Potassium Carbonate → HCID 57751160, compound

HRID 658558Notes

Reaction equation

HRID 658558 reaction equation
[C:1]([O:5][C:6]([NH:8][NH:9][C@H:10]([C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:11][CH2:12][CH3:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].C([O-])([O-])=O.[K+].[K+].[CH3:24][C:25]1[CH:26]=[C:27]([CH:31]=[C:32]([CH3:34])[CH:33]=1)[C:28](Cl)=[O:29]>C(Cl)Cl.O>[C:1]([O:5][C:6]([NH:8][N:9]([C@H:10]([C:14]([CH3:16])([CH3:15])[CH3:17])[CH2:11][CH2:12][CH3:13])[C:28](=[O:29])[C:27]1[CH:31]=[C:32]([CH3:34])[CH:33]=[C:25]([CH3:24])[CH:26]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 810883,5-Dimethylbenzoyl ChlorideHCID 57751169HCID 57751169, compound

Product 1

HCID 57751160HCID 57751160, compoundYield 19.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

(S)—N′-(1-tert-Butyl-butyl)-hydrazinecarboxylic acid tert-butyl ester (1 g, 4.09 mmoles) was dissolved in ca. 3 mL methylene chloride in a vial with a magnetic stir bar. A solution of 0.8 g K2CO3 (5.79 mmoles) in ca. 2 mL water was added, followed by 0.81 g (4.80 mmoles) 3,5-dimethylbenzoyl chloride. The reaction was stirred overnight, first on ice, and then allowed to warm to room temperature. Several mL each water and methylene chloride were then added to dissolve all solids. The aqueous layer was removed and the organic layer was dried over solid MgSO4. TLC indicated that the reaction was ca. 95% complete. The mixture was filtered through some glass wool into a vial. Solvent was evaporated with a stream of N2, chasing with 3:1 hexanes:ether and pentane. The residue was manipulated with a spatula to initiate crystallization, and after complete solidification, was triturated thrice with 2-3 mL pentane in a small fritted glass funnel. After drying in air, 300 mg (19.5%) (S)—N′-(1-tert-Butyl-butyl)-N′-(3,5-dimethyl-benzoyl)-hydrazinecarboxylic acid tert-butyl ester was obtained, indicated by TLC to be quite pure, chiral HPLC indicated e.e=93.3%. The product was dried in a vacuum oven at 50° C. for melting point determination. Rf=0.42 (4:1 hexanes:ethyl acetate, UV (strong), 12 (weak) visualization); mp=115.5-117.5° C.; [α]25589 −30.18 (c 2.02, CH3OH), 1H NMR (400 MHz, CDCl3) δ 7.15-7.03 (m, 3H), 6.07+6.00 (s+d, 1H), 4.52+4.40 (2 dd, 1H), 2.32+2.28+2.23 (3 s, 6H), 1.85-0.89 (m, 25H).

Workup

  1. dissolutionto dissolve all solids
  2. customThe aqueous layer was removed
  3. dry with materialthe organic layer was dried over solid MgSO4
  4. filtrationThe mixture was filtered through some glass wool into a vial
  5. customSolvent was evaporated with a stream of N2
  6. customcrystallization
  7. customafter complete solidification, was triturated thrice with 2-3 mL pentane in a small fritted glass funnel
  8. customAfter drying in air

Sources & evidence

ORD record
ord-4118bda2812e4ee3b448860ca7acb03c
Source dataset
uspto-grants-2011_12
Patent number
US08076517B2

Reaction notes

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