T&ma, Vol. 38, No. 2, pp. 217421, 1991 ~3~1~~1 $3.00 + 0.

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REDOX REACTIONS IN NON-AQUEOUS MEDIA:

DETERMINATION OF ORGANIC IS~T~I~YANATES
ALONE, IN FORMULATIONS AND IN
IMPORTANT MIXTURES

B. C. Vxnm*, S. B. KALu, V. S. JAMWAL, Sunma I&n&a, D. K. SW and ANUA Sun

Department of Chemistry, Himachal Pradesh University, Summer Hi, Shimla 171005, India

(Received 9 February 1990. Revised 1 June 1990. Accepted 12 June l!NO)

!%mmwy-A simple ~t~ti~et~c method for the dilation of or~o~~~~a~ is described.

The isothiocyanate is treated in acetonitrile medium with an excess of primary amine to convert it into
a substituted thiourea and the surplus amine is converted into a dithiocarbamate by addition of carbon
disulphide. The solution is then titrated with a copper solution in acetonitrile. The three-step titration
curve enables the results to be calculated on the basis of the dithiocarbamate and/or thiourea formed.
The method has been successfully applied to the analysis of a wmmercial insecticide formulation based
on isothiocyanate and important mixtures containing isothiocyanatcs.

The wide commercial use of organoisothio- The residual amine can be converted into a
cyanates necessitates convenient and reliable dithiocarbamate by treatment with carbon
procedures for their dete~nation. The method dis~phide:
described here is based on the following
reactions. In acetonitrile medium an excess of 2R’NH, + CS2--+R’HN-C-S- .(NH,R’)+
primary amine smoothly and quantitatively
converts isothiocyanates into the corresponding 1
substituted thioureas:
RNCS + R’NH,--,RHN-C-NHR Copper(I1) perchlorate in acetonitrile medium
oxidizes the thiourea to the corresponding sub-
!t! stituted formamidine disulphide’

and the dithiocarbamate to the corresponding

thiuram dis~phide2 in two well-defined steps:

4R’HN-C-S- + 2Cu2++R’HN--C-S-S-C-NHR’ + 2R’HN-C-SCu

1 1 !/ 1
2R’HN-C-SCu + 2Cu*+ + 16CH,CN+R’HN-C-S-!3--C!-NHR’ + 4[Cu(CH~C~~J
j !! !

*Author for correspondence.

