Ethyl Acetate → HCID 71150502, compound

HRID 407257

Reaction equation

[NH2:1][C:2]1[C:7]([F:8])=[C:6](Cl)[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1[S:14][CH3:15].[Cl:16][C:17]1[CH:22]=[CH:21][C:20](B2OC(C)(C)C(C)(C)O2)=[C:19]([F:32])[C:18]=1[O:33][CH3:34].C(#N)C.O.C(OCC)(=O)C>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([C:20]2[CH:21]=[CH:22][C:17]([Cl:16])=[C:18]([O:33][CH3:34])[C:19]=2[F:32])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[C:3]=1[S:14][CH3:15]

Participants

Conditions

Temperature: 115 °C

Procedure

Methyl 4-amino-6-chloro-5-fluoro-3-(methylthio)picolinate (300 mg, 1.2 mmol), 2-(4-chloro-2-fluoro-3-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (450 mg, 1.6 mmol) Cesium fluoride (370 mg, 2.4 mmol) and his (triphenylphosphine) palladium (II) chloride (84 mg, 0.12 mmol) were combined in 5 ml 1:1 acetonitrile-water and heated in a microwave reactor at 115° C. for 30 m. The mixture was shaken with 30 ml ethyl acetate and 10 ml water. The org. phase was washed with 10 ml sat. NaCl, dried (Na2SO3) and evaporated. The residue was chromatographed on silica with a 0-40% ethyl acetate-hexane gradient. The gummy material was stirred with hexane to produce the written compound as a white solid, 60 mg. Mp: 113-117° C. 1H NMR (400 MHz, CDCl3) δ 7.27-7.24 (m, 2H), 5.31 (s, 2H), 3.98 (d, J=1.1 Hz, 3H), 3.96 (s, 3H), 2.32 (s, 3H). 19F NMR (376 MHz, CDCl3) δ −127.97, −128.06, −140.43, −140.52. ESIMS m/z 375 ([M+H]+), 373 ([M−H]−).

Workup

washphase was washed with 10 ml sat. NaCl
dry with materialdried (Na2SO3)
customevaporated
customThe residue was chromatographed on silica with a 0-40% ethyl acetate-hexane gradient

Sources & evidence

ORD record: ord-acb849c9add04051938b958970a7c606
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08754229B2

Linked notes

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