Methanesulfonyl chloride → HCID 86605358, compound

HRID 132525Notes

Reaction equation

HRID 132525 reaction equation
[CH:1]([O:4][P:5]([CH2:11][O:12][CH2:13][N:14]1[C:22]([CH2:23][CH2:24][CH2:25]O)=[N:21][C:20]2[C:15]1=[N:16][C:17]([C:30]([C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)=[N:18][C:19]=2[NH:27][O:28][CH3:29])([O:7][CH:8]([CH3:10])[CH3:9])=[O:6])([CH3:3])[CH3:2].CS(Cl)(=O)=O.[N-:54]=[N+:55]=[N-:56].[Na+]>N1C=CC=CC=1.C(OCC)(=O)C>[CH:8]([O:7][P:5]([CH2:11][O:12][CH2:13][N:14]1[C:22]([CH2:23][CH2:24][CH2:25][N:54]=[N+:55]=[N-:56])=[N:21][C:20]2[C:15]1=[N:16][C:17]([C:30]([C:43]1[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=1)([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)=[N:18][C:19]=2[NH:27][O:28][CH3:29])([O:4][CH:1]([CH3:3])[CH3:2])=[O:6])([CH3:10])[CH3:9]

Participants

6

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 33557Sodium AzideHCID 86605356HCID 86605356, compound

Product 1

HCID 86605358HCID 86605358, compound

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

A solution of 36 (1.00 g, 1.48 mmol) in pyridine (20 mL) is treated with methanesulphonyl chloride (539 mg, 97%, 3.00 mmol) and the mixture is stirred for 20 h at room temperature. The reaction mixture is diluted with ethyl acetate (200 mL), washed with water (2×) and brine and the organic layer dried over MgSO4 followed by filtration and concentration. The residue containing 37 is dissolved in DMF (9 mL), treated with sodium azide (260 mg, 3.96 mmol) and the mixture stirred for 4 h at 100° C. The reaction mixture is diluted with ethyl acetate (300 mL), washed with water (2×) and brine and the organic layer dried over MgSO4. After filtration, the filtrate is concentrated and the residue was purified on a silica gel column using ethyl acetate:hexanes:methanol (1:1:0 to 1:1:0.2) as eluent to give 458 mg (44%, two steps) of product as a colorless film: 1H NMR (CDCl3): δ 8.04 (s, 1H), 7.89 (s, 1H), 7.40-7.18 (m, 13H), 6.79 (d, J=8.8 Hz, 2H), 4.87-4.76 (m, 1H), 4.73-4.60 (m, 2H), 4.19-3.68 (m, 4H), 3.77 (s, 3H), 3.41-3.32 (m, 1H), 3.22-3.10 (m, 1H), 2.47-2.32 (m, 1H), 2.24-2.12 (m, 1H), 1.29 (d, J=6.0 Hz, 6H), 1.24 (d, J=6.7 Hz, 6H). IR (neat, cm−1) 3017, 2103, 1605 and 1216. HRMS Calcd for C36H43N8O5P (M+H)+ 699.3172. Found: 699.3152.

Workup

  1. washwashed with water (2×) and brine
  2. dry with materialthe organic layer dried over MgSO4
  3. filtrationfollowed by filtration and concentration
  4. additionThe residue containing 37
  5. dissolutionis dissolved in DMF (9 mL)
  6. stirringthe mixture stirred for 4 h at 100° C
  7. washwashed with water (2×) and brine
  8. dry with materialthe organic layer dried over MgSO4
  9. filtrationAfter filtration
  10. concentrationthe filtrate is concentrated
  11. customthe residue was purified on a silica gel column
  12. customto give 458 mg (44%, two steps) of product as a colorless film

Sources & evidence

ORD record
ord-e8ac094e84df4c1a9068040134baf404
Source dataset
uspto-grants-2008_06
Patent number
US07388002B2

Reaction notes

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