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1-benzyl-4-methylenepiperidine → HCID 68587687, compound

HRID 2070893
Notes
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Reaction equation

HRID 2070893 reaction equation
[CH2:1]([N:3]1[CH2:8][CH2:7][CH:6]([CH2:9][C:10]2[N:15]3[N:16]=[C:17]([NH:19][C:20]4[CH:25]=[CH:24][C:23]([C:26]([F:29])([F:28])[F:27])=[CH:22][CH:21]=4)[N:18]=[C:14]3[CH:13]=[CH:12][CH:11]=2)[CH2:5][CH2:4]1)[CH3:2].C(N1CCC(=C)CC1)C1C=CC=CC=1.Br[C:45]1[N:50]2[N:51]=[C:52]([NH:54][C:55]3[CH:60]=[CH:59][C:58]([C:61]([F:64])([F:63])[F:62])=[CH:57][CH:56]=3)[N:53]=[C:49]2[CH:48]=[CH:47][CH:46]=1.C1(NC2N=C3C=CC=C(CC4CCNCC4)N3N=2)C=CC=CC=1.C(N1CCC(CC2N3N=C(NC4C=CC(C(F)(F)F)=CC=4)N=C3C=CC=2)CC1)C1C=CC=CC=1.N1CCC(CC2N3N=C(NC4C=CC(C(F)(F)F)=CC=4)N=C3C=CC=2)CC1>C(O)C.[Pd].C(O)(=O)C>[CH2:1]([N:3]1[CH2:4][CH2:5][CH:6]([CH2:9][C:10]2[N:15]3[N:16]=[C:17]([NH:19][C:20]4[CH:21]=[CH:22][C:23]([C:26]([F:28])([F:27])[F:29])=[CH:24][CH:25]=4)[N:18]=[C:14]3[CH:13]=[CH:12][CH:11]=2)[CH2:7][CH2:8]1)[CH3:2].[F:64][C:61]([F:62])([F:63])[C:58]1[CH:59]=[CH:60][C:55]([NH:54][C:52]2[N:53]=[C:49]3[CH:48]=[CH:47][CH:46]=[CH:45][N:50]3[N:51]=2)=[CH:56][CH:57]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

11

Reactant 6

HCID 38261121-benzyl-4-methylenepiperidineHCID 59276367HCID 59276367, compoundHCID 59276484HCID 59276484, compoundHCID 59276502HCID 59276502, compoundHCID 70921800HCID 70921800, compoundHCID 86675554HCID 86675554, compound

Product 2

HCID 59276484HCID 59276484, compoundHCID 68587687HCID 68587687, compoundYield 13.29%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolvent

Procedure

5-((1-Ethylpiperidin-4-yl)methyl)-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine. 541-Benzylpiperidin-4-yl)methyl)-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine was synthesized from 1-benzyl-4-methylenepiperidine and 5-bromo-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine following the procedure described for N-phenyl-5-(piperidin-4-ylmethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine. 5-((1-Benzylpiperidin-4-yl)methyl)-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine (0.165 g, 0.354 mmol) was dissolved in ethanol (30 mL) and treated with a catalytic amount of palladium on carbon (10 weight %). The reaction was stirred under an atmosphere of hydrogen gas overnight at room temperature. As only trace conversion was observed, a drop of acetic acid was added and the reaction was stirred at room temperature overnight. Most of the starting material was converted to the title compound contaminated with a minor amount of 5-(piperidin-4-ylmethyl)-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine. The catalyst was removed by filtration washed with methanol and the filtrate was concentrated under reduced pressure. The residue was purified by semi-preparative HPLC (20-70% acetonitrile+0.1% trifluoroacetic acid in water+0.1% trifluoroacetic acid, 3 injections, 30 min.). The desired fractions were combined and neutralized with a STRATA cationic resin exchange column. The eluate was concentrated under reduced pressure and dried in a vacuum oven for 5 h. 541-Ethylpiperidin-4-yl)methyl)-N-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine (0.019 g, 0.047 mmol, 13.29% yield) was isolated as a off-white solid. 1H NMR (400 MHz, DMSO-d6) δ (ppm) 10.18 (s, 1H), 7.91 (d, J=8.59 Hz, 2H), 7.64 (d, J=8.59 Hz, 2H), 7.48-7.59 (m, 2H), 6.95 (s, 1H), 3.03 (d, J=6.64 Hz, 2H), 2.82 (br s, 2H), 2.26 (s, 2H), 1.99 (br s, 1H), 1.78 (br s, 2H), 1.55 (br s, 2H), 1.33 (br s, 2H), 0.89-1.02 (m, 3H); 19F NMR (400 MHz, DMSO-d6) δ (ppm)-59.9 ppm; MS (ESI): m/z 404.2 [M+1]+.

Workup

  1. stirringthe reaction was stirred at room temperature overnight
  2. customThe catalyst was removed by filtration
  3. washwashed with methanol
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by semi-preparative HPLC (20-70% acetonitrile+0.1% trifluoroacetic acid in water+0.1% trifluoroacetic acid, 3 injections, 30 min.)
  6. concentrationThe eluate was concentrated under reduced pressure
  7. customdried in a vacuum oven for 5 h

Sources & evidence

ORD record
ord-74cb1cd09c554421a2adbceb703f7a88
Source dataset
uspto-grants-2012_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08299056B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes