4-Toluenesulfonyl chloride → HCID 24785948, compound

HRID 2422934Notes

Reaction equation

HRID 2422934 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:18][C:19](=[O:27])[NH:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH2:9][NH:10]C(=O)OC(C)(C)C)=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[S:34](Cl)([C:37]1[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=1)(=[O:36])=[O:35]>C(Cl)Cl.O1CCOCC1.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]([CH2:9][NH:10][S:34]([C:37]2[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=2)(=[O:36])=[O:35])[CH2:18][C:19]([NH:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)=[O:27])=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 11430Potassium CarbonateHCID 86628706HCID 86628706, compound

Product 1

HCID 24785948HCID 24785948, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 218864351,4-Dioxane--water (1/1)Solvent

Procedure

To a solution of 34 (0.106 g, 0.271 mmol) in DCM (2 ml) TFA (2 ml) was added. After stirring for 2 h at room temperature, the solvent was distilled under reduced pressure to give a brown solid. The crude residue was dissolved as obtained in 1,4-dioxane:H2O 1:1 (5 ml) and K2CO3 (0.225 g, 1.63 mmol, 6 eq) was added followed by tosyl chloride (0.056 g, 0.298 mmol, 1.1 eq) at room temperature. After stirring for 2 h at room temperature, the resulting mixture was evaporated in vacuo to dryness. Water (10 ml) was added and the resulting white solid was separated by filtration and dried. Pure 36 was obtained without further purification (0.079 g, 0.179 mmol, 66%), mp 200-202° C. 1H NMR (400 MHz, CD3OD) δ 2.39 (3H, s, Ar—CH3), 2.56 (1H, dd, J 9.2, 14.4 Hz, H—CHCO), 2.77 (1H, dd, J 6.8, 14.4 Hz, H—CHCO), 3.06 (1H, dd, J 8.2, 13.0 Hz, H—CHNH), 3.15 (1H, dd, J 6.8, 13.2 Hz, H—CHNH) 7.03-7.07 (1H, m, CH, Ar), 7.15 (2H, d, J 8.4 Hz, 2×CH, Ar), 7.21-7.26 (4H, s, 4×CH, Ar), 7.29 (2H, d, J 8.0 Hz, 2×CH, Ar), 7.36-7.38 (2H, m, 2×CH, Ar), 7.62 (2H, d, J 8.8 Hz, 2×CH, Ar). 13C NMR (400 MHz, DMSO-d6) δ21.63 (s) (Ar—CH3), 40.73 (s) (CH2CO), 41.87 (s) (CH2CHCH2), 48.13 (s) (CH2NH), 119.79 (s) (2×CH, Ar), 123.80 (s) (CH, Ar), 127.14 (s) (2×CH, Ar), 128.80 (s) (2×CH, Ar), 129.29 (s) (2×CH, Ar), 130.23 (s) (2×CH, Ar), 130.36 (s) (2×CH, Ar), 131.80 (s) (C, Ar), 138.14 (s) (C, Ar), 139.64 (s) (C, Ar), 141.53 (s) (C, Ar), 143.20 (s) (C, Ar), 169.81 (s) (C═O). νmax (pure sample)/(cm−1) 3340 (md) (N—H), 3141 (md) (N—H), 1665 (st) (C═O), 1598 (st), 1547 (st), 1493 (md), 1444 (st), 1154 (st), 1087 (md). MS (API-ES): m/z 443 [M+H]+ (100%), HRMS (API-ES) m/z found 443.1201 [M+H]+.

Workup

  1. distillationthe solvent was distilled under reduced pressure
  2. customto give a brown solid
  3. stirringAfter stirring for 2 h at room temperature
  4. customthe resulting mixture was evaporated in vacuo to dryness
  5. additionWater (10 ml) was added
  6. customthe resulting white solid was separated by filtration
  7. customdried
  8. customPure 36 was obtained without further purification (0.079 g, 0.179 mmol, 66%), mp 200-202° C

Sources & evidence

ORD record
ord-a8af23e32a5d4b2688af08408205c191
Source dataset
uspto-grants-2011_06
Patent number
US07960434B2

Reaction notes

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