tert-Butanol → Carbamic acid, (4-chloro-6,7-dimethoxy-3-quinolinyl)-, 1,1-dimethylethyl ester

HRID 989056Notes

Reaction equation

HRID 989056 reaction equation
[Cl:1][C:2]1[C:11]2[C:6](=[CH:7][C:8]([O:14][CH3:15])=[C:9]([O:12][CH3:13])[CH:10]=2)[N:5]=[CH:4][C:3]=1C(O)=O.[CH3:19][C:20]([OH:23])([CH3:22])[CH3:21].C([N:26]([CH2:29]C)CC)C.C1(P([N:45]=[N+]=[N-])(C2C=CC=CC=2)=[O:38])C=CC=CC=1>CN(C=O)C>[C:29]([NH:26][C:3]1[CH:4]=[N:5][C:6]2[C:11]([C:2]=1[Cl:1])=[CH:10][C:9]([O:12][CH3:13])=[C:8]([O:14][CH3:15])[CH:7]=2)([O:23][C:20]([CH3:22])([CH3:21])[CH3:19])=[O:38].[NH2:45][C:3]1[CH:4]=[N:5][C:6]2[C:11]([C:2]=1[Cl:1])=[CH:10][C:9]([O:12][CH3:13])=[C:8]([O:14][CH3:15])[CH:7]=2

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 180050224-Chloro-6,7-dimethoxyquinoline-3-carboxylic acid

Product 2

HCID 18005018Carbamic acid, (4-chloro-6,7-dimethoxy-3-quinolinyl)-, 1,1-dimethylethyl esterYield 65%HCID 22646632HCID 22646632, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

4-chloro-6,7-dimethoxy-3-quinolinecarboxylic acid (26 g) was suspended in DMF (1000 ml) with stirring under a nitrogen atmosphere, tBuOH (400 ml) was added followed by triethylamine (31 ml) and finally Diphenylphosphoryl azide (25 ml) The reaction was then heated to 100° C. for 7 hours with stirring. Cooled and then evaporated on a rotavapor. The residue was treated with dichloromethane, some solid was filtered off, the filtrate was then flash columned (Merck silica Art 9385) eluting with dichloromethane with a methanol gradient to 5%. To give 3-BOCamino-4-chloro-6,7-dimethoxyquinoline (21.6 g, 65%) and 3-amino-4-chloro-6,7-dimethoxyquinoline (4.4 g, 19%).

Workup

  1. stirringwith stirring
  2. temperatureCooled
  3. customevaporated on a rotavapor
  4. additionThe residue was treated with dichloromethane
  5. filtrationsome solid was filtered off
  6. washeluting with dichloromethane with a methanol gradient to 5%

Sources & evidence

ORD record
ord-7b3209080e1f48ccb8f5d0bbc4e5b634
Source dataset
uspto-grants-2003_10
Patent number
US06638945B1

Reaction notes

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