Chromatographic component of identification of the transformation products of 1,1-dimethylhydrazine in the presence of sulfur

Article abstract of DOI:10.1134/S1070363214060097

The gas-chromatographic retention indices of the products of 1,1-dimethylhydrazine transformations in the presence of sulfur allows one to confirm and, in ceratin cases, make more exact the results of their gas chromatography-mass spectrometry identificat

Full text of DOI:10.1134/S1070363214060097

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 6, pp. 1106–1114. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.G. Zenkevich, A.V. Ul’yanov, S.L. Golub, A.K. Buryak, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 6,
pp. 923–931.
Chromatographic Component of Identification
of the Transformation Products of 1,1-Dimethylhydrazine
in the Presence of Sulfur
I. G. Zenkevicha, A. V. Ul’yanovb, S. L. Golubb, and A. K. Buryakb
a St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
е-mail: izenkevich@mail15.com
b Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
Received November 18, 2013
Abstract—The gas-chromatographic retention indices of the products of 1,1-dimethylhydrazine transforma-
tions in the presence of sulfur allows one to confirm and, in ceratin cases, make more exact the results of their
gas chromatography–mass spectrometry identification. Features of identification of new compounds, including
1,1-dimethyl-2-thioxohydrazine are discussed.
Keywords: dialkyl polysulfides, 1,1-dimethylhydrazine, gas chromatography–mass spectrometry, retention index
DOI: 10.1134/S1070363214060097
1,1-Dimethylhydrazine (unsymmetrical dimethylhyd-
razine) (I) is a widely used component of rocket fuels
[1]. Like other hydrazine derivatives, this compound is
highly reactive toward a great variety of reagents [2],
which predetermines its diverse transformations in the
environment, in particular in soil. In this connection,
much effort has been devoted to detailed research of
the products of transformations of compound I in
natural media by means of gas chromatography–mass
spectrometry [1, 3, 4], and high-performance liquid
chromatography (HPLC), and ionic chromatography
[5–9]. As a result, a series of previously unknown
compounds were identified, including formic 2,2-
dimethylhydrazide [(CH3)2NNHCHO] [5], substituted
triazoles [9], etc. A contact of unsymmetrical hyd-
azine with sulfur and sulfur-enriched soils (shungites)
10] leads to formation of previously uncharacterized
compounds containing N–S bonds. They include
methyl (dimethylamino) polysulfides (CH3)2NSnCH3
graphic data, of which the best interlaboratory re-
producibility is characteristic of retention indices (RI)
on standard nonpolar polydimethylsiloxane phases [11].
In the present work we determined the RIs of the
transformation products of compound I, formed by its
reactions with elemental sulfur and sulfur-containing
soils and used the resulting RIs for a more detailed
identification of these compounds.
Even though a great number of compounds with N–
S and N=S bonds have been characterized by the
present time [12–14], they are fairly rarely used in
practical synthetic organic and analytical chemistry
and are considered quite “exotic” compounds. In most
major reference databases [15], no reliable estimates
for the N–S and N=S bond energies are available, and
the information on the physicochemical characteristics
of such compounds is fragmentary, not to speak of
chromatographic retention indices. The most known
compounds containing N–S bonds are heteroaromatic
isothiazoles, whose simplest homologs are among
components that impart odor to food products [16–20]
and are also comprised in essential oils of certain
plants. For example, 4,5-dimethylisothiazole was
found in the essential oil of Azadirachta indica A. juss
seeds [21]. The unusual properties of isothiazoles can
(n
≤
4) and bis(dimethylamino) polysulfides
(CH3)2NSnN(CH3)2 (n ≤ 4). Moreover, 1,1-dimethyl-2-
thioxohydrazine (a thio analog of N-nitrosamines) was
identified for the first time in natural objects [1, 3, 4].
The mentioned compounds were initially identified
exclusively by mass spectra. Therefore, we found it
necessary to cofirm this identification by chromato-
1106

