Triethylamine → HCID 376100, compound

HRID 1899059Notes

Reaction equation

HRID 1899059 reaction equation
O[CH2:2][CH2:3][N:4]([C:8]1[C:9]([N+:21]([O-:23])=[O:22])=[CH:10][C:11]([N+:18]([O-:20])=[O:19])=[C:12]([S:14]([NH2:17])(=[O:16])=[O:15])[CH:13]=1)[CH2:5][CH2:6]O.CCN(CC)CC.CS([Cl:35])(=O)=O.[Li+].[Cl-:37]>C1COCC1.CCOC(C)=O.CN(C=O)C>[Cl:37][CH2:2][CH2:3][N:4]([C:8]1[C:9]([N+:21]([O-:23])=[O:22])=[CH:10][C:11]([N+:18]([O-:20])=[O:19])=[C:12]([S:14]([NH2:17])(=[O:16])=[O:15])[CH:13]=1)[CH2:5][CH2:6][Cl:35]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 433294Lithium ChlorideHCID 10360491HCID 10360491, compound

Product 1

HCID 376100HCID 376100, compoundYield 69.9%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
130 °C

Procedure

A stirred solution of the above diol (IX) (1.90 g, 5.43 mmol) and Et3N (1.90 mL, 14 mmol) in dry THF (60 mL) was treated dropwise at 0° C. with methanesulfonyl chloride (0.89 mL, 11 mmol). After a further 15 min, the solution was diluted with EtOAc, washed well with water, and worked up to give the crude dimesylate (Id: X=OSO2Me, R=SO2NH2). This was immediately dissolved in DMF (50 mL) containing LiCl (20 g), and the mixture stirred at 130° C. for 15 min before solvent was removed under reduced pressure. The residue was partitioned between EtOAc and water, and the organic layer was worked up and chromatographed on silica gel. Elution with EtOAc gave 5-[N,N-bis(2-chloroethyl)amino]-2,4-dinitrobenzenesulfonamide (18) (Id: X=Cl, R=SO2NH2) (1.47 g, 64%), mp 153°-154° C. (EtOAc/petroleum ether). 1H NMR ((CD3)2CO) δ 8.54. (S, 1H, H-3), 7.99 (br, 2H, SO2NH2), 7.91 (S, 1H, H-6), 3.84 (t, J=5.6 Hz, 4H, CH2Cl), 3.67 (t, J=5.6 Hz, 4H, CH2N). 13C NMR ((CD3)2CO) δ 146.13 (C-5), 140.64 (C-1), 138.86, 136.93 (C-2,4), 124.95, 121.77 (C-3,6), 52.47 (CH2N), 41.62 (CH2Cl). Anal. (C10H12Cl2N4O6S) C,H,N,S.

Workup

  1. washwashed well with water
  2. customto give the crude dimesylate (Id: X=OSO2Me, R=SO2NH2)
  3. customwas removed under reduced pressure
  4. customThe residue was partitioned between EtOAc and water
  5. customchromatographed on silica gel
  6. washElution with EtOAc

Sources & evidence

ORD record
ord-58e099cbe67b4c2babec4188316728f8
Source dataset
uspto-grants-1996_11
Patent number
US05571845

Reaction notes

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