Nitrogen → Propan-2-yl 4,5-dichloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-picolinate

HRID 1424659Notes

Reaction equation

HRID 1424659 reaction equation
[Cl:1][C:2]1[C:7]([Cl:8])=[C:6](Cl)[N:5]=[C:4]([C:10]([O:12][CH:13]([CH3:15])[CH3:14])=[O:11])[CH:3]=1.[Cl:16][C:17]1[CH:22]=[CH:21][C:20](B2OCCCO2)=[C:19]([F:29])[C:18]=1[O:30][CH3:31].[F-].[Cs+].N#N>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O.C(#N)C>[Cl:1][C:2]1[C:7]([Cl:8])=[C:6]([C:20]2[CH:21]=[CH:22][C:17]([Cl:16])=[C:18]([O:30][CH3:31])[C:19]=2[F:29])[N:5]=[C:4]([C:10]([O:12][CH:13]([CH3:15])[CH3:14])=[O:11])[CH:3]=1

Participants

8

Reactant 4

HCID 947Nitrogen2×HCID 25953Cesium fluorideHCID 577824192-(4-Chloro-2-fluoro-3-methoxyphenyl)-1,3,2-dioxaborinaneHCID 71551715Propan-2-yl 4,5,6-trichloropicolinate

Product 1

HCID 70496077Propan-2-yl 4,5-dichloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-picolinate

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

A 100 mL Schlenk flask was charged with propan-2-yl 4,5,6-trichloropicolinate (10.46 g, 39.0 mmol), 2-(4-chloro-2-fluoro-3-methoxyphenyl)-1,3,2-dioxaborinane (13.27 g, 54.3 mmol) and CsF (11.76 g, 77.0 mmol). Acetonitrile (75 mL) and water (25 mL) were added. The reaction mixture was evacuated/backfilled with N2 (5×). Solid Pd(PPh3)2Cl2 (1.331 g, 1.896 mmol) was added. The solution was evacuated/backfilled with N2 (5×) and then stirred at reflux for 2 h. A white solid precipitated upon cooling to room temperature. The solid was filtered, washed with water and dried in air (10.56 g, 69%): mp 123.8-127.7° C.; 1H NMR (400 MHz, CDCl3) δ 8.20 (s, 1H, pyridine), 7.28 (dd, JH-H=8.5 Hz, JF-H=1.6 Hz, 1H), 7.13 (dd, JH-H=8.5 Hz, JF-H=6.8 Hz, 1H), 5.32 (septet, J=6.3 Hz, 1H, CHMe2), 3.99 (d, J=1.2 Hz, 3H, OMe), 1.41 (d, J=6.3 Hz, 6H, CHMe2); 13C{1H} NMR (101 MHz, CDCl3) δ 162.7 (CO2R), 153.8, 153.6 (d, JF-C=253 Hz, C2′), 146.7, 144.5 (d, JF-C=13 Hz), 144.0, 134.0, 130.0 (d, JF-C=3.4 Hz), 125.9, 125.3 (d, JF-C=3 Hz), 125.1 (d, JF-C=3 Hz), 70.4 (CHMe2), 61.6 (d, JF-C=4 Hz, OMe), 21.7 (CHMe2). Anal. Calcd for C16H13Cl3NO3: C, 48.94; H, 3.34; N, 3.57. Found: C, 48.91; H, 3.50; N, 3.51.

Workup

  1. temperatureat reflux for 2 h
  2. customA white solid precipitated
  3. filtrationThe solid was filtered
  4. washwashed with water
  5. customdried in air (10.56 g, 69%)

Sources & evidence

ORD record
ord-ac1a50714de64a2bb337e349c87cd624
Source dataset
uspto-grants-2015_01
Patent number
US08927731B2

Reaction notes

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