Ethyl chloroformate → HCID 22710460, compound

HRID 1061077Notes

Reaction equation

HRID 1061077 reaction equation
Cl.[Cl:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([S:13]([N:16]1[CH2:21][CH2:20][N:19]([C:22]([C:24]3[S:25][C:26]4[CH2:27][NH:28][CH2:29][CH2:30][C:31]=4[N:32]=3)=[O:23])[CH2:18][CH2:17]1)(=[O:15])=[O:14])[CH:7]=[CH:6]2.O.[C:34](O)(=O)[CH:35]=[O:36].ClC(OCC)=O.[BH4-].[Na+]>O1CCCC1.O.C(N(CC)CC)C>[ClH:2].[Cl:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([S:13]([N:16]1[CH2:17][CH2:18][N:19]([C:22]([C:24]3[S:25][C:26]4[CH2:27][NH:28][CH:29]([CH2:34][CH2:35][OH:36])[CH2:30][C:31]=4[N:32]=3)=[O:23])[CH2:20][CH2:21]1)(=[O:14])=[O:15])[CH:7]=[CH:6]2

Participants

8

Reactant 4

HCID 10928Ethyl chloroformateHCID 4311764Sodium borohydrideHCID 11272253HCID 11272253, compoundHCID 15620607Glyoxylic acid, monohydrate

Product 1

HCID 22710460HCID 22710460, compoundYield 72.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

In a similar manner to Example 91 except for the use of 1-[(6-chloronaphthalen-2-yl)sulfonyl]-4-[(4,5,6,7-tetrahydrothiazolo[5,4-c]pyridin-2-yl)carbonyl]piperazine hydrochloride (132 mg) and glyoxylic acid hydrate (82 mg) as the raw materials, the reaction was conducted, whereby a crude product was obtained. The product was suspended in tetrahydrofuran (50 ml), followed by the addition of triethylamine (0.22 ml) and ethyl chloroformate (0.03 ml) under ice cooling. After stirring at room temperature for 15 minutes, sodium borohydride (50 mg) and water (10 ml) were added and the resulting mixture was stirred at room temperature for one hour. The reaction mixture was concentrated under reduced pressure. The concentrate was diluted with dichloromethane, washed with saturated saline and then dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by chromatography on a silica gel column (dichloromethane˜dichloromethane:methanol=100:3). The purified product was dissolved in saturated ethanol hydrochloride (1 ml), followed by concentration under reduced pressure. The concentrate was pulverized and washed in ethyl acetate, whereby the title compound (52 mg, 33%) was obtained.

Workup

  1. customwhereby a crude product was obtained
  2. stirringthe resulting mixture was stirred at room temperature for one hour
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. additionThe concentrate was diluted with dichloromethane
  5. washwashed with saturated saline
  6. dry with materialdried over anhydrous sodium sulfate
  7. customThe residue obtained
  8. distillationby distilling off the solvent under reduced pressure
  9. customwas purified by chromatography on a silica gel column (dichloromethane˜dichloromethane:methanol=100:3)
  10. dissolutionThe purified product was dissolved in saturated ethanol hydrochloride (1 ml)
  11. concentrationfollowed by concentration under reduced pressure
  12. washwashed in ethyl acetate

Sources & evidence

ORD record
ord-52c27a54338b400f9321c8cdab5c9048
Source dataset
uspto-grants-2003_02
Patent number
US06525042B1

Reaction notes

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