TAL3W?-li 217
218 B. C. VERMA
The first of these steps results in simul-
taneous formation of thiuram disulphide and
copper(I) dithiocarbamate, the organic moiety
of which is then also oxidized to thiuram
disulphide.
Potentiometric titration of this system gives a
curve with three distinct inflection points. The
dithiocarbamate is completely titrated before
the potential rises enough to begin the oxidation
of the substituted thiourea. This has been
confirmed by titration of various mixtures of
dithiocarbamates and thioureas.
The method gives the option of calculat-
ing the results on the basis of the frrst and/or
second inflection points (corresponding to
the amount of dithiocarbamate) or the third
inflection point (corresponding to the amount
of thiourea formed). The method has been
used for analysis of a commercial insecticide
formulation (based on methyl isothiocyanate)
and analysis of isothiocyanate-isocyanate and
isothiocyanate-thiourea mixtures.
Isothiocyanates and isocyanates are similar
both in structure and their reactions with am-
monia and amines to form substituted thioureas
and ureas respectively. Treatment of a mixture
(containing one of each species) with an excess
of amine and then with carbon disulphide in
acetonitrile followed by potentiometric titration
with copper(I1) could be used to determine both
components. The first two steps in the titration
curve correspond to the amount of dithiocarba-
mate (and consequently indirectly to the
amount of isothiocyanate and isocyanate pre-
sent in the mixture) and the third corresponds
to the amount of thiourea produced and hence
the isothiocyanate content of the mixture.
The amount of isocyanate can be found by
difference.
The analysis of isothiocyanat+thiourea mix-
tures is also of importance since isothiocyanates
serve as the starting materials for the prep-
aration of thioureas and the method can again
be used.
EXPERIMENTAL
Reagents
Acetonitrile (Merck). Distilled twice from
phosphorus pentoxide (5 g/l.).
Copper(H) perchlorate standard solution in
acetonitrile. Prepared and standardized as de-
scribed earlier.3
Organoisothiocyanates. Allyl, methyl and
phenyl isothiocyanates (Fluka) were distilled
et al.
before use. Other alkyl isothiocyanates were
prepared by a known method.4
Organoisocyanates. n-Butyl and a-naphthyl
isocyanates (Fluka) were distilled before use.
Phenyl isocyanate was prepared by the method
of Allen and Bell5
Thioureas. Thiourea (Sarabhai M. Chemicals)
was recrystallized before use. Alkyl thioureas
were prepared from their corresponding
isothiocyanates.4
Apparatus
Potentiometric titrations were performed
with a bright platinum wire as indicator elec-
trode, a modified calomel electrode (tilled with
saturated methanolic potassium chloride sol-
ution) as reference, and a Toshniwal (India)
CL06A type potentiometer.
Potentiometric determination of isothiocyanates
with copper@) perchlorate
Aliquots of isothiocyanate solution in aceto-
nitrile were added with stirring to known vol-
umes of standard (0.02M) n-butylamine in
acetonitrile, in glass-stoppered vessels and the
volumes made up to 2625 ml with acetonitrile.
The vessels were stoppered, swirled to mix the
reactants and set aside for 5 min to complete the
reaction. Each solution was mixed with 1 or 2
drops of carbon disulphide and titrated at room
temperature (N 23”) with standard (0.2M) cop-
per(I1) perchlorate potentiometrically. Figure 1
shows the profile of a typical three-step poten-
tiometric titration. The results calculated on the
basis of the first (residual amine) and third
(thiourea formed) breaks are given in Table 1.
Analysis of formulations
The experimental details are the same as
described above for organoisothiocyanates, the
only difference being that aliquots of an aceto-
nitrile solution of the liquid formulation (in-
stead of the isothiocyanate) were added to
known volumes of standard n-butylamine sol-
ution. The profiles of the potentiometric ti-
trations are similar to those obtained for
isothiocyanates. The results (Table 2) are com-
pared with those obtained by an independent
method.6
Analysis of isothiocyanate-isocyanate mixtures
Aliquots of acetonitrile solutions of isothio-
cyanate and isocyanate in various proportions
were analysed by the procedure already given
 Determination of organic isothiocyanates 219

0.9 r Table 2. Recovery of methyl isothiocyanate from technical

formulation containing 23.5% active ingredient (mean f
standard deviation of 5 dewminations)
O.? - Comparison
Present method methods
Active
ingredient Found, Recovery, Found, Recovery,
taken, mg mg % w %
2.82 2.78 98.6 f 0.36 2.77 98.4 f 0.42
5.64 5.58 98.9 f 0.68 5.56 98.6 f 0.58
8.46 8.39 99.2 f 0.52 8.32 98.3 f 0.60
11.28 11.09 98.3 f 0.48 11.11 98.5*0.50

