tert-Butyl carbazate → HCID 86659601, compound

HRID 1972750Notes

Reaction equation

HRID 1972750 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH2:14][CH:13]([C:17](=O)[CH2:18][CH2:19][CH:20]([O:23][CH3:24])[O:21][CH3:22])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:26]([O:30][C:31](=[O:34])[NH:32][NH2:33])([CH3:29])([CH3:28])[CH3:27]>C(Cl)Cl.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH2:1]([O:8][C:9]([N:11]1[CH2:16][CH2:15][CH2:14][C@@H:13]([C:17](=[N:33][NH:32][C:31]([O:30][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:34])[CH2:18][CH2:19][CH:20]([O:23][CH3:24])[O:21][CH3:22])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 70091tert-Butyl carbazateHCID 76814076HCID 76814076, compound

Product 1

HCID 86659601HCID 86659601, compoundYield 94.2%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 6344DichloromethaneSolvent

Procedure

The product from step 1 (16.32 g, 46.70 mmol) was dissolved in 100 mL of CH2Cl2 and treated with tert-butylcarbazate (6.48 g, 49.04 mmol) followed by para-toluensulfonic acid monohydrate (0.44 g, 2.33 mmol) and the mixture was stirred 4 h. The mixture was poured into a separatory funnel and extracted with 50 mL 2M aq. Na2CO3. The aqueous phase was extracted with 50 mL of CH2Cl2 and the combined organic phases were dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified using an ISCO® instrument (Red-Sep 330, 30%-100% EtOAc hexanes) to give 20.40 g of a clear oil. 1H NMR (300 MHz, DMSO-d6) δ 9.48 (bs, 1H), 7.40-7.28 (m, 5H), 5.04 (s, 2H), 4.32 (m, 1H), 4.05 (bd, 1H), 3.96 (bd, 1H), 3.20 (m, 6H), 2.88-2.63 (m, 2H), 2.31-2.11 (m, 1H), 1.87 (m, 1H), 1.66, (m, 1H), 1.59 (m, 1H), 1.42 (s, 9H), 1.40-1.24 (m, 5H). ES-MS m/z 463.9 [M+Na]+, HPLC RT (min) 3.67

Workup

  1. additionThe mixture was poured into a separatory funnel
  2. extractionextracted with 50 mL 2M aq. Na2CO3
  3. extractionThe aqueous phase was extracted with 50 mL of CH2Cl2
  4. dry with materialthe combined organic phases were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified

Sources & evidence

ORD record
ord-79472c035ddf4adb9ef73492f8fe4390
Source dataset
uspto-grants-2013_04
Patent number
US08431695B2

Reaction notes

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