甲酸 → 6-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6-H-[1]benzothieno[3,2-c][1]benzopyran

HRID 1708

反应方程式

HRID 1708 反应方程式
FC(F)(F)S(O[C:7]1[CH:46]=[CH:45][C:10]2[C:11]3[S:32][C:31]4[CH:33]=[C:34](OS(C(F)(F)F)(=O)=O)[CH:35]=[CH:36][C:30]=4[C:12]=3[CH:13]([C:15]3[CH:20]=[CH:19][C:18]([O:21][CH2:22][CH2:23][N:24]4[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]4)=[CH:17][CH:16]=3)[O:14][C:9]=2[CH:8]=1)(=O)=O.C1(P(CCC)C2C=CC=CC=2)C=CC=CC=1.C(O)=O.C(N(CC)CC)C>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:24]1([CH2:23][CH2:22][O:21][C:18]2[CH:17]=[CH:16][C:15]([CH:13]3[C:12]4[C:30]5[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=5[S:32][C:11]=4[C:10]4[CH:45]=[CH:46][CH:7]=[CH:8][C:9]=4[O:14]3)=[CH:20][CH:19]=2)[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1

参与物

7

反应物 4

HCID 284甲酸HCID 8471三乙胺HCID 82100二苯基丙基磷HCID 158713633,9-Bis(trifluoromethanesulfonyloxy)-6-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6-H-[1]benzothieno[3,2-c][1]benzopyran

产物 1

HCID 107656216-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6-H-[1]benzothieno[3,2-c][1]benzopyran收率 57%

试剂、催化剂与溶剂 2

HCID 167845palladium acetate催化剂HCID 6228N,N-二甲基甲酰胺溶剂

实验过程

A solution of the product of Example 6 (780 mg, 1.06 mmol), palladium(II) acetate (42 mg, 0.19 mmol), 1,2-bis(diphenylphosphinopropane (149 mg, 0.36 mmol), formic acid (0.6 mL), and triethylamine (3.0 mL) in anhydrous dimethylformamide (40 mL) was stirred at ambient temperature for 4 d. After concentration, the residue was subjected chromatography (silica gel, 1:1 hexane:ethylacetate, 2-10% methanol, 0.1% ammonium hydroxide). Product containing fractions were concentrated, partitioned between methylene chloride (100 mL) and saturated sodium bicarbonate (100 mL), and the aqueous layer extracted with methylene chloride (50 mL). The combined organic extracts were dried (sodium sulfate), concentrated, and the residue purified by chromatography (silica gel, 1:1 hexane:ethylacetate, 2-10% methanol, 0.1% ammonium hydroxide) to give 267 mg (57%) of the title compound as an oil which gave a white, crystalline solid, mp 107° C., upon trituration with ether/hexane: 1H NMR (300 MHz, CDCl3) d 7.86 (d, J=7.4 Hz, 1H), 7.40 (m, 1H), 7.1-7.3 (m, 6H), 6.97 (t, J=7.3 Hz, 1H), 6.89 (d, J=8.1 Hz, 1H), 6.84 (d, J=8.6 Hz, 2H), 6.66 (s, 1H), 4.07 (t, J=6.1 Hz, 2H), 2.75 (t, J=6.1 Hz, 2H), 2.49 (m, 4H), 1.5-1.7 (m, 4H), 1.4-1.5 (m, 2H); 13C NMR (125 MHz, CDCl3) d 159.1, 151.6, 139.3, 137.1, 133.0, 131.5, 129.8, 129.1, 126.8, 124.6, 124.4, 123.7, 122.6, 121.5, 121.5, 119.3, 116.9, 114.6, 77.6, 65.7, 57.7, 54.9, 25.8, 24.0; MS (FD+) m/e 441 (M+); Anal. calc'd for C28H27NO2 S: C, 76.15; H, 6.17; N, 3.17. Found: C, 75.93; H, 6.44; N, 3.01.

后处理

  1. concentrationAfter concentration
  2. additionProduct containing fractions
  3. concentrationwere concentrated
  4. custompartitioned between methylene chloride (100 mL) and saturated sodium bicarbonate (100 mL)
  5. extractionthe aqueous layer extracted with methylene chloride (50 mL)
  6. dry with materialThe combined organic extracts were dried (sodium sulfate)
  7. concentrationconcentrated
  8. customthe residue purified by chromatography (silica gel, 1:1 hexane:ethylacetate, 2-10% methanol, 0.1% ammonium hydroxide)

来源与证据

ORD记录
ord-37dabead809445b0a1f66e1d5ecbac91
来源数据集
uspto-grants-1998_03
专利号
US05726186

关联笔记

加载中…