Hydrochloric Acid → HCID 86706870, compound

HRID 717890Notes

Reaction equation

HRID 717890 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](I)[CH:5]=[C:4]([C:9]([F:12])([F:11])[F:10])[N:3]=1.C([Li])CCC.[O:18]1[CH2:22][CH2:21]OS1(=O)=O.Cl.O.[OH-].[Na+]>O1CCCC1.[Cl-].[Na+].O>[Cl:1][C:2]1[CH:7]=[C:6]([CH2:21][CH2:22][OH:18])[CH:5]=[C:4]([C:9]([F:12])([F:11])[F:10])[N:3]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 962WaterHCID 140751,3,2-Dioxathiolane, 2,2-dioxideHCID 14798Sodium HydroxideHCID 108597852-Chloro-4-iodo-6-(trifluoromethyl)pyridineHCID 178418339Butyllithium

Product 1

HCID 86706870HCID 86706870, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-78 °C

Procedure

2-Chloro-4-iodo-6-(trifluoromethyl)pyridine (0.50 g, 1.6 mmol, European Journal of Organic Chemistry, (18), 3793-3798, 2004) was dissolved in tetrahydrofuran (9.0 mL) and cooled to −78° C. 2.5 M n-Butyllithium in hexanes (0.98 mL, 2.4 mmol) was added dropwise. The reaction was stirred at −78° C. for 45 minutes, at which time 1,3,2-dioxathiolane 2,2-dioxide (0.24 g, 2.0 mmol, Aldrich) in Tetrahydrofuran (2.2 mL) was added. The mixture was then allowed to warm to ambient temperature and stir over 1.5 hours. 12.0 M hydrogen chloride in water (0.81 mL, 9.8 mmol) was added to the mixture and the reaction was stirred overnight. 1N NaOH was then added to achieve a pH between 8 and 9, and brine was also added. The product was extracted with EtOAc, and the organic layer was dried over sodium sulfate, filtered and concentrated. Flash chromatography using a 40 g silica gel cartridge, eluting with a gradient from 0-40% EtOAc in hexanes afforded product as a mixture of isomers, which contained about 50% of the desired isomer (0.09 g, 24%). LCMS (M+H)+: 226.0/228.1.

Workup

  1. additionwas added
  2. temperatureto warm to ambient temperature
  3. stirringthe reaction was stirred overnight
  4. additionwas also added
  5. extractionThe product was extracted with EtOAc
  6. dry with materialthe organic layer was dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. washeluting with a gradient from 0-40% EtOAc in hexanes afforded product as a mixture of isomers, which

Sources & evidence

ORD record
ord-c46cebcb9f0d4b138e9aa3632173c81c
Source dataset
uspto-grants-2015_11
Patent number
US09193733B2

Reaction notes

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