1-Tetradecyne → Ethyl oxo{(4-tetradec-1-ynylbenzyl)[4-(trifluoromethyl)benzyl]amino}acetate

HRID 735876Notes

Reaction equation

HRID 735876 reaction equation
[CH2:1]([O:3][C:4](=[O:27])[C:5]([N:7]([CH2:19][C:20]1[CH:25]=[CH:24][C:23](Br)=[CH:22][CH:21]=1)[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][CH:10]=1)=[O:6])[CH3:2].[CH:28]#[C:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41]>CCN(CC)CC.Cl.[Cu]Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[O:6]=[C:5]([N:7]([CH2:19][C:20]1[CH:25]=[CH:24][C:23]([C:28]#[C:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])=[CH:22][CH:21]=1)[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][CH:10]=1)[C:4]([O:3][CH2:1][CH3:2])=[O:27]

Participants

7

Reactant 2

HCID 698231-TetradecyneHCID 67186610Ethyl{(4-bromobenzyl)[4-(trifluoromethyl)benzyl]amino}(oxo)acetate

Product 1

HCID 67187897Ethyl oxo{(4-tetradec-1-ynylbenzyl)[4-(trifluoromethyl)benzyl]amino}acetateYield 50%

Reagents, catalysts & solvents 4

HCID 24593copper(I) bromideCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 313Hydrochloric AcidSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of ethyl{(4-bromobenzyl)[4-(trifluoromethyl)benzyl]amino}(oxo)acetate (100 mg, 0.23 mmol), 1-tetradecyne (66 mg, 0.34 mmol), copper(I) bromide (4.5 mg, 0.031 mmol) and palladium tetrakis(triphenylphosphine) (11 mg, 0.0095 mmol) in Et3N (1 mL) was heated at 90° C. for 75 min. After cooling to rt, the reaction mixture was diluted with an aqueous HCl solution (1N, 10 mL) and extracted with Et2O (2×20 mL). The combined organic layers were dried over MgSO4 and the solvent was removed under reduce pressure. The residue was purified by flash chromatography (cyclohex./Et2O 4:1) to give the title compound as yellow oil (63 mg, 50%). 1H NMR (CDCl3, 300 MHz) δ 7.61 (m, 2H), 7.33 (m, 4H), 7.14 (m, 2H), 4.51 (s, 1H), 4.47 (s, 1H), 4.34 (m, 4H), 2.40 (m, 2H), 1.58-1.26 (m, 23H), 0.88 (m, 3H). HPLC (Condition A), Rt: 8.21 min (HPLC purity: 99.3%).

Workup

  1. temperatureAfter cooling to rt
  2. extractionextracted with Et2O (2×20 mL)
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. customthe solvent was removed
  5. customThe residue was purified by flash chromatography (cyclohex./Et2O 4:1)

Sources & evidence

ORD record
ord-e40195fd509e4838b0f8975d02241470
Source dataset
uspto-grants-2009_09
Patent number
US07592477B2

Reaction notes

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