Sodium borohydride → 3-[1-(Aminomethyl)-2-(1-trityltetrazol-5-yl)ethyl]-4-methyl-aniline

HRID 1053704Notes

Reaction equation

HRID 1053704 reaction equation
[BH4-].[Na+].[H][H].[CH3:5][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-])=O)=[CH:8][C:7]=1[CH:15]([CH2:41][N+:42]([O-])=O)[CH2:16][C:17]1[N:21]([C:22]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[N:20]=[N:19][N:18]=1>CO.O.O.O.O.O.O.[Ni](Cl)Cl>[NH2:42][CH2:41][CH:15]([C:7]1[CH:8]=[C:9]([CH:10]=[CH:11][C:6]=1[CH3:5])[NH2:12])[CH2:16][C:17]1[N:21]([C:22]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[N:20]=[N:19][N:18]=1

Participants

6

Reactant 3

HCID 4311764Sodium borohydride2×HCID 1182769595-[2-(2-Methyl-5-nitro-phenyl)-3-nitro-propyl]-1-trityl-tetrazoleHCID 178418361HCID 178418361, compound

Product 1

HCID 1182770853-[1-(Aminomethyl)-2-(1-trityltetrazol-5-yl)ethyl]-4-methyl-aniline

Reagents, catalysts & solvents 2

HCID 11791229Dichloronickel;hexahydrateCatalystHCID 887MethanolSolvent2×

Procedure

Adapting a literature known protocol (Osby and Ganem, Tetrahedron Lett., 1985, 26(52), 6413-6416), a mixture of nickel(II) dichloride hexahydrate (NiCl2 6H2O) (1.19 g, 5.0 mmol) in methanol (MeOH) (80 mL) is sonicated to effect complete dissolution. Solid sodium borohydride (NaBH4) (567 mg, 15.0 mmol) is added in small portions upon a black precipitate (Ni2B) is generated immediately and hydrogen gas is generated (exotherm!). After about 30 min, a solution of 5-[2-(2-methyl-5-nitro-phenyl)-3-nitro-propyl]-1-trityl-tetrazole (20b) (5.35 g, 10.0 mmol) in MeOH (20 mL) is added followed by portion-wise addition of more NaBH4 (1.13 g, 30.0 mmol) at room temperature. The reaction is monitored by TLC and/or LCMS to completion. The reaction mixture is filtered over Celite® 545 and the filter residue is washed with additional MeOH. The combined filtrates are evaporated to dryness under reduced pressure using a rotary evaporator. The crude material (20c) is used directly in the next step without further isolation and purification.

Workup

  1. customis sonicated
  2. dissolutiondissolution
  3. filtrationThe reaction mixture is filtered over Celite® 545
  4. washthe filter residue is washed with additional MeOH
  5. customThe combined filtrates are evaporated to dryness under reduced pressure
  6. customa rotary evaporator
  7. customThe crude material (20c) is used directly in the next step without further isolation and purification

Sources & evidence

ORD record
ord-f1bfe7e08a71478cac2e88ae99be2987
Source dataset
uspto-grants-2016_07
Patent number
US09394236B2

Reaction notes

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