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14. Single Step

70%

Overview
Steps/Stages Notes
Reactants: 1, Reagents: 2, Solvents: 1, Steps:
1.1 R:N=O, R:KOH, S:MeOH, rt 60C, 250 kPa; 24 h, 60C, 250 1, Stages: 1, Most stages in any one step: 1
kPa
References
A New Synthetic Route to 3-Oxo-4-amino-
1,2,3-oxadiazole from the Diazeniumdiolation
of Benzyl Cyanide: Stable Sydnone Iminium
N-Oxides
By Bohle, D. Scott and Perepichka, Inna
From Journal of Organic Chemistry, 74(4),
1621-1626; 2009
Experimental Procedure
Preparative Conditions for the Selective Synthesis of 6. Under nitrogen in a glass pressure reaction
bottle 0.50 g (4.27mmol) of benzyl cyanide was added to a solution of potassium hydroxide in absolute
methanol (30 mL). The reaction flask was repeatedly flushed with nitrogen, pressurized with nitric
oxide (250 kPa), and warmed to 60 C (oil bath) for 24 h. After completion of the reaction, the yellow
reaction mixture was flushed with nitrogen and the solvent was evaporated. Recrystallization of the
crude product from acetone/hexane gave pure compound 6, yield 0.42 g (70%). mp 102-104 C (lit.12
mp 100 C); 1H NMR (DMSO, 300 MHz, ppm) 7.49 - 7.55 (m), 7.69-7.72 (m), 7.92-7.95 (m), 13.8 (s);
13C NMR (CDCl , 300 MHz, ppm) 109.3, 126.5, 129.1, 129.3, 131.7, 149.9; IR (KBr, cm-1) 3360 s,
3
2975 w, 2815 w, 2236 m, 1569 w, 1498 m, 1450 m, 1417 m, 1318 w, 1282 s, 1060 s, 1030 m, 1001 m,
967 s, 920 w, 765 s, 689 s, 675 s, 661 m, 607 m, 480 m; UV/vis (CH3OH, max, nm) 260. Anal. Calcd
for C8H6N2O: C, 65.74; H, 4.13; N 19.16. Found: C, 65.47; H 3.81; N, 19.07.
Reaction Protocol
Procedure 1. Add (4.27mmol) of benzyl cyanide to a solution of potassium hydroxide in absolute methanol (30
mL) under nitrogen in a glass pressure reaction bottle.
2. Flush the reaction flask with nitrogen.

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CASREACT : Copyright 2017 American Chemical Society. All Rights Reserved. CASREACT contains reactions
from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations
database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006
John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced
under license. All Rights Reserved.
22. Single Step
 SciFinder Page 2

83%

Overview
Steps/Stages Notes
Reactants: 2, Reagents: 3, Solvents: 3, Steps:
1.1 R:t-BuOCl, S:CH2Cl2, S:Me2CHOH 1, Stages: 4, Most stages in any one step: 4
1.2 R:Et3N, S:H2O References
1.3 S:CH2Cl2 A convenient synthesis of -
hydroxyiminoacetonitriles from aldoximes
1.4 R:H2SO4, S:H2O
By Ma, Jun-An et al
From Synthetic Communications, 29(22),
3863-3868; 1999
Experimental Procedure
General procedure (a single-vessel reaction) A solution of tert-butyl hypochlorite (6.0mmol) in
dichloroethane (5ml) was added dropwise at -12~10C to aromatic aldoximes (1a~g 6.0mmol) in
dichloroethane (10ml) and isopropyl alcohol (2.5ml) with vigorous stirring. After 30 minutes a solution
of triethylamine (6.0mmol) and sodium cyanide (7.2mmol) in water (5ml) was added at -5~10 C. The
mixture was stirred for 4 hours at ambient temperature, diluted with dichloroethane (30ml) and
separated. The organic layer was washed with water, aqueous sulphuric acid (5%) and water, then
dried (MgSO4). The solvent was removed under reduced pressure to afford the crude products (3a~g),
which was purified by recrystallization from dichloroethane-light petroleum. Spectral data and
elemental analyses are given as follows: 3a: yield 83.2%. colorless laths. m.p.122~124C (lit.10,
m.p.132~133C), IR (KBr) max/cm-1: 3317, 2263, 1634, 1600, 1560, 1377, 954. 1HNMR (CDCl3)
ppm: 7.40~7.92 (m, 5H, C6H5), 8.96 (3, 1H, N-O-H).
CASREACT : Copyright 2017 American Chemical Society. All Rights Reserved. CASREACT contains reactions
from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations
database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006
John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced
under license. All Rights Reserved.