Water → HCID 71007327, compound

HRID 716187Notes

Reaction equation

HRID 716187 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH:5]=[C:6](B2OC(C)(C)C(C)(C)O2)[CH:7]=1.Cl[C:26]1[CH:31]=[CH:30][N:29]=[CH:28][C:27]=1[N+:32]([O-:34])=[O:33].C([O-])([O-])=O.[Na+].[Na+].O>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][C:2]1[CH:3]=[C:4]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:22])([CH3:21])[CH3:23])[CH:5]=[C:6]([C:26]2[CH:31]=[CH:30][N:29]=[CH:28][C:27]=2[N+:32]([O-:34])=[O:33])[CH:7]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 27357814-Chloro-3-nitropyridineHCID 71007260Carbamic acid, N-[3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-, 1,1-dimethylethyl ester

Product 1

HCID 71007327HCID 71007327, compoundYield 100%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

tert-butyl (3-methyl-5-(3-nitropyridin-4-yl)phenyl) carbamate. A glass microwave reaction vessel was charged with tert-butyl (3-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamate (200 mg, 0.60 mmol), 4-chloro-3-nitropyridine (114 mg, 0.72 mmol, Alfa-Aesar), Pd(dppf)Cl2 (25 mg, 0.030 mmol) and 2 M Na2CO3 (aq., 1.20 mL, 2.40 mmol) in dioxane (3 mL). The reaction mixture was stirred and heated in a Initiator microwave reactor (Personal Chemistry, Biotage AB, Inc., Upssala, Sweden) at 120° C. for 30 min. Water was then added and the mixture was extracted with EtOAc (3×). The combined organic layers were dried over anh. Na2SO4, filtered and concentrated. The crude material was purified by silica gel chromatography (0-50% EtOAc in hexanes) to provide tert-butyl (3-methyl-5-(3-nitropyridin-4-yl)phenyl)carbamate (198 mg, 0.60 mmol, 100% yield) as a tan solid. MS (ESI, pos. ion) m/z: 330.0 (M+1). 1H NMR (400 MHz, CDCl3) δ ppm 9.06 (s, 1 H), 8.78 (d, J=4.89 Hz, 1 H), 7.42 (d, J=4.89 Hz, 1 H), 7.24-7.27 (m, 1 H), 6.80 (s, 1 H), 6.53 (s, 1 H), 2.37 (s, 3 H), 1.48-1.55 (m, 9 H).

Workup

  1. customA glass microwave reaction vessel
  2. extractionthe mixture was extracted with EtOAc (3×)
  3. dry with materialThe combined organic layers were dried over anh. Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude material was purified by silica gel chromatography (0-50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-a495d4681714446c9bf8823d6b6d4eb7
Source dataset
uspto-grants-2015_11
Patent number
US09187486B2

Reaction notes

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