Tetrahydrothiopyran-4-one → 10-amino-3,4-dihydro-7-trifluoromethyl-1H-thiopyrano[4,3-b]quinoline
Reaction equation
[F:1][C:2]([F:13])([F:12])[C:3]1[CH:4]=[C:5]([NH2:11])[C:6](=[CH:9][CH:10]=1)[C:7]#[N:8].[S:14]1[CH2:19][CH2:18][C:17](=O)[CH2:16][CH2:15]1>[N+](C1C=CC=CC=1)([O-])=O.[Cl-].[Zn+2].[Cl-]>[NH2:8][C:7]1[C:6]2[CH:9]=[CH:10][C:3]([C:2]([F:12])([F:13])[F:1])=[CH:4][C:5]=2[N:11]=[C:17]2[CH2:18][CH2:19][S:14][CH2:15][C:16]=12Participants
Conditions
- Temperature
- 50 °C
Procedure
To a solution of 4-trifluoromethyl anthranilonitrile (12.2 g) in 50 ml of nitrobenzene was added freshly fused and pulverized zinc chloride (13.4 g). This was stirred at 50° C. for 1.5 hours after which was added tetrahydrothiopyran-4-one (9.9 g). The reaction mixture was stirred at 130° C. for 2 hours and allowed to cool, and the resulting complex was filtered and rinsed with ethyl ether. The solid was partitioned between 2-butanone (MEK) and NH4OH and the aqueous phase was extracted with MEK (2x). The organics were washed with water, dried (saturated NaCl, MgSO4) and concentrated to give 10.2 g of a yellow powder m.p. 253°-259° C. d. A 3.7 g portion was recrystallized from methanol/water to give 3.0 g of an off-white powder, m.p. 258°-262° C. d.
Workup
- stirringThe reaction mixture was stirred at 130° C. for 2 hours
- temperatureto cool
- filtrationthe resulting complex was filtered
- washrinsed with ethyl ether
- customThe solid was partitioned between 2-butanone (MEK) and NH4OH
- extractionthe aqueous phase was extracted with MEK (2x)
- washThe organics were washed with water
- dry with materialdried (saturated NaCl, MgSO4)
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-f8607f1da51e4fc0a5e13f66e907da24
- Source dataset
- uspto-grants-1991_03
- Patent number
- US05002955
Reaction notes
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