N,N'-Bis(tert-butoxycarbonyl)-1H-pyrazole-1-carboxamidine → HCID 69296208, compound

HRID 1624340Notes

Reaction equation

HRID 1624340 reaction equation
[NH:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[CH2:10][N:11]([CH:15]1[C:24]2[N:23]=[CH:22][CH:21]=[CH:20][C:19]=2[CH2:18][CH2:17][CH2:16]1)[CH2:12][CH2:13][NH2:14].[C:25]([O:29][C:30]([NH:32][C:33](N1C=CC=N1)=[N:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])=[O:31])([CH3:28])([CH3:27])[CH3:26]>C1COCC1>[C:38]([O:37][C:35]([NH:34][C:33]([NH:32][C:30]([O:29][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:31])=[N:14][CH2:13][CH2:12][N:11]([CH2:10][C:2]1[NH:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=2[N:1]=1)[CH:15]1[C:24]2[N:23]=[CH:22][CH:21]=[CH:20][C:19]=2[CH2:18][CH2:17][CH2:16]1)=[O:36])([CH3:41])([CH3:40])[CH3:39]

Participants

4

Reactant 2

HCID 4428040N,N'-Bis(tert-butoxycarbonyl)-1H-pyrazole-1-carboxamidineHCID 10149770N-(1H-benzimidazol-2-ylmethyl)-N-(5,6,7,8-tetrahydroquinolin-8-yl)-ethane-1,2-diamine

Product 1

HCID 69296208HCID 69296208, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Using General Procedure B: Reaction of N-(tert-butoxycarbonyl)-2-amino-acetaldehyde (0.204 g, 1.28 mmol) and (1H-Benzimidazol-2-ylmethyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amine (0.284 g, 1.02 mmol) with NaBH(OAc)3 (0.430 g, 2.03 mmol) in CH2Cl2 (10 mL) provided 0.71 g of a yellow foam. The foam was dissolved in THF (10 mL) and treated with 6N hydrochloric acid (10 mL). The resultant solution was stirred at room temperature overnight. The solution was neutralized with solid K2CO3 (5 g), diluted with water (5 mL) and extracted with CH2Cl2 (3×20 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by column chromatography on silica gel (20:1:1 CH2Cl2—CH3OH—NH4OH) provided 0.205 g (64%) of N1-(1H-Benzimidazol-2-ylmethyl)-1-(5,6,7,8-tetrahydro-quinolin-8-yl)-ethane-1,2-diamine as a yellow solid. To a solution of N1-(1H-Benzimidazol-2-ylmethyl)-N1-(5,6,7,8-tetrahydro-quinolin-8-yl)-ethane-1,2-diamine (0.205 g, 0.64 mmol) in dry THF (6 mL) was added N.N′-bis-(tert-butoxycarbonyl)-1H-pyrazole-1-carboxamidine (Tetrahedron Lett. 1993, 34, 3389.) (0.201 g, 0.64 mmol) and the resultant mixture was stirred at room temperature for 18 hours. The mixture was concentrated and the resultant oil was purified by column chromatography on silica gel (40:1:1 CH2Cl2—CH3OH—NH4OH) and provided 0.267 g (74%) of N,N′-bis(tert-butoxycarbonyl)-N″-{2-[(1H-Benzimidazol-2-ylmethyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amino]-ethyl}-guanidine as a white foam.

Workup

  1. concentrationThe mixture was concentrated
  2. customthe resultant oil was purified by column chromatography on silica gel (40:1:1 CH2Cl2—CH3OH—NH4OH)

Sources & evidence

ORD record
ord-94af3cbd7af24319a8320117c6c7f704
Source dataset
uspto-grants-2014_07
Patent number
US08778967B2

Reaction notes

Loading…