Water → HCID 19107627, compound

HRID 260406Notes

Reaction equation

HRID 260406 reaction equation
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[CH:25])[C:22]34[O:26][C:17]3([CH:18]([O:27][Si](CC)(CC)CC)[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:35][CH2:36][C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=4[N+:43]([O-:45])=[O:44])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC(S)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.O>C1COCC1.C(OCC)C>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[CH:25])[C:22]34[O:26][C:17]3([CH:18]([OH:27])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:35][CH2:36][C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=4[N+:43]([O-:45])=[O:44])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 962WaterHCID 6387tert-Butyl mercaptanHCID 2724141Tetrabutylammonium FluorideHCID 22401240HCID 22401240, compound

Product 1

HCID 19107627HCID 19107627, compoundYield 88.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

A solution of Compound 325 (45.27 g, 72.3 mmol) and tert-butylthiol (5.70 mL, 50.6 mmol) in THF (250 mL) was treated at zero degrees C with tetra-n-butylammonium fluoride (TBAF, 75.9 mL, 1.0M solution in THF, 75.9 mmol). The reaction mixture was stirred at 20° C. for 30 minutes, diluted with ethyl ether (750 mL), poured into water (1500 mL), and separated. The organic layer was washed with water (2×2000 mL), dried over anhydrous MgSO4, and evaporated in vacuo. The residue was purified by suspending it in hot acetonitrile (500 mL), cooling to 10° C., and filtering. The white solid was washed with acetonitrile (100 mL) and ethyl ether (200 mL) to give 32.70 g (88 percent) of Compound 326: white crystalline solid (about 3:1 mixture of diastereomers as determined by 1H NMR); mp 207°-209° C. (acetonitrile); Rf =0.46 (silica, 10 percent ethyl acetate in dichloromethane); IR (CHCl3) νmax 3469, 3196, 2950, 2922, 1689, 1521, 1495, 1386 cm-1 ; 1H NMR (500 MHz, DMSO-d6) δ 8.13 (dd, J=7.8, 1.2 Hz, 1 H, aromatic), 7.84 (br dd, J=7.8, 1.2 Hz, 1 H, aromatic), 7.79 (td, J=7.8, 1.2 Hz, 1 H, aromatic), 7.63 (td, J=7.8, 1.2 Hz, 1 H, aromatic), 7.60 (d, J=2.7 Hz, 1 H, H1, major isomer), 7.55 (d, J=2.7 Hz, 1 H, H1, minor isomer), 7.49-7.13 (m, 6 H, aromatic), 7.04 (dd, J=8.8, 2.7 Hz, 1 H, H3, major isomer), 7.01 (dd, J=8.8, 2.7 Hz, 1 H, H3, minor isomer), 5.65-5.44 (m, 2 H, benzylic; 1 H, OH; 1 H, H6, minor isomer), 5.31 (m, 1 H, H6, major isomer), 4.67 (br s, 1 H, H10, minor isomer), 4.48 (dt, J=9.0, 6.5 Hz, 1 H, H10, major isomer), 2.27 (dd, J=14.1, 6.7 Hz, 1 H, CH2, minor isomer), 2.22 (dd, J=14.8, 5.4 Hz, 1 H, CH2, major isomer), 1.80-1.20 (m, 5 H, CH2); 13CNMR (125 MHz, DMSO-d6) δ 155.6, 153.3, 150.8, 147.6, 134.0, 132.2, 129.5, 129.4, 129.3, 128.5, 128.2, 125.8, 124.8, 121.7, 115.8, 115.4, 114.1, 78.5, 76.0, 72.8, 67.0 and 66.7, 66.0, 62.4 and 60.2, 47.5, 29.1 and 27.3, 25.1 and 23.7, 22.4 and 19.8; MS (FAB+) m/e (rel intensity) 513 (M+H, 100), 391 (86); HRMS for C27H25N2O7 (M+H), calcd 513.1662, found 513.1662. Anal. Calcd for C29H24N2O7 : C, 67.96; H, 4.72; N, 5.47. Found: C, 67.71; H, 4.84; N, 5.36.

Workup

  1. customseparated
  2. washThe organic layer was washed with water (2×2000 mL)
  3. dry with materialdried over anhydrous MgSO4
  4. customevaporated in vacuo
  5. customThe residue was purified
  6. temperaturecooling to 10° C.
  7. filtrationfiltering
  8. washThe white solid was washed with acetonitrile (100 mL) and ethyl ether (200 mL)

Sources & evidence

ORD record
ord-0b8ee855fc564310b4c94ad74ea5cb3e
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

Loading…