1,2-Diaminocyclohexane → N-benzyl-2-(3-benzyl-2-(cyanoimino)imidazolidin-1-yl)-4-methylthiazole-5-carboxamide

HRID 2067570Notes

Reaction equation

HRID 2067570 reaction equation
[CH2:1]([NH:8][C:9]([C:11]1[S:15][C:14](Br)=[N:13][C:12]=1[CH3:17])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:18]([N:25]1[CH2:29][CH2:28][NH:27][C:26]1=[N:30][C:31]#[N:32])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C1(N)CCCCC1N.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O.[Cu]I>[CH2:1]([NH:8][C:9]([C:11]1[S:15][C:14]([N:27]2[CH2:28][CH2:29][N:25]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:26]2=[N:30][C:31]#[N:32])=[N:13][C:12]=1[CH3:17])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 46101,2-DiaminocyclohexaneHCID 11430Potassium CarbonateHCID 579593962-Bromo-4-methyl-thiazole-5-carboxylic acid benzylamideHCID 178512076HCID 178512076, compound

Product 1

HCID 59481237N-benzyl-2-(3-benzyl-2-(cyanoimino)imidazolidin-1-yl)-4-methylthiazole-5-carboxamideYield 8%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of N-benzyl-2-bromo-4-methylthiazole-5-carboxamide (0.25 g, 0.80 mmol), N-(1-benzylimidazolidin-2-ylidene)cyanamide (0.18 g, 0.88 mmol), copper(I) iodide (0.030 g, 0.16 mmol), cyclohexane-1,2-diamine (0.018 g, 0.16 mmol) and potassium carbonate (0.17 g, 1.20 mmol) in anhydrous N,N-dimethylformamide (15 mL) was heated at 100° C. under nitrogen atmosphere for 16 hours. The solvent was removed in vacuo, diluted with ethyl acetate (250 mL), washed with saturated sodium bicarbonate solution (50 mL) and brine (50 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was recrystallized from ethyl acetate and hexane. The solid was collected by filtration and washed with methanol and hexane to afford the title compound as a colourless solid in 8% yield (0.030 g): mp 226-228° C. (ethyl acetate/hexanes); 1H NMR (300 MHz, DMSO-d6) δ 8.59 (t, J=5.9 Hz, 1H), 7.49-7.17 (m, 10H), 4.99 (s, 2H), 4.35 (d, J=5.9 Hz, 2H), 4.14-4.08 (m, 2H), 3.66-3.60 (m, 2H), 2.44 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 161.9, 156.1, 153.3, 151.5, 140.0, 135.4, 129.3, 128.7, 128.4, 128.1, 127.7, 127.1, 119.8, 113.9, 49.0, 46.6, 44.72, 43.1, 17.5; MS (ES+) m/z 431.3 (M+1).

Workup

  1. customThe solvent was removed in vacuo
  2. additiondiluted with ethyl acetate (250 mL)
  3. washwashed with saturated sodium bicarbonate solution (50 mL) and brine (50 mL)
  4. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was recrystallized from ethyl acetate and hexane
  8. filtrationThe solid was collected by filtration
  9. washwashed with methanol and hexane

Sources & evidence

ORD record
ord-2cbbd0d022de4f61baa092eda9c7ac01
Source dataset
uspto-grants-2012_10
Patent number
US08293768B2

Reaction notes

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