3,4-Diaminotoluene → HCID 178423469, compound

HRID 1842499Notes

Reaction equation

[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([C:12](O)=O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1N=CN(C(N2C=NC=C2)=O)C=1.[CH3:27][C:28]1[CH:29]=[C:30]([NH2:35])[C:31]([NH2:34])=[CH:32][CH:33]=1>CN(C=O)C.N1C=CC=CC=1>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([C:12]2[NH:34][C:31]3[CH:32]=[CH:33][C:28]([CH3:27])=[CH:29][C:30]=3[N:35]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 100 °C

Procedure

To the mixture of 1-(tert-butoxycarbonyl)azetidine-3-carboxylic acid (4.94 g, 24.6 mmol) in DMF (30 mL) and pyridine (30 mL) was added CDI (4.38 g, 27 mmol) at 45° C. and the mixture was stirred for another 2 h at this temperature. Then 4-methyl-benzene-1,2-diamine (3 g, 24.6 mmol) was added and the mixture was stirred at RT overnight. Solvents were removed in vacuo and the residue was dissolved in HOAc (30 mL) and heated for 1 h at 100° C. Then the reaction mixture was concentrated and the residue was partitioned between DCM and aqueous of Na2CO3. The organic layer was dried over Na2SO4 and concentrated to give the crude product which was purified by column chromatography (ethyl acetate:petroleum ether=1:2) to give the compound (4.6 g, yield 61%) as yellow solid.

Workup

stirringthe mixture was stirred at RT overnight
customSolvents were removed in vacuo
dissolutionthe residue was dissolved in HOAc (30 mL)
concentrationThen the reaction mixture was concentrated
customthe residue was partitioned between DCM and aqueous of Na2CO3
dry with materialThe organic layer was dried over Na2SO4
concentrationconcentrated
customto give the crude product which
customwas purified by column chromatography (ethyl acetate:petroleum ether=1:2)

Sources & evidence

ORD record: ord-492f1094d3124446bc3d51e37e487463
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08946230B2

Reaction notes

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