Nitrogen → 2-Amino-5-benzylbenzonitrile

HRID 853755Notes

Reaction equation

HRID 853755 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1Cl)[CH2:5]Cl.N#N.[NH2:13][C:14]1[CH:21]=[CH:20][C:19](I)=[CH:18][C:15]=1[C:16]#[N:17]>C1COCC1.[Zn]>[NH2:13][C:14]1[CH:21]=[CH:20][C:19]([CH2:5][C:4]2[CH:7]=[CH:8][CH:9]=[CH:2][CH:3]=2)=[CH:18][C:15]=1[C:16]#[N:17]

Participants

6

Reactant 3

HCID 947NitrogenHCID 76093,4-Dichlorobenzyl chlorideHCID 99648032-Amino-5-iodobenzonitrile

Product 1

HCID 109436972-Amino-5-benzylbenzonitrile

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst2×HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
68 °C

Procedure

A suspension of active Zn metal in THF (0.76 M, 6.3 mL calculated to contain 4.8 mmol or a 20% theoretical excess) was placed in a thoroughly dried three-necked flask which was flushed continuously with a gentle stream of dry N2. A solution of 3,4-dichlorobenzyl chloride (790 mg, 4 mmol) in dry THF (2 mL) was then added slowly to the flask at room temperature, and the reaction mixture was stirred at 68° C. for 10 h and left to stand for 3 h to allow the excess Zn metal to settle to the bottom. The dark-brown solution of organozinc reagent was transferred via a cannula using gentle N2 pressure into another three-necked flask, to which was then added dropwise a solution of 9 (244 mg, 1 mmol) in dry THF (1 mL). Standard workup as for 10a afforded 10e as a pale-yellow powder (172 mg; 65%): mp 104-107° C.; 1H NMR (CDCl3) δ 3.80 (s, 2H, CH2), 4.35 (br s, 2H, NH2), 6.68 (d, J=8.4 Hz, 1H-3), 6.97 (dd, J=8.0 Hz, 2.0 Hz, 1H, H-6′), 7.11 (s, J=8.4 Hz, H-4), 7.16 (s, 1H, H-6), 7.22 (d, J=2.0 Hz, 1H, H-2), 7.35 (d, J 8.0 Hz, 1H, H-5′).

Workup

  1. customwas flushed continuously with a gentle stream of dry N2
  2. waitleft
  3. waitto stand for 3 h

Sources & evidence

ORD record
ord-eade7e18778945ee8efd5b038d41bfde
Source dataset
uspto-grants-2007_08
Patent number
US07256197B2

Reaction notes

Loading…