Hexane → 5-[2-(2-Methyl-5-nitro-phenyl)-3-nitro-propyl]-1-trityl-tetrazole

HRID 1053703Notes

Reaction equation

HRID 1053703 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1/[CH:11]=[CH:12]/[N+:13]([O-:15])=[O:14].[CH3:16][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.C(=O)=O.CC(C)=O.C([Li])CCC.CCCCCC>O1CCCC1>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[CH:11]([CH2:12][N+:13]([O-:15])=[O:14])[CH2:16][C:17]1[N:21]([C:22]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[N:20]=[N:19][N:18]=1

Participants

7

Reactant 5

HCID 8058HexaneHCID 18522661Acetone cardice2×HCID 581652125-Methyl-1-trityl-tetrazole2×HCID 1182770521-Methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene2×HCID 178418339Butyllithium

Product 1

HCID 1182769595-[2-(2-Methyl-5-nitro-phenyl)-3-nitro-propyl]-1-trityl-tetrazole

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Adapting literature known protocols (Huff et al., Tetrahedron Lett., 1996, 37(12), 3655-3658; Baylis, Tetrahedron Lett., 1995, 36(51), 9385-9388; and Xu, et al., U.S. Pat. No. 8,344,028 (2013)), 5-[2-(2-methyl-5-nitro-phenyl)-3-nitro-propyl]-1-trityl-tetrazole (20b) is prepared from 1-methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene (19a) through 1,4-conjugate addition of lithiated 5-methyl-1-trityl-tetrazole (Huff et al., Tetrahedron Lett., 1996, 37(12), 3655-3658). 5-Methyl-1-trityl-tetrazole (3.92 g, 12.0 mmol) in anhydrous tetrahydrofuran (THF) (15 mL) is lithiated under a nitrogen atmosphere and at a temperature of about −78° C. (dry ice/acetone bath) with n-butyllithium (nBuLi) in hexane (12.0 mL, 12.0 mmol) and added via a cannula to a cooled solution (−78° C.; dry ice/acetone bath, nitrogen atmosphere) of (19a) (2.08 g, 10.0 mmol) in anhydrous tetrahydrofuran (THF) (15 mL). Aqueous work-up and purification by silica gel column chromatography using ethyl acetate (EtOAc) and hexanes mixtures afford the title compound (20b).

Workup

  1. customAqueous work-up and purification by silica gel column chromatography

Sources & evidence

ORD record
ord-819c9c71431a4d819527ffd23f07315e
Source dataset
uspto-grants-2016_07
Patent number
US09394236B2

Reaction notes

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