Diisopropylethylamine → HCID 71060942, compound

HRID 1911032Notes

Reaction equation

HRID 1911032 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([OH:10])=O)=[N:6][CH:7]=1.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C.[NH2:44][C:45]1[CH:46]=[CH:47][C:48]2[CH2:54][CH2:53][CH2:52][C:51]([C:55]([O:57][CH3:58])=[O:56])=[C:50]([CH3:59])[C:49]=2[CH:60]=1>ClCCl.C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([NH:44][C:45]2[CH:46]=[CH:47][C:48]3[CH2:54][CH2:53][CH2:52][C:51]([C:55]([O:57][CH3:58])=[O:56])=[C:50]([CH3:59])[C:49]=3[CH:60]=2)=[O:10])=[N:6][CH:7]=1

Participants

7

Reactant 4

HCID 81531DiisopropylethylamineHCID 27628725-Chloro-2-picolinic acidHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 86685426methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate

Product 1

HCID 71060942HCID 71060942, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 5-chloropicolinic acid (354 mg, 2.248 mmol) in dichloromethane (5 mL) was added HATU (940 mg, 2.473 mmol) and DIPEA (0.589 mL, 3.37 mmol). After stirring for 10 min, methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate from preparation J, step J1 (260 mg, 1.124 mmol) was added. The mixture was stirred at rt for 4 h. Ethyl acetate (100 mL) was added and the organic layer was washed with water. After concentration of the organic layer, the residue was purified using silica gel column chromatography (hexanes-100% EtOAc) to give methyl 2-(5-chloropicolinamido)-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate (345 mg, 0.930 mmol, 83% yield). LCMS (M+H)+=371.3. 1H NMR (400 MHz, chloroform-d) δ 9.84 (s, 1H), 8.56 (dd, J=2.4, 0.6 Hz, 1H), 8.25 (dd, J=8.4, 0.6 Hz, 1H), 7.88 (dd, J=8.4, 2.4 Hz, 1H), 7.73 (d, J=2.3 Hz, 1H), 7.63 (dd, J=8.0, 2.3 Hz, 1H), 7.20 (d, J=8.3 Hz, 1H), 3.82 (s, 3H), 2.55 (t, J=6.5 Hz, 2H), 2.44 (s, 3H), 2.18-2.08 (m, 4H).

Workup

  1. additionwas added
  2. stirringThe mixture was stirred at rt for 4 h
  3. washthe organic layer was washed with water
  4. customAfter concentration of the organic layer, the residue was purified

Sources & evidence

ORD record
ord-5bfbc6eedf66489390e40f144a0dde6c
Source dataset
uspto-grants-2013_12
Patent number
US08604024B2

Reaction notes

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