Potassium Iodide → Tyclopyrazoflor

HRID 1774302Notes

Reaction equation

HRID 1774302 reaction equation
[H-].[Na+].[Cl:3][C:4]1[C:8]([NH:9][C:10](=[O:20])[CH2:11][CH2:12][S:13][CH2:14][CH2:15][C:16]([F:19])([F:18])[F:17])=[CH:7][N:6]([C:21]2[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=2)[N:5]=1.[CH2:27](Br)[CH3:28].[I-].[K+]>S1(CCCC1)(=O)=O>[Cl:3][C:4]1[C:8]([N:9]([CH2:27][CH3:28])[C:10](=[O:20])[CH2:11][CH2:12][S:13][CH2:14][CH2:15][C:16]([F:18])([F:17])[F:19])=[CH:7][N:6]([C:21]2[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=2)[N:5]=1

Participants

6

Reactant 4

HCID 4875Potassium IodideHCID 6332Ethyl BromideHCID 24758Sodium hydrideHCID 86700584N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide

Product 1

HCID 86700627Tyclopyrazoflor

Reagents, catalysts & solvents 1

HCID 31347SulfolaneSolvent2×

Procedure

To 3-neck round bottomed flask (50 mL) was added sodium hydride (60% in oil, 0.130 g, 3.28 mmol) and sulfolane (16 mL). The gray suspension was stirred for 5 minutes then N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((3,3,3-trifluoropropyl)thio)propanamide (1.20 g, 3.16 mmol) dissolved in sulfolane (25 mL) was slowly added dropwise over 5 minutes. The mixture became a light gray suspension after 3 minutes and was allowed to stir for 5 minutes after which time ethyl bromide (0.800 mL, 10.7 mmol) and potassium iodide (0.120 g, 0.720 mmol) were added sequentially. The cloudy suspension was then allowed to stir at room temperature. The reaction was quenched after 6 hours by being poured drop-wise into cooled ammonium formate/acetonitrile solution (30 mL). The resulting orange colored solution was stirred and tetrahydrofuran (40 mL) was added. The mixture was assayed, using octanophenone as a standard, and found to contain 1.09 g (85%) of the desired product with a selectivity versus the retro-Michael-like decomposition product of 97:3.

Workup

  1. additionwas slowly added dropwise over 5 minutes
  2. customafter 3 minutes
  3. additionwere added sequentially
  4. stirringto stir at room temperature
  5. customThe reaction was quenched after 6 hours
  6. additionby being poured drop-wise
  7. temperatureinto cooled ammonium formate/acetonitrile solution (30 mL)
  8. stirringThe resulting orange colored solution was stirred
  9. additiontetrahydrofuran (40 mL) was added

Sources & evidence

ORD record
ord-4616fa7045b84acba0f2355591bc6e19
Source dataset
uspto-grants-2016_02
Patent number
US09260396B2

Reaction notes

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