HCID 10694981, compound → HCID 10741550, compound

HRID 636547Notes

Reaction equation

HRID 636547 reaction equation
[C:1]1([CH3:32])[CH:6]=[CH:5][C:4]([S:7]([N:10]2[CH2:19][CH:18]([C:20]3[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[C:22]([O:28][CH3:29])[C:21]=3[CH2:30]O)[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH2:11]2)(=[O:9])=[O:8])=[CH:3][CH:2]=1>S(=O)(=O)(O)O>[CH3:29][O:28][C:22]1[C:23]([O:26][CH3:27])=[CH:24][CH:25]=[C:20]2[C:21]=1[CH2:30][C:16]1[C:17]3[CH:18]2[CH2:19][N:10]([S:7]([C:4]2[CH:5]=[CH:6][C:1]([CH3:32])=[CH:2][CH:3]=2)(=[O:8])=[O:9])[CH2:11][C:12]=3[CH:13]=[CH:14][CH:15]=1

Participants

3

Reactant 1

HCID 10694981HCID 10694981, compound

Product 1

HCID 10741550HCID 10741550, compoundYield 82.7%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
-5 °C

Procedure

Powdered compound 13 (427 mg, 0.98 mmol) was added in several portions to 50 mL of cold concentrated sulfuric acid (50 mL) at −40° C. under nitrogen with vigorous mechanical stirring. After the addition, the reaction mixture was warmed to −5° C. over 2 h and then poured onto crushed ice (450 g) and left stirring for 1 h. The product was extracted with dichloromethane (2×150 mL), washed with water (2×150 mL ), dried (MgSO4), filtered and evaporated to afford an oil that on trituration with ether at 0° C. yielded compound 14 (353 mg, 82%) as a white solid that was used for the next step without further purification. An analytical sample was prepared by centrifugal rotary chromatography using 50% ethyl acetate-hexane as the eluent followed by recrystallization from EtOAc/Hexane: mp 204-206° C.; 1H NMR (CDCl3) δ 2.40 (s, 3 H, CH3), 2.80 (m, 1 H, H-1a), 3.50 (dd, 1 H, J=4.5, 17.5 Hz, H-1b), 3.70 (dd, 1 H, J=7, 14 Hz, H-3a), 3.828 (s, 3 H, OCH3), 3.832 (s, 3H, OCH3), 3.9 (m, 1H, H-11b), 4.31 (d, 1H, J=17.6 Hz, H-7a), 4.74 (ddd, 1 H, J=1.7, 6.0, 11.2 Hz, H-7b), 4.76 (d, 1 H, J=14.8 Hz, H-3b), 6.77 (d, 1 H, J=8.3 Hz, ArH), 6.87 (d, 1 H, J=8.4 Hz, ArH), 6.94 (d, 1 H, J=7.6 Hz, ArH), 7.13 (t, 1 H, J=7.5 Hz, Ar-H-5), 7.18 (d, 1 H, J=7.2 Hz, ArH), 7.33 (d, 2 H, J=8.1 Hz, ArH), 7.78 (d, 2 H, J=8.2 Hz, ArH); MS (CI) m/z 436 (55), 198 (86), 157 (100); HRCIMS Calculated for C25H25NO4S: 436.1583; Found 436.1570; Anal. (C25H25NO4S) C, H, N.

Workup

  1. additionAfter the addition
  2. additionpoured
  3. waitleft
  4. extractionThe product was extracted with dichloromethane (2×150 mL)
  5. washwashed with water (2×150 mL )
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customto afford an oil that on trituration with ether at 0° C.

Sources & evidence

ORD record
ord-f768eef3059d4723941ee1175c920512
Source dataset
uspto-grants-2001_02
Patent number
US06194423B1

Reaction notes

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