Sodium Bicarbonate → HCID 18638245, compound

HRID 1165917Notes

Reaction equation

HRID 1165917 reaction equation
[CH2:1]([NH:4][C:5](=[O:25])[C@H:6]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[NH:7]C(OCC1C=CC=CC=1)=O)[CH:2]=[CH2:3].C([O-])(O)=O.[Na+].[Br:31][C:32](Br)=[N:33][OH:34].[CH3:36][CH2:37][O:38][C:39](C)=[O:40].[CH3:42][CH2:43][CH2:44][CH2:45][CH2:46]C>CCOC(C)=O.O>[CH2:37]([O:38][C:39]([N:4]([CH2:1][CH:2]1[O:34][N:33]=[C:32]([Br:31])[CH2:3]1)[C:5](=[O:25])[C@H:6]([CH2:18][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[NH2:7])=[O:40])[C:36]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

7

Reactant 4

HCID 516892Sodium BicarbonateHCID 27632191-bromo-N-hydroxymethanecarbonimidoyl bromideHCID 7613133HCID 7613133, compoundHCID 21226206Ethyl acetate hexane

Product 1

HCID 18638245HCID 18638245, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of N-benzyloxycarbonyl-L-phenylalanine allyl amide, 700 mg, in 40 ml of EtOAc and 0.75 ml of water, was added 870 mg of NaHCO3 and in small portions, dibromoformaldoxime, 631 mg. The progress of the reaction was monitored by tlc (40% EtOAc/hexane). After completion of the reaction (2-4 hrs), the reaction mixture was transferred to a separatory funnel and washed repeatedly with 5% NaHCO3, brine, and dried over anh. MgSO4. Filtration and concentration gave a light yellow viscous oil. Purification by chromatography on silica gel (15% EtOAc/hexane) gave product as a 1:1 mixture of stereoisomers. Crystallization from CHCl3 /hexane gave crystalline product, m.p. 122°-125° C. Anal. Calcd for C21H22BrN3O4 : C, 54.79; H, 4.82; N, 9.13. Found: C, 54.82; H, 4.70; N, 8.94. 13C NMR (20 MHz, CDCl3): delta 172.0, 171.9 (CON), 155.82 (OCONH), 137.7, 137.6 (BrC=N), 136.2, 135.9 (Ph), 126.9-129.2 (Ph), 80.2 (CHO), 66.9 (PhCH2O), 56.3 (CHN), 43.8, 43.6 (CH2CHO), 41.4, 41.6 (CH2N), 38.4, 38.5 (PhCH2). The individual isomers were separated by HPLC on silica gel. More polar isomer: m.p., 151°-153° C. IR (KBr): 3320, 1690, 1650, 1522 cm-1. 1H NMR (80 MHz, CDCl3): delta 7.12-7.41 (m, 10H, Ph), 6.18-6.41 (m, 1H, NH), 5.27 (d, 1H, NH), 5.07 (s, 2H, PhCH2O), 4.55-4.92 (:m, 1H, CHO), 4.28-4.56 (m, 1H, CHN), 3.4-3.57 (m, 2H:, CH2NH), 3.08 (d, 2H, PhCH2), 2.62-3.21 (m, 2H, CH2CHO). [α]D23 =+49.6 (c 0.03, CHCl3). Less polar isomer: m.p. 155°-157° C. IR (KBr): 3320, 1688, 1650, 1528 cm-1. 1H NMR (300 MHz, CDCl3): delta 7.13-7.39 (m, 10H, Ph), 6.21-6.28 (broad, 1H, NH), 5.23 (d, 1H, NH), 5.1 (s, 2H, PhCH2O), 4.66-4.78 (m, 1H, CHO), 4.37-4.46 (m, 1H, CHN), 3.46-3.53 (m, 2H, CH2N), 3.17 (dd, 1H, CHCHO), 3.08 (d, 2H, PhCH2), 2.84 (dd, 1H, CHCHO). [α]D23 =-58.7° C. (c 0.03, CHCl3).

Workup

  1. customAfter completion of the reaction (2-4 hrs)
  2. customthe reaction mixture was transferred to a separatory funnel
  3. washwashed repeatedly with 5% NaHCO3, brine
  4. dry with materialdried over anh. MgSO4
  5. filtrationFiltration and concentration
  6. customgave a light yellow viscous oil
  7. customPurification by chromatography on silica gel (15% EtOAc/hexane)
  8. customgave product
  9. additionas a 1:1 mixture of stereoisomers
  10. customCrystallization from CHCl3 /hexane
  11. customgave crystalline product, m.p. 122°-125° C
  12. customThe individual isomers were separated by HPLC on silica gel
  13. customm.p., 151°-153° C
  14. custom[α]D23 =-58.7° C. (c 0.03, CHCl3)

Sources & evidence

ORD record
ord-ed930e9be95048228678dedc5b324eb8
Source dataset
uspto-grants-1990_03
Patent number
US04912120

Reaction notes

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