Diisopropylethylamine → Carbamic acid, N-(3-bromo-5-chloro-2-fluorophenyl)-, 1,1-dimethylethyl ester

HRID 629507Notes

Reaction equation

HRID 629507 reaction equation
[Br:1][C:2]1[C:3]([F:12])=[C:4]([CH:8]=[C:9]([Cl:11])[CH:10]=1)C(O)=O.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:20])C=CC=CC=1.CC[N:32]([CH:36](C)C)C(C)C.[C:39]([OH:43])([CH3:42])([CH3:41])[CH3:40].C1(C)C=CC=CC=1>>[Br:1][C:2]1[C:3]([F:12])=[C:4]([NH:32][C:36](=[O:20])[O:43][C:39]([CH3:42])([CH3:41])[CH3:40])[CH:8]=[C:9]([Cl:11])[CH:10]=1

Participants

5

Reactant 4

HCID 81531DiisopropylethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 22595558Toluene tert-butyl alcoholHCID 510344623-Bromo-5-chloro-2-fluorobenzoic acid

Product 1

HCID 51034463Carbamic acid, N-(3-bromo-5-chloro-2-fluorophenyl)-, 1,1-dimethylethyl ester

Procedure

A solution of crude Intermediate 3-bromo-5-chloro-2-fluorobenzoic acid (2.03 g, 8 mmol), diphenylphosphoryl azide (2.07 mL, 9.6 mmol, 1.2 eq), and DIPEA (1.67 mL, 9.6 mmol, 1.2 eq) in 1:1 t-butanol/toluene (25 ml) was heated at 110° C. for 36 h. The mixture was concentrated, then partitioned between ethyl acetate and water. The organic layer was washed with brine, and was then dried over sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel chromatography (30:1 to 10:1 hexanes/ethyl acetate eluant) to provide the title compound. MS m/z: 267.8 (M+H)+. (M−tBu).

Workup

  1. concentrationThe mixture was concentrated
  2. custompartitioned between ethyl acetate and water
  3. washThe organic layer was washed with brine
  4. dry with materialwas then dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel chromatography (30:1 to 10:1 hexanes/ethyl acetate eluant)

Sources & evidence

ORD record
ord-dddba90b6da8415e89cd82b210fd93da
Source dataset
uspto-grants-2016_04
Patent number
US09314464B2

Reaction notes

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