with primary amines to form substituted

Volume of copper (II) perchlorate 002M)odded
Fig. I
for isothiocyanates. The results for a mixture of
phenyl isothiocyanate and phenyl isocyanate are
given in Table 3.
Analysis of isothiocyanate-thiourea mixtures
Aliquots of acetonitrile solutions of isothio-
cyanates and thioureas in various proportions
were also analysed in the same way as isothio-
cyanate solutions. The results for analysis of a
mixture of n-butyl isothiocyanate and n-butyl
thiourea are given in Table 4.
RESULTS AND DISCU3SION
Organoisothiocyanates are quite resistant to
oxidation and reduction. However, they react
thioureas, which can be easily oxidized. Hence,
this reaction could serve as an important
tool for the determination of isothiocyanates.
Because isothiocyanates are insoluble in water
but react with it’ and substituted thioureas are
sparingly soluble in water, a non-aqueous sol-
(ml)
vent is required for the transformation of iso-
thiocyanates into thioureas and oxidimetric
determination of the latter. Acetonitrile has
been chosen as the solvent for the following
reasons.
(i) It is a versatile solvent for non-aqueous
redox titrations because of its high dielectric
constant, resistance to oxidation reduction, con-
venient liquid range, ready availability, wide
electrochemical range and low toxicity.8~9
(ii) A solution of copper@) perchlorate in
acetonitrile is very stable and is a powerful
oxidizing agent.8*9
(iii) In this solvent, carbon disulphide
converts amines quantitatively into dithiocarba-
mates, so isothiocyanates can also be deter-
mined through measurement of the residual
amine from the derivatization reaction.

Table 1. Potentiomctric determination of organoisothiocyanates with copper(H) perchlorate (mean f

standard deviation of 10 determinations)
on the basis of excess of
amine as dithiocarbamate On the basis of thiourea formed
Amount Amount Amount Amount
found*, found?, found*, foundt,
Isothiocyanates w w mg w
Ally1 2.50 f 0.021 4.95 f 0.040 2.48 f 0.021 4.97 & 0.046
Methyl 2.48 f 0.020 4.96 f 0.051 2.47 f 0.022 4.95 f 0.058
n-Propyl 2.49 f 0.030 5.04 f 0.052 2.52 f 0.034 4.96 f 0.061
Isopropyl 2.52 f 0.020 4.97 f 0.041 2.48 f 0.017 5.05 f 0.048
n-Butyl 2.5 1 f 0.030 4.96 f 0.039 2.49 f 0.036 4.95 f 0.043
Isobutyl 2.47 f 0.020 5.03 f 0.030 2.52 f 0.022 5.04 f 0.038
Phenyl 2.52 f 0.015 4.98 f 0.050 2.51 f 0.018 4.96 f 0.056
*Amount taken, 2.5 mg.
tAmount taken, 5.0 mg.
220 B. C. VEXMAet al.

Table 3. Analysis of a mixture containin phenyl isothiocyanate and phenyl isocyanate

(mean f standard deviation of 10 determinations)
Phenyl isothiocyanate Phenyl isocyanate Ratio of
in the mixture in the mixture isothiocyanate to
isocyanate in the
Taken, mg Found, mg Taken, mg Found, mg mixture
4.00 4.04 f 0.032 4.00 4.04 & 0.028 1:l
4.00 4.03 f 0.036 8.00 1.96 f 0.024 1:2
4.00 3.96 f 0.032 12.00 12.06 f 0.048 1:3
4.00
8.00 4.00
7.94 ff 0.018
0.012 16.00
4.00 15.92
4.05 ff 0.036
0.072 ;;;
12.00 11.93 f 0.056 4.00 4.04 f 0.032 3:l
16.00 16.12 f 0.067 4.00 3.91 f 0.032 4:l

Copper(I1) oxidizes both a dithiocarbamate components. The synthetic mixtures of phenyl

