Diethyl Ether → HCID 89704777, compound

HRID 928940Notes

Reaction equation

HRID 928940 reaction equation
[F:1][C:2]1[C:3]([NH:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[F:30])=[C:4]([CH:9]=[C:10]([S:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)[C:11]=1F)[C:5]([O:7][CH3:8])=[O:6].[N-:31]=[N+:32]=[N-:33].CCOCC.S1(CCCC1)(=O)=O>CN(C)C(=O)C.CN(C)C=O.CN1C(=O)N(C)CCC1.CN(P(N(C)C)(N(C)C)=O)C.CS(C)=O>[N:31]([C:11]1[C:10]([S:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)=[CH:9][C:4]([C:5]([O:7][CH3:8])=[O:6])=[C:3]([NH:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[F:30])[C:2]=1[F:1])=[N+:32]=[N-:33]

Participants

10

Reactant 4

HCID 3283Diethyl EtherHCID 31347SulfolaneHCID 33558AzideHCID 89704803HCID 89704803, compound

Product 1

HCID 89704777HCID 89704777, compound

Reagents, catalysts & solvents 5

HCID 679Dimethyl SulfoxideSolventHCID 6228DimethylformamideSolventHCID 12679HexamethylphosphoramideSolventHCID 31374DimethylacetamideSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Procedure

Methyl 3,4-difluoro-2-((2-fluorophenyl)amino)-5-((4-methoxy benzyl)thio)benzoate can be reacted with azide (such as NaN3, KN3) at high temperature (60-120° C., prefer 80-100° C.) in appropriate solvent (include aliphatic and aromatic hydrocarbon (such as pentane, hexane, heptane, cyclohexane, petroleum ether, petrol, gasoline, benzene, toluene, xylene), aliphatic and aromatic halo-hydrocarbon (such as dichloromethane, 1,2-dichloroethane, chloroform, phenixin, chlorobenzene, o-dichlorobenzene), ether (such as diethyl ether, dibutyl ether, glycol dimethyl ether, 2-methoxyethyl ether, tetrahydrofuran, dioxane), ketone (such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone), ester (such as ethyl acetate, methyl acetate), nitrile (such as acetonitrile, propiononitrile), amide (such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidin-2-one), DMSO, sulfolane, HMPA, DMPU, prefer N,N-dimethylformamide and N,N-dimethylacetamide) for some time (1-12 h, prefer 3-10 h). Methyl 4-azido-3-fluoro-2-((2-fluorophenyl)amino)-5-((4-methoxybenzyl)thio)benzoate is obtained after conventional workup.

Sources & evidence

ORD record
ord-975fb8954b5d475787dca9c48bd8f4c1
Source dataset
uspto-grants-2016_03
Patent number
US09290468B2

Reaction notes

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