Hydrochloric Acid → HCID 101039217, compound

HRID 2228857Notes

Reaction equation

HRID 2228857 reaction equation
[NH:1]([CH3:20])[C:2]([C:5]([NH:7][C@H:8]([C:16]([O:18][CH3:19])=[O:17])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:6])([CH3:4])[CH3:3].Cl.[N+:22]([C:25]1[CH:33]=[CH:32][C:28]([C:29](Cl)=[O:30])=[CH:27][CH:26]=1)([O-:24])=[O:23]>C(Cl)Cl>[N+:22]([C:25]1[CH:33]=[CH:32][C:28]([C:29]([N:1]([CH3:20])[C:2]([C:5]([NH:7][C@H:8]([C:16]([O:18][CH3:19])=[O:17])[CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[O:6])([CH3:3])[CH3:4])=[O:30])=[CH:27][CH:26]=1)([O-:24])=[O:23]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 85024-Nitrobenzoyl chlorideHCID 131723399HCID 131723399, compound

Product 1

HCID 101039217HCID 101039217, compoundYield 24%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of H—NMeAib—Phe—OMe, HCl salt (0.3 g, 1.0 mmol) in CH2Cl2 (3mL) was added TEA (0.28 mL, 2.0 mmol). After stirring for 5 min at room temperature p-nitrobenzoyl chloride (0.15 g, 1 mmol) was added. The resulting solution was stirred at room temperature for 24 h. The solvent was removed in vacuo and redissolved in ethyl acetate (30 mL). The ethyl acetate layer was washed with 1M HCl (3×10 mL) brine (10 mL), 10% aq. Na2CO3 (3×10 mL), brine (10 mL), and dried over Na2SO4. Evaporation of the solvent was followed by column chromatography of the product with CHCl3—MeOH-Acetic Acid (90:10:0.1 v:v:v) provided 7a (see Table 1) (100 mg 24%) as a pale yellow amorphous solid: mp.65-70° C.; 1H NMR (360 MHz CDCl3 δ) 1.54 &1.52 (2s, 6H, β-MeAib), 2.87 (s, 3H, N—CH3), 3.15 (d, 2H, J=5.04 Hz, β-H), 3.69 (s, 3H, O—CH3), 4.86 (m, 1H, α-H); 6.35 (d, 1H, J=6.35 Hz, N—H), 7.20 (m, 5H, Aromatic Phe), 7.55 (d, 2H, J=8.64 Hz, Benzyl-H), 8.64 (d, 2H, J=8.64 Hz, Benzyl-H), FAB-MS m/z (relative intensity) 428 (35%), 450 (40%), 249 (100%); [α]D20−16.15° (c 0.014, MeOH).

Workup

  1. additionwas added
  2. customThe solvent was removed in vacuo
  3. dissolutionredissolved in ethyl acetate (30 mL)
  4. washThe ethyl acetate layer was washed with 1M HCl (3×10 mL) brine (10 mL), 10% aq. Na2CO3 (3×10 mL), brine (10 mL)
  5. dry with materialdried over Na2SO4
  6. customEvaporation of the solvent

Sources & evidence

ORD record
ord-dcbcfeeb820a46bc9c025ed19fa1781b
Source dataset
uspto-grants-2002_07
Patent number
US06417397B1

Reaction notes

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