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HRID628190

反应详情

EQUATION

反应方程式

HRID 628190 的结构方程式

REACTANTS

反应物

4
结构：O=C(OO)c1cccc(Cl)c1
HCID70297

Benzenecarboperoxoic acid, 3-chloro-

C7H5ClO3

结构：CCN(CC)P1OCc2ccccc2CO1
HCID4196879

2,4,3-Benzodioxaphosphepin-3-amine, N,N-diethyl-1,5-dihydro-

C12H18NO2P

结构：C=CCOC(=O)O[C@H]1[C@H](O)[C@@H](COCc2ccccc2)O[C@@H](O[Si](C)(C)C(C)(C)C)[C@@H]1N=[N+]=[N-]
HCID16216114

未命名化合物

结构：c1nnn[nH]1
HCID178418441

未命名化合物

PRODUCTS

生成物

1
结构：C=CCOC(=O)O[C@@H]1[C@@H](N=[N+]=[N-])[C@H](O[Si](C)(C)C(C)(C)C)O[C@H](COCc2ccccc2)[C@H]1OP1(=O)OCc2ccccc2CO1
HCID16216115

未命名化合物

收率 89%

AUXILIARIES

试剂、催化剂与溶剂

1
结构：ClCCl
溶剂HCID6344

Dichloromethane

CH2Cl2

PROCEDURE

实验过程

To a solution of compound 9 (1.30 g, 2.50 mmol) and 1H-tetrazole (3% wt, 10.0 mmol) in DCM (30 mL) was added N,N-diethyl-1,5-dihydro-3H-2,4,3-benzodioxaphosphepin-3-amine (1.20 g, 1.05 mmol). After the reaction mixture was stirred at room temperature for 15 min, it was cooled (−20° C.), stirred for another 10 min and then mCPBA (3.40 g, 50-55% wt, 10.0 mmol) was added. The reaction mixture was stirred at −20° C. for 20 min, and then quenched by the addition of saturated aqueous NaHCO3 (40 mL) and diluted with DCM (30 mL). The organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL), dried (MgSO4) and filtered. Next, the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1, v/v) to give 10 as a pale yellow oil (1.48 g, 89%). Rf=0.40 (hexane/ethyl acetate, 1/1, v/v). [α]25D=−10.3° (c=1.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.35-7.15 (m, 9H, aromatic), 5.98-5.85 (m, 1H, OCH2CH═CH2), 5.65 (d, 1H, J=1.2 Hz, J=17.4 Hz, OCH2CH═CH2), 5.50 (d, 1H, J=1.2 Hz, J=10.5 Hz, OCH2CH═CH2), 5.18-5.01 (m, 4H, C6H4(CH2O)P), 3.81 (dd, 1H, J2,3=10.5 Hz, J3,4=9.3 Hz, H-3), 4.64-4.52 (m, 6H, H-1, H-4, OCH2CH═CH2, CH2Ph), 3.82 (d, 1H, J6a,6b=9.0 Hz, H-6a), 3.72-3.61 (m, 2H, H-5, H-6b), 3.41 (dd, 1H, J1,2=7.4 Hz, J2,3=10.5 Hz, H-2), 0.92 (s, 9H, SiC(CH3)3), 0.16 (s, 3H, Si(CH3)), 0.15 (s, 3H, Si(CH3)). 13C NMR (75 MHz, CDCl3): δ 154.38 (C═O), 138.02-127.56 (aromatic), 131.33 (OCH2CH═CH2), 118.99 (OCH2CH═CH2), 97.13 (C-1), 76.77 (C-3), 74.27 (C-4), 74.08 (C-5), 73.50 (CH2Ph), 69.06 (OCH2CH═CH2), 68.74 (C-6), 68.55 (OC6H4(CH2O)P), 68.50 (OC6H4(CH2O)P), 65.97 (C-2), 25.53 (SiC(CH3)3), 17.92 (SiC(CH3)3), −4.35 (Si(CH3)2), −5.28 (Si(CH3)2). HR MS (m/z) calculated for C31H42N3O10PSi[M+Na]+, 698.2275. found, 698.2315.

WORKUP

后处理

  1. temperatureit was cooled (−20° C.)
  2. stirringstirred for another 10 min
  3. stirringThe reaction mixture was stirred at −20° C. for 20 min
  4. customquenched by the addition of saturated aqueous NaHCO3 (40 mL)
  5. additiondiluted with DCM (30 mL)
  6. washThe organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationNext, the filtrate was concentrated in vacuo
  10. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1