Hydrochloric Acid → Ethyl 1,4-diazepane-1-carboxylate

HRID 637030Notes

Reaction equation

HRID 637030 reaction equation
[NH:1]1[CH2:7][CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.CN(C1C=CC(N=NC2C=CC(S(O)(=O)=O)=CC=2)=CC=1)C.Cl.Cl[C:31]([O:33][CH2:34][CH3:35])=[O:32].C([O-])(=O)C.[Na+].[OH-].[Na+]>O>[CH2:34]([O:33][C:31]([N:1]1[CH2:7][CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1)=[O:32])[CH3:35]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 10928Ethyl chloroformateHCID 11037Benzenesulfonic acid, 4-(2-(4-(dimethylamino)phenyl)diazenyl)-HCID 14798Sodium Hydroxide2×HCID 68163Hexahydro-1,4-diazepineHCID 517045Sodium Acetate

Product 1

HCID 15289249Ethyl 1,4-diazepane-1-carboxylate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Combine [1,4]diazepane (33.9 g, 340 mmol) and water (250 mL). Add methyl orange and adjust the pH using 3 M aqueous hydrochloric acid solution until the indicator turns red. Add dropwise, ethyl chloroformate (38 mL, 400 mmol) over about 2.5 hours while maintaining the pH using first aqueous sodium acetate and then aqueous sodium hydroxide solution. After the addition is complete adjust the pH to 8 using aqueous sodium hydroxide solution and extract three times with diethyl ether. Discard the organic extracts and saturate the aqueous layer with potassium carbonate. Extract three times with diethyl ether. Combined organic layers from the second extraction, dry the over Na2SO4, filter, and evaporate in vacuo to give a 1-ethoxycarbonyl[1,4]diazepane.

Workup

  1. additionAdd dropwise
  2. additionAfter the addition
  3. extractionextract three times with diethyl ether
  4. concentrationsaturate the aqueous layer with potassium carbonate
  5. extractionExtract three times with diethyl ether
  6. extractionCombined organic layers from the second extraction
  7. dry with materialdry the over Na2SO4
  8. filtrationfilter
  9. customevaporate in vacuo

Sources & evidence

ORD record
ord-1b1dc35b49b14793a463d634b624473a
Source dataset
uspto-grants-2001_02
Patent number
US06194406B1

Reaction notes

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