4-Toluenesulfonyl chloride → HCID 87269179, compound

HRID 1516058Notes

Reaction equation

HRID 1516058 reaction equation
C([N:5]1[C:10](=[O:11])[C:9]([Cl:12])=[C:8]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH2:22][CH:23]([OH:25])[CH3:24])=[CH:17][CH:16]=2)[CH:7]=[N:6]1)(C)(C)C.[S:26](Cl)([C:29]1[CH:35]=[CH:34][C:32]([CH3:33])=[CH:31][CH:30]=1)(=[O:28])=[O:27].[CH2:37](N(CC)CC)C.CC[CH2:46][CH2:47][CH3:48]>ClCCl.CN(C1C=CN=CC=1)C.O.C(OCC)(=O)C>[C:47]([CH:14]([O:13][C:8]1[CH:7]=[N:6][NH:5][C:10](=[O:11])[C:9]=1[Cl:12])[C:15]1[CH:16]=[CH:17][C:18]([O:21][CH2:22][CH:23]([O:25][S:26]([C:29]2[CH:35]=[CH:34][C:32]([CH3:33])=[CH:31][CH:30]=2)(=[O:28])=[O:27])[CH3:24])=[CH:19][CH:20]=1)([CH3:46])([CH3:48])[CH3:37]

Participants

9

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8003PentaneHCID 8471TriethylamineHCID 59678685HCID 59678685, compound

Product 1

HCID 87269179HCID 87269179, compoundYield 58%

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the product of Example 6C (200 mg, 0.546 mmol) dissolved in anhydrous dichloromethane (6.0 mL) was added TsCl (125 mg, 0.656 mmol), DMAP (100 mg, 0.819 mmol) and triethylamine (0.0914 mL, 0.656 mmol). The reaction mixture continued stirring at room temperature. After 22 hours the reaction mixture was diluted with water. The aqueous layer was separated and extracted with ethyl acetate (3×). All combined organic layers were dried over Na2SO4, filtered, and concentrated to provide an oil. The crude material was purified using silica gel:chromatography (70:30 pentane:ethyl acetate) to provide the desired product (166 mg, 0.319 mmol) in 58% yield. 1H (CDCl37.80 (2H, d, 600 MHz): δ J=8.3 Hz), 7.72 (1H, s), 7.32 (2H, d, J=7.9 Hz), 7.29 (2H, d, J=8.7 Hz), 6.74 (2H, d, J=8.7 Hz), 5.22 (2H, s), 4.19 (1H, m), 4.02 (1H, dd, J=10.4, 6.0 Hz), 3.93 (1H, dd, J=10.4, 4.5 Hz), 2.44 (3H, s), 1.63 (9H, s) 1.42 (3H, d, J=6.5 Hz); 13C (CDCl3 158.9, 150 MHz): δ 158.3, 153.6, 144.6, 133.8, 129.6, 128.8, 127.8, 127.4, 125.1, 118.0, 114.7, 76.8, 71.5, 69.7, 66.2, 27.7, 21.5, 17.6.; HRMS calcd for C25H29ClN2O6S: 521.150762, found 521.1505.

Workup

  1. customThe aqueous layer was separated
  2. extractionextracted with ethyl acetate (3×)
  3. dry with materialAll combined organic layers were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto provide an oil
  7. customThe crude material was purified

Sources & evidence

ORD record
ord-d0fcdb825a8f430da23b134cd088858e
Source dataset
uspto-grants-2012_07
Patent number
US08226929B2

Reaction notes

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