Iodine → Trifluoroacetic acid

HRID 859022Notes

Reaction equation

HRID 859022 reaction equation
[F:1][C:2]([F:7])([F:6])[C:3]([OH:5])=[O:4].[I:8][C:9]1[S:10][C:11]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:24]=[C:23]([C:25]4[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:33])[F:32])=[CH:27][CH:26]=4)[N:22]=[CH:21][N:20]=3)[C:12]=2[N:13]=1.FC(F)(F)C(O)=O.[F:42][C:43]([F:67])([F:66])[C:44]1[CH:49]=[CH:48][C:47]([C:50]2[N:55]=[CH:54][N:53]=[C:52]([O:56][C:57]3[C:62]4[N:63]=[CH:64][S:65][C:61]=4[CH:60]=[CH:59][CH:58]=3)[CH:51]=2)=[CH:46][CH:45]=1.FC(F)(F)C1C=CC(C2N=CN=C(OC3C4N=C(N)SC=4C=CC=3)C=2)=CC=1.N(OCCC(C)C)=O.[I-].[Cs+].II>[Cu]I.COCCOC>[C:3]([OH:5])([C:2]([F:7])([F:6])[F:1])=[O:4].[I:8][C:9]1[S:10][C:11]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:24]=[C:23]([C:25]4[CH:26]=[CH:27][C:28]([C:31]([F:34])([F:32])[F:33])=[CH:29][CH:30]=4)[N:22]=[CH:21][N:20]=3)[C:12]=2[N:13]=1.[F:66][C:43]([F:42])([F:67])[C:44]1[CH:49]=[CH:48][C:47]([C:50]2[N:55]=[CH:54][N:53]=[C:52]([O:56][C:57]3[C:62]4[N:63]=[CH:64][S:65][C:61]=4[CH:60]=[CH:59][CH:58]=3)[CH:51]=2)=[CH:46][CH:45]=1

Participants

11

Reactant 6

HCID 807IodineHCID 8053Isoamyl NitriteHCID 24601Cesium iodideHCID 100916504-[6-(4-Trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazol-2-ylamineHCID 21865277HCID 21865277, compoundHCID 21865299HCID 21865299, compound

Product 3

HCID 6422Trifluoroacetic acidYield 0.1%HCID 10022213HCID 10022213, compoundHCID 10413592HCID 10413592, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
65 °C

Procedure

2-Iodo-4-[6-(4-trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazole trifluoroacetate and 4-[6-(4-Trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazole trifluoroacetate. A mixture of 4-[6-(4-trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazol-2-ylamine, (Example 65), (100 mg, 0.26 mmol), isoamyl nitrite (0.21 mL, 1.6 mmol, Aldrich), CsI (68 mg, 0.26 mmol, Aldrich), I2 (33 mg, 0.13 mol, Aldrich), CuI (15 mg, 0.079 mmol, Aldrich) and DME (5 mL) was heated at 65° C. for 1.5 h. The mixture was allowed to cool to room temperature and the solvent was removed under reduced pressure. The resulting mixture was purified by prep. LC (10–90% CH3CN/H2O modified with 0.1% TFA) to give 2-iodo-4-[6-(4-trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazole as a white solid [(30 mg, 23%), MS (ESI, pos. ion.) m/z: 500 (M+1)] and 4-[6-(4-trifluoromethyl-phenyl)-pyrimidin-4-yloxy]-benzothiazole as a brown solid [MS (ESI, pos. ion.) m/z: 374 (M+1)].

Workup

  1. temperatureto cool to room temperature
  2. customthe solvent was removed under reduced pressure
  3. customThe resulting mixture was purified by prep

Sources & evidence

ORD record
ord-443846e6a2cb4ffc86d25b963946eca8
Source dataset
uspto-grants-2006_12
Patent number
US07148221B2

Reaction notes

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