and a thiourea in a mixture of the two, giving isothiocyanate and phenyl isocyanate with
a three-step titration curve (Fig. 1). The redox ratios in the range 1: 4-4: 1 were analysed
potentials of thioureas and dithiocarbamates with an average standard deviation of 0.7%
are sufficiently different to permit selective for phenyl isothiocyanate and 0.6% for
titration [E” for diethyldithiocarbamate-tetra- phenyl isocyanate (Table 3). The method has
ethyl thiuram disulphide is - 0.58 V (vs. SCE);” been extended to other mixtures such as ethyl
E” for thiourea-formamidine disulphide is isothiocyanate/ethyl isocyanate; n-propyl iso-
+0.42 V (us. SCE)“]. The results in Table 1 thiocyanate/n-propyl isocyanate; isopropyl
show that the overall standard deviations calcu- isothiocyanate/isopropyl isocyanate; n-butyl
lated from the pooled data of all the titrations isothiocyanate/n-butyl isocyanate, with similar
performed with 2.5 and 5 mg of each isothio- performance to that for the model mixture.
cyanate are 0.022 and 0.043 mg, respectively The method has also been applied to the
(on the basis of the tist potential break, for analysis of mixtures of isothiocyanates and
residual amine) and 0.024 and 0.050 mg, re- thioureas. The results recorded in Table 4 for
spectively (on the basis of the third potential the analysis of synthetic mixtures of n-butyl
break, for thiourea formed). The recoveries of isothiocyanate and n-butylthiourea with ratios
methyl isothiocyanate in the analysis of the in the range 1: 44 : 1 have an average standard
formulation were in the range 98.~99.2% with deviation of 0.6% for both components. The
standard deviations in the range O&0.7% method has been extended to other mixtures
(Table 2). such as methyl isothiocyanate/methyl thiourea;
The proposed methods for the analysis of ethyl isothiocyanate/ethyl thiourea; n-propyl
isothiocyanate-isocyanate and isothiocyanate- isothiocyanate n-propyl thiourea; isobutyl
thiourea mixtures, besides being simple, accu- isothioycyanate/isobutyl thiourea; pentyl iso-
rate and reliable, have the added advantage thiocyanate/pentyl thiourea, with performance
that the complete analysis can be conducted similar to that for the model mixtures.
with the same sample solution, resulting in a
saving of time and effort. A single potentio- Mcnowledgement-The authors thank the Council of
metric titration with copper(I1) perchlorate Scientific and Industrial Research, New Delhi, for financial
enables each mixture to be analysed for both assistance.

Table 4. Determination of a mixture containing n-butyl isothiocyanate and n-butylthiourea

(mean
. f- standard deviation of 10 determinations)
ndutvl isothiocvanate ndutyl thiourea Ratio of n-butyl
in the mixture in the mixture isothiocyanate to
n-butylthiourea in
Taken, mg Found, mg Taken, mg Found, mg the mixture
4.00 4.03 f 0.020 4.00 4.04 f 0.038 1:l
4.00 3.96 f 0.022 8.00 7.95 f 0.034 1:2
4.00 4.04 f 0.036 12.00 11.94 f 0.056 1:3
4.00 3.91 f 0.022 16.00 15.94 f 0.069 1:4
8.00 1.92 f 0.056 4.00 4.00 f 0.036 2:l
12.08 11.93 f 0.062 4.00 4.03 f 0.028 3:l
16.00 16.08 f 0.068 4.00 3.96 f 0.018 4:l
 Determination of organic isothiocyanates
REFERENCES
1. B. Kratochvil and D. A. Zatbo, Anal. Chem., 1968,
40, 422.
2. B. C. Verrna, S. Chauhan, A. Sood, D. K. Shartna and
H. S. Sidhu, Talanru, 1985, 35 139.
3. P. F. Quirk and B. Kratochvil, Anal. Chem., 1970,
42, 535.
4. N. L. Drake, Org. Synrh, 1941, 21, 81, 83.
5. C. F. H. Allen and A. Bell, Org. Synth., Collective
Vol. III, 1955, p. 846.
221
6. M. Ottnad, N. A. Jenny and C.-H. Rdder, in G. Zweig
(ed.), Anal. Methodr Pestic. Plant Growth Regul., 1978,
X, 563.
7. J. H. Karchmer, The Analytical Chemistry of Sulphur
and its Compounds, Part II, p. 715. Wiley-Interscience,
New York, 1972.
8. B. Kratochvil, Chem. Canada, 1968, 20, 19.
9. Idem, CRC Crit. Rev. Anal. Chem., 1971, 1, 415.
10. P. W. Preisler and L. Berger, J. Am. Chem. Sot., 1947,
69, 322.
11. E. C. Gregg and W. P. Tyler, ibid., 1950, 72, 4561.