Hydrochloric Acid → Diethyl {2-[(3-phenoxybenzyl)thio]-4,5,6,7-tetrahydro-1,3-benzothiazol-7-yl}malonate

HRID 1163311Notes

Reaction equation

HRID 1163311 reaction equation
[O:1]([C:8]1[CH:9]=[C:10]([CH:23]=[CH:24][CH:25]=1)[CH2:11][S:12][C:13]1[S:14][C:15]2[CH:21](O)[CH2:20][CH2:19][CH2:18][C:16]=2[N:17]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S(Cl)(Cl)=O.[C:30]([O:38][CH2:39][CH3:40])(=[O:37])[CH2:31][C:32]([O:34][CH2:35][CH3:36])=[O:33].[H-].[Na+].Cl>O1CCCC1.C1(C)C=CC=CC=1>[O:1]([C:8]1[CH:9]=[C:10]([CH:23]=[CH:24][CH:25]=1)[CH2:11][S:12][C:13]1[S:14][C:15]2[CH:21]([CH:31]([C:32]([O:34][CH2:35][CH3:36])=[O:33])[C:30]([O:38][CH2:39][CH3:40])=[O:37])[CH2:20][CH2:19][CH2:18][C:16]=2[N:17]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 24386Thionyl ChlorideHCID 24758Sodium hydrideHCID 587552452-[(3-Phenoxybenzyl)thio]-4,5,6,7-tetrahydro-1,3-benzothiazol-7-ol

Product 1

HCID 58755254Diethyl {2-[(3-phenoxybenzyl)thio]-4,5,6,7-tetrahydro-1,3-benzothiazol-7-yl}malonateYield 98.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 2-[(3-phenoxybenzyl)thio]-4,5,6,7-tetrahydro-1,3-benzothiazol-7-ol (2.00 g, 5.41 mmol), thionyl chloride (0.723 mL) and toluene (10 mL) was stirred at room temperature for 3 hr. The reaction mixture was concentrated, and the residue was dissolved in tetrahydrofuran (10 mL). The solution was added to a mixture of diethyl malonate (1.60 g, 10 mmol), sodium hydride (60% in oil, 400 mg) and tetrahydrofuran (20 mL) at room temperature, and the mixture was stirred at the same temperature for 3 hr. The reaction mixture was neutralized with 1 M hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (AcOEt:hexane=1:19-2:1) to give the title compound (2.73 g, quantitative) as a pale-yellow oil.

Workup

  1. concentrationThe reaction mixture was concentrated
  2. dissolutionthe residue was dissolved in tetrahydrofuran (10 mL)
  3. stirringthe mixture was stirred at the same temperature for 3 hr
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed successively with water and saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel column chromatography (AcOEt:hexane=1:19-2:1)

Sources & evidence

ORD record
ord-ccc5017c5a694dff8d21fbd537370287
Source dataset
uspto-grants-2010_10
Patent number
US07820837B2

Reaction notes

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