Acetonitrile → HCID 57938623, compound

HRID 1435801Notes

Reaction equation

HRID 1435801 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:12]=[N:13][C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:10]3[CH2:9][N:8]=[C:7]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:6]=2[CH:26]=1.CC#N.[CH3:30][C:31]([CH3:35])([CH3:34])[C:32]#[CH:33]>C(N(CC)CC)C.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:18]([O:17][C:15]([C:14]1[N:13]=[CH:12][N:11]2[C:5]3[CH:4]=[CH:3][C:2]([C:33]#[C:32][C:31]([CH3:35])([CH3:34])[CH3:30])=[CH:26][C:6]=3[C:7]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)=[N:8][CH2:9][C:10]=12)=[O:16])[CH3:19]

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 135123,3-Dimethyl-1-butyneHCID 21930956Ethyl 8-bromo-6-phenyl-4H-benzo[f]imidazo[1,5-a][1,4]diazepine-3-carboxylate

Product 1

HCID 57938623HCID 57938623, compoundYield 439%

Reagents, catalysts & solvents 2

HCID 178419050HCID 178419050, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 5 (300 mg, 0.732 mmol) available from procedure [0051] in triethyl amine (5 mL) and CH3CN (8 mL) was stirred with 3,3-dimethyl-1-butyne (12.3 mg, 0.15 mmol) and bis(triphenylphosphine)palladium (II) acetate (38.3 mg, 0.051 mmol) and heated to reflux under nitrogen. After 5 hours, the reaction mixture was cooled to rt and filtered. The filtrate was concentrated under vacuum and the residue was treated with H2O (10 mL), and extracted with CH2Cl2 (3×10 mL). The organic layers were combined and washed with brine and dried (Na2SO4). After removal of solvent under reduced pressure, the residue was purified via flash chromatography (silica gel, EtOAc/hexanes: 1/1) to furnish the t-butylacetylene 24(XLi340) as a yellow powder (271 mg, 90%): mp: 155-156° C.; IR (KBr) 2358, 1717, 1489, 1248, 1074, 803, 668 cm−1; 1HNMR (CDCl3) δ 1.25 (s, 9H), 1.45 (t, 3H, J=7.1 Hz), 4.05 (d, 1H, J=12.3), 4.45 (2H, J=7.1 Hz), 5.95 (d, 1H, J=12.3 Hz), 7.3-7.7 (m, 8H), 7.95 (s, 1H); MS (EI) m/e (relativity intensity) 412 (M+, 46), 365 (46), 337 (100), 322 (8), 277 (16), 219 (14). Anal. Calcd. For C26H25N3O2.½H2O, C 74.26, H 6.23, N 9.99. Found. C, 74.50; H, 6.29; N, 9.89.

Workup

  1. temperatureheated
  2. temperatureto reflux under nitrogen
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under vacuum
  5. additionthe residue was treated with H2O (10 mL)
  6. extractionextracted with CH2Cl2 (3×10 mL)
  7. washwashed with brine
  8. dry with materialdried (Na2SO4)
  9. customAfter removal of solvent under reduced pressure
  10. customthe residue was purified via flash chromatography (silica gel, EtOAc/hexanes: 1/1)

Sources & evidence

ORD record
ord-39b6a7802fd14e9ba32f70ab2c361274
Source dataset
uspto-grants-2009_11
Patent number
US07618958B2

Reaction notes

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