2-Methyl-2-butene → HCID 86723412, compound

HRID 508564Notes

Reaction equation

HRID 508564 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH:10]2[CH2:12][CH2:11]2)[N:5]=[C:4]([CH:13]=[O:14])[C:3]=1[Cl:15].CC(=CC)C.P([O-])([O-])(O)=[O:22].[Na+].[Na+].Cl([O-])=O.[Na+]>O.C(O)(C)(C)C>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH:10]2[CH2:11][CH2:12]2)[N:5]=[C:4]([C:13]([OH:22])=[O:14])[C:3]=1[Cl:15]

Participants

7

Reactant 4

HCID 105532-Methyl-2-buteneHCID 24203Sodium Phosphate, DibasicHCID 23668197Sodium ChloriteHCID 86723403HCID 86723403, compound

Product 1

HCID 86723412HCID 86723412, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Conditions

Temperature
70 °C

Procedure

A microwave vial equipped with a magnetic stir bar was charged with 4-amino-3-chloro-6-(cyclopropylmethyl)-5-fluoropicolinaldehyde (63 mg, 0.276 mmol) and t-butanol (1.378 mL). The mixture was treated with H2O (0.459 mL), 2-methylbut-2-ene (0.3 mL, 0.276 mmol), sodium hydrogenphosphate (78 mg, 0.551 mmol), and finally sodium chlorite (74.8 mg, 0.827 mmol) was added in one portion. The mixture was heated to 70° C. in the microwave for 2 h. An aliquot of the reaction mixture was analyzed by LC-MS. LC-MS analysis showed one major product with the correct mass for the desired product. The reaction mixture was evaporated to dryness under N2. Purification via reverse phase chromatography yielded 4-amino-3-chloro-6-(cyclopropylmethyl)-5-fluoropicolinic acid (6.2 mg, 9.5%); 1H NMR (400 MHz, CDCl3) δ 11.60 (s, 1H), 5.00 (m, 2H), 2.70 (dd, J=7.0, 2.6 Hz, 2H), 1.17-1.02 (m, 1H), 0.60-0.48 (m, 2H), 0.27 (m, 2H); 19F NMR (376 MHz, CDCl3) δ −139.97; ESIMS m/z 243.2 ([M−H]−).

Workup

  1. customA microwave vial equipped with a magnetic stir bar
  2. additionwas added in one portion

Sources & evidence

ORD record
ord-63d5d66f237347ebb231a751e84c1c68
Source dataset
uspto-grants-2015_08
Patent number
US09096526B2

Reaction notes

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