Cyanidation of halogen compounds and esters catalyzed by PEG400 without solvent

Article abstract of DOI:10.1081/SCC-100104474

Primary aliphatic and aromatic nitriles were synthesized in excellent yields (84-96%) and purity by the cyanidation of halogen compounds and esters with dry powdered sodium cyanide catalysed by phase transfer catalyst PEG400 under solvent-free conditions.

Full text of DOI:10.1081/SCC-100104474

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CYANIDATION OF HALOGEN COMPOUNDS AND ESTERS
CATALYZED BY PEG400 WITHOUT SOLVENT
Yu-Qing Cao a , Bao-Hua Chen a & Ben-Gao Pei a
a Department of Chemistry, Hebei University, Baoding, 071002, P. R. China
Version of record first published: 09 Nov 2006.
To cite this article: Yu-Qing Cao , Bao-Hua Chen & Ben-Gao Pei (2001): CYANIDATION OF HALOGEN COMPOUNDS AND
ESTERS CATALYZED BY PEG400 WITHOUT SOLVENT, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:14, 2203-2207
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SYNTHETIC COMMUNICATIONS, 31(14), 2203–2207 (2001)
CYANIDATION OF HALOGEN
COMPOUNDS AND ESTERS CATALYZED
BY PEG400 WITHOUT SOLVENT
Yu-Qing Cao,* Bao-Hua Chen, and Ben-Gao Pei
Department of Chemistry, Hebei University, Baoding 071002,
P. R. China
ABSTRACT
Primary aliphatic and aromatic nitriles were synthesized in
excellent yields (84–96%) and purity by the cyanidation of
halogen compounds and esters with dry powdered sodium
cyanide catalysed by phase transfer catalyst PEG400 under
solvent-free conditions.
Nitriles are among the important organic compounds and many ways
have been disclosed for their synthesis. The direct nucleophilic substitution
of organic halides, esters, tertiary amines and quaternary ammonium salts
1,2,3
etc. by metalcyanides in protic
or aprotic solvents4,5 is the most useful
method. Higher yields and shorter reaction times may be obtained by phase
transfer catalysts(PTC), such as crown ethers6,7 and quaternary ammonium
salts.8 But major drawbacks have to be noted. Solvolysis and the formation
of isocyanides in protic solvents, particularly in water, are obvious. Using
large amounts of organic solvents is dangerous and costly either in labora-
tory or in industry. Otherwise, disposalof a alrge amount of waste water
containing cyanides must be thought highly.
* Corresponding author.
2203
Copyright & 2001 by MarcelDekker, Inc.
www.dekker.com

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CAO, CHEN, AND PEI
Developing green chemistry is one of the most important purposes of
organic synthesis methodology at present. Organic synthesis at the absence
of sovl ents is a powerfultoolfor this purpose and the generation of struc-
turally diverse molecules due to higher selectivity and ease of set-up and
work-up, and arouses a growing interest.9,10,11
Polyethylene glycols(PEG) have been widely used as catalysts
in many organic reactions12,13 owing to their stability, low cost, poisonless
and easy availability. It has been proved that PEGS incorporating 7–9 units
are more effective in catalyzing the reactions of metal salts without
solvents.14
Here we wish to report our investigation on the facile cyanidation of
organic halides and esters catalysed by PEG400 without solvents. The
results are listed in Table 1.
Scheme.
RESULTS AND DISCUSSION
The reactions were carried out smoothly for the liquid reactants and
nitriles under the designed temperature with an amount of 3 mole%
PEG400. 30% excess of dried and fine powdered sodium cyanide is necess-
ary for insuring the complete conversion of the substrates in appropriate
reaction periods.
Excellent yields were obtained for the reactants 1, 9, 11, 15, which
can solvolysis easily in protic solvents, and the advantages are obvious
comparing with the procedures reported for the synthesis of nitriles g15
h16 i17 m.18
As shown in Table 1, satisfactory results can be achieved for the pri-
mary aliphatic halides and aromatic halides with electron-driving groups.
Competitive elimination reaction may be the major reason for the lower
yields of substitution products of the secondary halides(5, 6).
Gas chromatography results showed no isocyanide in the cyanidation
of n-butylbromide(3). It supported the idea that sodium cyanide was a close
ion-pair in the reaction system.13
The distinct advantages of the process over the others for the syn-
thesis of nitriles lie in the higher yields, versatile substrates and simpler
procedures.

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CYANIDATION OF HALOGEN COMPOUNDS AND ESTERS
2205
Table 1. Cyanidation Results of Some Organic Halides or Esters
EXPERIMENTAL SECTION
GC: GC–9A, 2 m column of silicon–FFAP. Melting points were deter-
mined on a microscopy apparatus and uncorrected. Melting points and
boiling points were compared with the literature values. Chloropyrazine

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CAO, CHEN, AND PEI
and phthalide were prepared according to the procedures described by
Cheeseman19 and Gardner.20 Benzylchloride and dimethylsulfate were redis-
tilled before use. Other reagents were obtained from commercial supplier
and were used without further purification.
General Procedures
A dry, 250 mL three-necked, round-bottomed flask equipped with a
sealed mechanical stirrer and a reflux condenser connected to gas bubble
holding a 30% NaOH solution, was charged with reaction substrate
(0.40 mol), 26 g (0.52 mol) of dry powdered sodium cyanide and 4.8 g
(12 mmol) of PEG400. The reaction was processed with heating and vigo-
rous stirring under reflux or designed temperature. After the reflux or the
spot of substrate on a TLC plate was not obvious, heating and stirring were
continued for 30 min. The final mixture was disposed as following:
A. The liquid products were distilled directly or under reduced
pressure.
B. For products k and l: 50 mL of hydrochloric acid (3 mol/L) was
placed in a pressure-equalizing dropping funnel and added to the cooled
mixture with stirring over a 20 min period. The precipitate was isolated by
filtration and washed with water (two portions of 50 mL).
C. For m: 50 mL of hydrochloric acid (12 mol/L) took the place of
hydrochloric acid in B. The other processes were identical to B.
REFERENCES
1. Allen, F.H. Org. Syn. Coll. 1, 1941, 156.
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4. Cinquini, M. and Tundo, P. Synthesis 1976, 516.
5. Harusana, S.; Yoneda, R.; Omori, Y. and Kurihara, T. Tetrahedron
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6. Friedman, L. and Shechter, H. J. Org. Chem. 1961, 26, 2522.
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2207
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Received in The Netherlands October 14, 2000

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