Preparation of alkyl nitrates, nitrites, and thiocyanates from alcohols utilizing trichloroisocyanuric acid with triphenylphosphine

Article abstract of DOI:10.1081/SCC-200025580

Alcohols in acetonitrile are converted into alkyl nitrates, nitrites, or thiocyanates by the action of triphenylphosphine and trichloroisocyanuric acid along with silver nitrate, silver nitrite, or sodium thiocyanate, respectively.

Full text of DOI:10.1081/SCC-200025580

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Preparation of Alkyl Nitrates,
Nitrites, and Thiocyanates
from Alcohols Utilizing
Trichloroisocyanuric Acid with
Triphenylphosphine
Gene A. Hiegel a , Jeremiah Nguyen a & Yan Zhou a
a Department of Chemistry and Biochemistry,
California State University, Fullerton, Fullerton,
California, 92834, USA
Version of record first published: 10 Jan 2011.
To cite this article: Gene A. Hiegel , Jeremiah Nguyen & Yan Zhou (2004):
Preparation of Alkyl Nitrates, Nitrites, and Thiocyanates from Alcohols Utilizing
Trichloroisocyanuric Acid with Triphenylphosphine, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry,
34:14, 2507-2511
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 14, pp. 2507–2511, 2004
Preparation of Alkyl Nitrates, Nitrites,
and Thiocyanates from Alcohols
Utilizing Trichloroisocyanuric
Acid with Triphenylphosphine
*
Gene A. Hiegel, Jeremiah Nguyen, and Yan Zhou
Department of Chemistry and Biochemistry, California State University,
Fullerton, California, USA
ABSTRACT
Alcohols in acetonitrile are converted into alkyl nitrates, nitrites, or thio-
cyanates by the action of triphenylphosphine and trichloroisocyanuric
acid along with silver nitrate, silver nitrite, or sodium thiocyanate,
respectively.
Key Words: Alcohols; Alkyl nitrates; Alkyl nitrites; Alkyl thiocyanates;
Substitution; Preparation; Synthesis; Trichloroisocyanuric acid;
Triphenylphosphine.
*
Correspondence: Gene A. Hiegel, Department of Chemistry and Biochemistry,
California State University, Fullerton, Fullerton, CA 92834, USA; E-mail: ghiegel@
fullerton.edu.
2507
DOI: 10.1080/SCC-200025580
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

2508
Hiegel, Nguyen, and Zhou
INTRODUCTION
Recently we have shown that the combination of trichlorisocyanuric
acid (1) [1,3,5-trichloro-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; TCICA,
C3Cl3N3O3] with triphenylphosphine will convert alcohols into alkyl chlor-
ides and carboxylic acids to acid chlorides.[1,2] In these substitution reactions,
it has been proposed that 1 and triphenylphosphine react to form a water sen-
sitive species that is capable of reaction with an alcohol to make the oxygen a
good leaving group. We report here a related procedure for the conversion of
alcohols into alkyl nitrates, alkyl nitrites, and alkyl thiocyanates.
Nitrate esters were prepared by dissolving silver nitrate, triphenylphos-
phine, and an alcohol in anhydrous acetonitrile and then slowly adding 1.
The reaction was heated for 3 hr, and after filtration to remove the precipitate
of cyanuric acid, water was added and the ester was extracted with pentane
and purified by flash chromatography (Eq. 1). Using the same general pro-
cedure, nitrite esters were prepared from silver nitrite and thiocyanates were
prepared from sodium thiocyanate. The results are shown in Table 1.
CH3(CH2)7CH2OH þ AgNO3 þ (C6H5)3P þ C3Cl3N3O3 ꢀ!
CH3(CH2)7CH2ONO2
(1)
The order of addition is important. If the triphenylphosphine and 1 were
first combined, as is done in the previously reported synthetic reactions, and
then the silver nitrate followed by the alcohol were added, most of the
alcohol was recovered unchanged. If the triphenylphosphine and 1 were com-
bined and then the alcohol was added followed by the silver nitrate, the alkyl
chloride was the major product along with some nitrate ester.
Conversion of cyclohexanol into the corresponding nitrate and
nitrite esters gives low yields of products, but the two authentic standards
were also formed in low yield.[3,4] Benzyl alcohol was converted into benzal-
dehyde instead of benzyl nitrite when using the procedure described here and
also when using sodium nitrite, sulfuric acid, and benzyl alcohol in an attempt
to prepare the authentic sample. Cyclohexyl thiocyanate was not formed from
either the procedure described here or the literature procedure.
EXPERIMENTAL
All reagents were used as received unless otherwise stated. Anhydrous
acetonitrile, 1-nonanol, 1-octanol, cyclohexanol, benzyl alcohol, 1-chlorono-
nane, 1-chlorooctane, chlorocyclohexane, benzyl bromide, triphenylphos-
phine, sodium nitrite, and silver nitrite were obtained from Aldrich. 1 (99%)

