Pyridine → HCID 86658326, compound

HRID 1890275Notes

Reaction equation

HRID 1890275 reaction equation
[CH3:1][S:2](Cl)(=[O:4])=[O:3].[C:6]1([C:12]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[N:13][NH:14][C:15](=[O:21])[CH2:16][CH2:17][CH:18]([OH:20])[CH3:19])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.N1C=CC=CC=1.C(OCC)(=O)C.O>ClCCl>[CH3:1][S:2]([O:20][CH:18]([CH2:17][CH2:16][C:15]([NH:14][N:13]=[C:12]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1)=[O:21])[CH3:19])(=[O:4])=[O:3]

Participants

6

Reactant 4

HCID 1049PyridineHCID 31297Methanesulfonyl chlorideHCID 22728543Water ethylacetateHCID 86658323HCID 86658323, compound

Product 1

HCID 86658326HCID 86658326, compoundYield 46.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

At 0° C., 0.25 ml (3.2 mmol) of methanesulphonyl chloride is added dropwise to a solution of 0.64 g (2.2 mmol) of N′-(diphenylmethylene)-4-hydroxypentane hydrazide, 0.19 ml (2.4 mmol) of pyridine and 0.01 mg of N—N-dimethylaminopyridine in 5 ml of dichloromethane. The reaction mixture is stirred at room temperature for 2 h, and ethyl acetate/water is then added. The organic phase is separated off and the aqueous phase is extracted with 3×100 ml of ethyl acetate. The combined organic phases are dried over Na2SO4 and freed from the solvent under reduced pressure. Purification by column chromatography on silica gel (cyclohexane/ethyl acetate) gives 0.38 g (44% pure) of 5-[2-(diphenylmethylene)hydrazino]-5-oxopentan-2-yl methanesulphonate; (log P(HCOOH): 2.82 with LC-MS: m/z=375 [M+]+). The product is taken up again in 2 ml of tetrahydrofuran, and 0.04 g (1.0 mmol) of sodium hydride is added at 0° C. After 16 h of stirring at room temperature, ethyl acetate/saturated aqueous NH4Cl solution is added, the organic phase is separated off and the aqueous phase is extracted with 3×100 ml of ethyl acetate. The combined organic phases are dried over Na2SO4 and freed from the solvent under reduced pressure. This gives 0.21 g (61%) of the desired product; (log P(HCOOH): 2.73); 1H-NMR (ppm): δ (DMSO-d6)=1.22 (d, 3H), 2.05-2.15 (m, 4H), 3.86 (sextet, 1H), 7.24-7.26 (m, 2H), 7.40-7.43 (m, 4H), 7.48-7.53 (m, 4H); LC-MS: m/z=279 [M+H]+.

Workup

  1. customThe organic phase is separated off
  2. extractionthe aqueous phase is extracted with 3×100 ml of ethyl acetate
  3. dry with materialThe combined organic phases are dried over Na2SO4
  4. customPurification by column chromatography on silica gel (cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-a5d6dd1eb4f04c508fef84cf78434ab2
Source dataset
uspto-grants-2013_08
Patent number
US08507472B2

Reaction notes

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