6. extractionextracted with ethyl acetate (2×50 mL)
  7. customThe organic layer was separated
  8. washwashed twice with aqueous saturated sodium chloride (2×30 mL)
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-9aeb12b8ac724711b637d517d0227baf
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091372B2

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