Acetic Acid → HCID 70266149, compound

HRID 2289568Notes

Reaction equation

HRID 2289568 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([O:17][CH2:18][CH3:19])(=[O:16])[C:14]#[CH:15].[N+:20]([C:23]1[C:30]([NH:31][C:32](=[O:39])[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[C:29]([O:40][CH2:41][CH2:42][CH2:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[CH:28]=[CH:27][C:24]=1[CH:25]=[O:26])([O-:22])=[O:21].C(O)(=O)C>O1CCCC1>[OH:26][CH:25]([C:24]1[CH:27]=[CH:28][C:29]([O:40][CH2:41][CH2:42][CH2:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)=[C:30]([NH:31][C:32](=[O:39])[C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[C:23]=1[N+:20]([O-:22])=[O:21])[C:15]#[C:14][C:13]([O:17][CH2:18][CH3:19])=[O:16]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 7912DiisopropylamineHCID 12182Ethyl propiolateHCID 86755559HCID 86755559, compoundHCID 178418339Butyllithium

Product 1

HCID 70266149HCID 70266149, compoundYield 105%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of diisopropylamine (0.6 ml, 4.26 mmol) in tetrahydrofuran (12 ml) was added, at -78° C. under an argon atmosphere, 1.5 N butyllithium (2.66 ml, 3.99 mmol). The mixture was stirred for 30 min. Ethyl propiolate (0.49 ml, 4.79 mmol) and a solution of 2-nitro-4-phenylbutoxybenzoylaminobenzaldehyde (1.1 g, 2.66 mmol) in tetrahydrofuran (3 ml) were added in that order, and the mixture was stirred at -78° C. for additional one hr. A solution of acetic acid (0.47 ml, 8.25 mmol) in tetrahydrofuran (3 ml) was then added thereto, followed by extraction with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, water, a saturated aqueous sodium bicarbonate solution, and saturated brine in that order. It was then dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give ethyl 4-hydroxy-4-(2-nitro-4-phenylbutoxybenzoylaminophenyl)-2-butynoate as an oil (1.443 g). Ethyl 4-hydroxy-4-(2-nitro-4-phenylbutoxybenzoylaminophenyl)-2-butynoate thus prepared was dissolved in toluene (10 ml), 4-methoxybenzylazide (1.3 g, 7.98 mmol) was added to the solution, and the mixture was stirred at 100° C. for 5 hr. The reaction mixture was cooled to room temperature, and the resultant crystal was collected by filtration to give ethyl 4-hydroxy-1-(4-methoxybenzyl)-(2-nitro-4-phenylbutoxybenzoylaminophenyl)methyl-1,2,3-triazole-5-carboxylate (a-1) (550.4 mg, 26%). Further, the filtrate was concentrated, and the resultant powder was washed with hexane:ethyl acetate (1:1) and dried to give ethyl 5-hydroxy-1-(4-methoxybenzyl)-(2-nitro-4-phenylbutoxybenzoylaminophenyl)methyl-1,2,3-triazole-4-carboxylate (a-2) (466.3 mg, 30%).

Workup

  1. stirringthe mixture was stirred at -78° C. for additional one hr
  2. extractionfollowed by extraction with ethyl acetate
  3. washThe organic layer was washed with dilute hydrochloric acid, water
  4. dry with materialIt was then dried over anhydrous magnesium sulfate
  5. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-87dc4dabca24448db2f1a0c0b30bd668
Source dataset
uspto-grants-2000_07
Patent number
US06093714

Reaction notes

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