Conversion of alcohols into alkyl chlorides using trichloroisocyanuric acid with triphenylphosphine

Article abstract of DOI:10.1081/SCC-120006034

Trichloroisocyanuric acid with triphenylphosphine in anhydrous acetonitrile will convert alcohols into alkyl halides.

Full text of DOI:10.1081/SCC-120006034

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CONVERSION OF ALCOHOLS INTO ALKYL CHLORIDES
USING TRICHLOROISOCYANURIC ACID WITH
TRIPHENYLPHOSPHINE
a
a
Gene A. Hiegel & Mark Rubino
a
Department of Chemistry and Biochemistry , California State University , Fullerton,
Fullerton, CA, 92834, U.S.A.
Published online: 20 Aug 2006.
To cite this article: Gene A. Hiegel & Mark Rubino (2002) CONVERSION OF ALCOHOLS INTO ALKYL CHLORIDES USING
TRICHLOROISOCYANURIC ACID WITH TRIPHENYLPHOSPHINE, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:17, 2691-2694, DOI: 10.1081/SCC-120006034
To link to this article: http://dx.doi.org/10.1081/SCC-120006034
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 17, pp. 2691–2694, 2002
CONVERSION OF ALCOHOLS INTO
ALKYL CHLORIDES USING
TRICHLOROISOCYANURIC ACID WITH
TRIPHENYLPHOSPHINE
Gene A. Hiegel* and Mark Rubino
Department of Chemistry and Biochemistry,
California State University, Fullerton, Fullerton,
CA 92834, USA
ABSTRACT
Trichloroisocyanuric acid with triphenylphosphine in anhy-
drous acetonitrile will convert alcohols into alkyl halides.
Key Words: Alkyl chlorides; Alcohols; Trichloroisocyanuric
acid; Triphenylphosphine; Synthesis; Preparation
A variety of reagents can be used to convert alcohols into alkyl
[1]
chlorides. Many of these reagents are water reactive and do not store
well. Recently we reported that a freshly prepared mixture of trichloroiso-
cyanuric acid (1) [1,3,5-trichloro-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione;
TCICA] (CAS Reg. No. [87-90-1]) and triphenylphosphine (Ph P) in anhy-
3
drous acetonitrile is an effective reagent for carrying out a variety of
[
2]
substitution reactions for which PCl and similar reagent are often used.
5
It is reasonable to assume that 1 transfers a chlorine to the phosphorus to
*
Corresponding author. E-mail: ghiegel@fullerton.edu
691
2
DOI: 10.1081/SCC-1200060340039-7911 (Print); 1532-24
Copyright & 2002 by Marcel Dekker, Inc.
32 (Online)
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692
HIEGEL AND RUBINO
þ
ꢀ
ꢀ
form a reactive complex of the type Ph P Cl Z , where Z is the remaining
3
portion of 1. The overall reaction is shown in the equation.
The triphenylphosphine oxide produced in these reaction can be diffi-
cult to separate from the products, however. In order to accomplish this
separation, all of the reaction reported in our previous paper were carried
out on a small scale with purification by means of flash chromatography.
Now we report the results of reactions carried out on an 8 g scale with
isolation by means of extraction with pentane, which effectively separated
the triphenylphosphine oxide, and purification by distillation.
After an initial examination of the reaction between 1 and Ph P, it was
3
determined that with a 1.05 : 1 equivalent ratio of 1 : Ph P neither reagent
3
would be present in excess. Since there are three equivalents per mole of 1,
the corresponding mole ratio is 0.35 : 1.
In the general reaction procedure 1.50 equivalents of Ph P was dis-
3
solved in anhydrous acetonitrile, and 1.58 equivalents of 1 was added slowly
because the reaction is highly exothermic. The yellow mixture was then
ꢁ
heated in a 60 C oil bath, 1.0 equivalent of the alcohol was added, and
the mixture stirred for 2 h. Two different work-up procedures were used.
For compounds which did not contain an aromatic ring, a large amount of
water was added to the reaction mixture, the solid (cyanuric acid) was
removed by filtration, the filtrate was then extracted with pentane, the pen-
tane solution dried, and the product distilled. This procedure was not satis-
factory for compounds with an aromatic ring. In those cases, the reaction
was quenched with a small amount of water, and after filtration, most of the
solvent was removed with a rotary evaporator. The residue was extracted
with pentane, the pentane solution dried, and the product distilled.
Primary alcohols gave the best yields and secondary and benzyl alco-
hols gave lower yields of chlorides. Cyclohexanol gave a low yield of cyclo-
hexene. The results are summarized in Table 1.
Both 1 and Ph P are stable and inexpensive, but when combined, they
3
form a reactive complex capable of converting alcohols to the corresponding
alkyl chlorides.

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TRICHLOROISOCYANURIC ACID
2693

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2
694
HIEGEL AND RUBINO
EXPERIMENTAL
All alcohols were of 97% or greater purity and were used as received
except for benzyl alcohol and cyclohexanol which were distilled before use.
Alkyl chloride and alkene standards were commercially available except for
2-chlorooctane which was prepared from 2-octanol using thionyl chloride.
Anhydrous acetonitrile was used for all reactions and was obtained from
Aldrich. Trichloroisocyanuric acid (1) (99% pure) was obtained from Chem
Lab Products. Pentane was distilled prior to use. IR spectra were recorded
using a Perkin Elmer 1650 FT-IR spectrometer. NMR were recorded using
a Bruker AC-200 spectrometer. GC analyses were performed with a Hewlett
Packard 5890 Series II instrument with a 6 ft. by 1/8 in. 10% Carbowax
20 M column. All reaction products were compared with standards by
means of IR, NMR, and GC.
Preparation of 1-Chlorodecane
To a 300-mL three-neck round-bottom flask were added a magnetic stir
bar, a reflux condenser, and 100 mL acetonitrile by syringe. Ph P, 19.88 g
3
(75.79 mmol), was added through a funnel, and 10 mL of acetonitrile was
used to rinse the funnel. While stirring, 6.17 g (26.55 mmol) of 1 was added
over about a 10 min period through a funnel and then 10 mL of acetonitrile
ꢁ
was used to rinse the funnel. The flask was placed in a 60 C oil bath, 7.98 g
(
50.41 mole) of 1-decanol was added to the mixture by syringe, and the reac-
tion was stirred for 2 h. Then 30 mL water was added, the mixture filtered, and
the solid washed with pentane. The filtrate was transferred to a separatory
funnel and extracted with pentane (60 mL and 3 ꢂ 40 mL). The combined
pentane solution was washed with sat. NaCl solution (50 mL) and dried
over MgSO . After filtration and removal of the pentane, the residue was
4
distilled to give 6.61 g (74%, 99.4% pure) of 1-chlorodecane. The GC reten-
tion time and the IR and NMR spectra were identical to those of the standard.
REFERENCES
1
2
. Larock, R.C. Comprehensive Organic Transformations—A Guide to
Functional Group Preparations, 2nd Ed.; John Wiley & Sons, Inc.:
New York, 1999; 690–693.
. Hiegel, G.A.; Ramirez, J.; Barr, R.K. Synth. Commun. 1999, 29(8), 1415.
Received in the USA September 4, 2001