Allyl bromide → HCID 13126002, compound

HRID 1112096Notes

Reaction equation

HRID 1112096 reaction equation
[F:1][CH:2]1[N:8]=[C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:6]2[CH:15]=[C:16]([Cl:19])[CH:17]=[CH:18][C:5]=2[NH:4][C:3]1=[O:20].Br[CH2:22][CH:23]=[CH2:24].[H-].[Na+].[H][H]>C1COCC1.C(Cl)Cl.O>[F:1][CH:2]1[N:8]=[C:7]([C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:6]2[CH:15]=[C:16]([Cl:19])[CH:17]=[CH:18][C:5]=2[N:4]([CH2:24][CH:23]=[CH2:22])[C:3]1=[O:20]

Participants

8

Reactant 4

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 131259877-Chloro-3-fluoro-5-phenyl-1,3-dihydro-2H-1,4-benzodiazepin-2-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 13126002HCID 13126002, compoundYield 43.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a well stirred solution of 3.0 g (0.01 mol) of 3-fluoro-1,3-dihydro-7-chloro-5-phenyl-2H-1,4-benzodiazepin-2-one, 75 ml of dry THF and 21.78 g (0.18 mol) of 3-bromopropene, was added a suspension of 0.48 g (0.02 mol) of sodium hydride in 20 ml of THF. There was an immediate evolution of hydrogen. The contents of the flask were stirred under a nitrogen atmosphere for exactly two hours. The product mixture was poured into 100 ml of water and methylene chloride was added to extract the product. The organic layer was washed twice with 50 ml portions of water, and then allowed to dry over magnesium sulfate. Evaporation of the solvent under reduced pressure gave an orange gluey material which was recrystallized from 450 ml of hot heptane to give 1.42 g of 3-fluoro-1-(allyl)-7-chloro-5-phenyl-2H-1,4-benzodiazepin-2-one as a very pale orange powder: mp 138°-140°, 1H nmr (CDCl3) δ 7.2-7.9 ppm (m, 8H), δ 5.6 ppm (d, J = 57.5 Hz, 1H), δ 4.85-5.95 ppm (m, 3H, olefinic), δ 4.58 ppm (2H, N--CH2); 19F nmr (CDCl3) δ 161.97 ppm.

Workup

  1. additionwas added
  2. extractionto extract the product
  3. washThe organic layer was washed twice with 50 ml portions of water
  4. dry with materialto dry over magnesium sulfate
  5. customEvaporation of the solvent under reduced pressure
  6. customgave an orange gluey material which
  7. customwas recrystallized from 450 ml of hot heptane

Sources & evidence

ORD record
ord-cf707a30d6594b4e8670b2c29d2abb37
Source dataset
uspto-grants-1978_10
Patent number
US04120856

Reaction notes

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