Preparation of Alkyl Nitrates, Nitrites, and Thiocyanates
2509
Table 1. Conversion of alcohols into alkyl nitrates, nitrites, and thiocyanates.
Yielda
(%)
GC purity
(%)
Alcohol
Product
1-Nonanol
1-Octanol
2-Octanol
1-Nonyl nitrate
1-Octyl nitrate
2-Octyl nitrate
75b
63
72
27
46
65
60
39
9
99.6
99.7
95.8
99.2
96.2
97.8
95.9
96.6
96.5
96.2
95.9
99.1
81.4c
Cyclohexanol
Benzyl alcohol
1-Nonanol
Cyclohexyl nitrate
Benzyl nitrate
1-Nonyl nitrite
1-Octanol
2-Octanol
1-Octyl nitrite
2-Octyl nitrite
Cyclohexanol
Benzyl alcohol
1-Nonanol
Cyclohexyl nitrite
Benzaldehyde
23
75
71
76
1-Nonyl thiocyanate
1-Octyl thiocyanate
2-Octyl thiocyanate
No thiocyanate formed
Benzyl thiocyanate
1-Octanol
2-Octanol
Cyclohexanol
Benzyl alcohol
62
94.7
aPurified by flash chromatography.
bPurified by distillation.
cContains 17.5% of an unknown component which may be 2-octyl isothiocyanate
based on the FT-IR spectrum: 2152 cm21 (RSCN) and 2102 cm21 (RNCS).[5]
was obtained from Chem Lab Products and OMNI. Silver nitrate and sodium
thiocyanate were obtained from Baker. 2-Octanol and potassium thiocyanate
were obtained from Fisher Scientific. 2-Chlorooctane was prepared from
2-octanol.[2] Pentane was distilled prior to using. Silver nitrate, silver nitrite,
and sodium thiocyanate were dried under full pump vacuum for 24 hr
before use.
All products were compared with authentic samples by means of 1H NMR
and FT-IR spectra and GC retention time. Alkyl nitrate samples were prepared
from the alkyl halides and silver nitrate.[3] Alkyl nitrite samples were prepared
from the alcohols, sodium nitrite, and sulfuric acid.[4] Alkyl thiocyanate
samples were prepared from the alkyl nitrates and potassium thiocyanate.[3]
All authentic samples were purified by flash chromatography.
1H NMR spectra were recorded in CDCl3 using an Anasazi-modified
Varian EFT 90 MHz spectrometer. FT-IR spectra were recorded using a
Perkin Elmer 1650 spectrometer. GC analyses were carried out with a
Hewlett-Packard 5890 Series II on a 6 ft ꢁ 1/8 in. 10% Carbowax 20M
column. The procedure below for preparation of 1-nonyl nitrate was also used
for preparation alkyl nitrites and thiocyanates but silver nitrite and sodium

2510
Hiegel, Nguyen, and Zhou
thiocyanate, respectively, were used in place of silver nitrate. All products and
authentic samples, except for 1-nonyl nitrate, were prepared using about half a
gram of alcohol or starting compound.
Conversion of 1-Nonanol into 1-Nonyl Nitrate
To an oven-dried, nitrogen-flushed, 500-mL three-neck round bottom
flask fitted with a condenser, a nitrogen inlet, and two glass stoppers were
added a magnet, vacuum dried silver nitrate, 8.943 g (52.6 mmol), and
200 mL anhydrous acetonitrile (via syringe). After 15 min stirring, 5.408 g
(37.5 mmol) 1-nonanol and 13.973 g (53.3 mmol) triphenylphosphine were
added. After 15 min of stirring, 4.299 g (18.5 mmol, 55.5 meq) of 1 was
added over 1 min, and the flask was placed in an 828C oil bath for 3 hr. The
reaction mixture was vacuum filtered to remove the cyanuric acid and the
solid washed with pentane. Water, 100 mL, was added to the filtrate which
was then extracted with pentane (4 ꢁ 75 mL). The combined pentane extract
was washed with water (100 mL) and saturated NaCl solution (75 mL). After
drying over MgSO4 and filtering, the pentane was removed with a rotary evap-
orator and the residue vacuum distilled through a concentric tube column to
give 5.317 g. [75%, bp 77.5–80.38C (27.5 torr)] of 1-nonyl nitrate. Analysis
by GC showed a purity of 99.6%, and the retention time was identical to
1
that of an authentic sample. The FT-IR and H NMR spectra were identical
to those of an authentic sample.
ACKNOWLEDGMENT
This research was supported in part by an award from Rohm and
Haas Company: Otto Haas Award for Technical Excellence (courtesy of
Robert K. Barr).
REFERENCES
1. Hiegel, G.A.; Ramirez, J.; Barr, R.K. Chlorine substitution reactions using
trichloroisocyanuric acid with triphenylphosphine. Synth. Commun. 1999,
29 (8), 1415–1419.
2. Hiegel, G.A.; Rubino, M. Conversion of alcohols into alkyl chlorides using
trichloroisocyanuric acid with triphenylphosphine. Synth. Commun. 2002,
32 (17), 2691–2694.

Preparation of Alkyl Nitrates, Nitrites, and Thiocyanates
2511
3. Pattison, E.; Brown, G. Organic nitrates as synthetic reagents — preparations
of nitrates and some representative reactions. Can. J. Chem. 1956, 34,
879–884.
4. Noyes, W.A. n-Butyl nitrite. In Organic Syntheses; Wiley: New York,
1943; Collect. Vol. II, 108–109.
5. Conley, R.T. Infrared Spectroscopy; Allyn and Bacon: Boston, 1966; 117.
Received in the USA March 2, 2004