CHROMATOGRAPHIC COMPONENT OF IDENTIFICATION
1107
be illustrated by their normal boiling points: If the
boiling point of isoxazole is higher compared to oxa-
zole (95 and 68–70°С, respectively), with isothiazol
and thiazol we deal with the reverse situation (114 and
116.8°С). Bis(dimethylamino) sulfide [(CH3)2N]2S (bp
127–130°С) was characterized by RIs on standard
nonpolar stationary phases (811 ± 15); mass spectral
data were reported for bis(dimethylamino) disulfide
[(CH3)2N]2S2 [22].
Determination of chromatographic retention indices
of analytes suggests additional determination of reten-
tion times of reference n-alkanes either in mixtures
with the analytes or in separate chromatographic runs
but in absolutely identical separation conditions [11].
The second approach is commonly used in the analysis
of complex mixtures or unknown samples to exclude
possible overlaps of analyte and reference peaks. If, by
one or another reason, the mixture of reference n-al-
kanes was not analyzed, all detected compounds
remain to be characterized exclusively by retention
times; the latter are not infrequently considered
impossible to recalculate into retention indices. The
results of gas chromatography–mass spectrometry
(GCMS) identification of the reaction products of
compound I with sulfur-containing materials were
presented just in this form [1, 3, 4]. The data set for
each compound includes retention time, mass spectral
information [molecular masses and mass numbers of
the base peaks in the mass spectra (m/z)100], and
identification result.
Aliphatic amines and hydrazines catalyze certain
reactions of elemental sulfur, including the transforma-
tions of sulfides or disulfides to polysulfides [23–27].
R2S + S8 → R2Sx (x ≥ 2).
Sulfur, too, activates certain reactions of hyd-
razines, for example, the condensation with aldehydes
to form both hydrazones and azines [28]. Secondary
aliphatic amines react with diaryl disulfides to form
sulfenamides [29] (the role of oxidant in this reaction
appears to belong to air oxygen).
Ar2S2 + R2NH → ArSNR2.
Nevertheless, even in such cases there is a way to
find retention index for each component. To this end
one can make use of the following approach: retention
indices can be calculated not only by the retention
indices of n-alkanes CnH2n+2 (their retention indices are
postulated to be 100n), but also with the retention
indices of any components, provided these values are
determined with a sufficient level of reliability. To
minimize the so-called interpolation errors associated
with the nonlinearity of the dependence of retention
index on retention time for chosen reference
components, this approach is expedient to apply to
calculate linear logarithmic rather than linear retention
indices [37, 38]. In view of the fact that the calculation
formula for RIx [Eq. (1)] contains a variable coefficient
q, such dependences can be linearized at any reference
components. The nonlinearity of RI(tR) can be
compensated for by varying q.
The reaction mixtures of elemental sulfur with
hydrazine hydrate solutions [25] and substituted
hydrazines (the most characterized of the latter are 1,1-
disubstituted hydrazines) acquire intense colors (from
red orange to purple); thioxohydrazines are suggested
as primary reaction products [15].
R2NNH2 + 1/4S8 → R2N–N=S + H2S.
The color of compounds of this class is provided by
the N=S chromophore which is similar to the C=S
chromophore. Thioxohydrazines are unstable when
stored in solutions at room temperature, still less on
when distilled; the main reason for this feature is their
tendency for polymerization, probably, due to a
considerable contribution of bipolar structures [14].
R2N–N=S ↔ R2N+=N–S–.
The same reason explains the high reactivity of thi-
oxohydrazines as dienophiles in Diels–Alder reactions
[14]. As little as three thioxihydrazines were isolated
in the free state: 1,1-dimethyl-2-thioxohydrazine, N-
thioxopiperidine, and N-thioxoazepan-1-amines [30].
1,1-Dimethyl-2-thioxohydrazine forms low-melting
purple crystals. A lot of complexes of 1,1-dimethyl-
and 1,1-diphenylthioxohydrazines with such cоmpounds
as Pt(II) and Pd(II) dichlorides, triphenylphosphine
[31–34], and chromium pentacarbonyl, for example,
[(CH3)2NNS]Cr(CO)5 [35, 36], have been characterized.
RIx = RIn + (RIn+k – RIn) [f(tR,x) – f(tR,n)]/[f(tR,n+k) – f(tR,n)]. (1)
Here tR,x, tR,n, and tR,n+k are the retention times of the
analyte and reference components with the retention
indices RIn and RIn+k, f(tR) = tR + qlogtR. The parameter
q is calculated from the retention times of three
reference compound; to this end, it is more convenient
to use the simplest software (QBasic) [39].
As an example, we would like to describe the
recalculation of the retention times (Table 1) of the
reaction products of unsymmetrical dimethylhydrazine
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1108
ZENKEVICH et al.
Table 1. Recalculation of retention times to retention indices for the reaction products of 1,1-dimethylhydrazine with sulfur
(aqueous extract)a
tR, min
M/(m/z)100
Reaction product
Dimethyl disulfide
RIb (q –2.71)
5.9
9.4
94/94
120/76
115/44
123/76
126/126
90/90
730±9 (730±9)
815(811±15)
868 (868±2)
904
Bis(dimethylamino) sulfide
1,1,4,4-Tetramethylamidrazone
(Dimethylamino) methyl sulfide
Dimethyl trisulfide
11.3
12.5
14.1
15.6
15.9
18.6
19.6
20.6
21.6
23.7
24.3
25.9
952±10 (952±10)
999
1,1-Dimethyl-2-thioxohydrazine
N,N-Dimethylthioformamide
Bis(dimethylamino) disulfide
(Dimethylamino) methyl trisulfide
Naphthalene-d8
89/89
1008 (1004±7)
1095
152/44
155/76
136/136
158/79
184/42
129/129
187/76
1127
1160 (1160)
1193 (1191±6)
1264
Dimethyl tetrasulfide
Bis(dimethylamino) trisulfide
Dimethylaminoacetaldehyde dimethylhydrazone
(Dimethylamino) methy tetrasulfide
1284
1338
a
The data for compounds chosen as reference components for calculation of the retention indices of the other components (no less than
three) are printed bold. bParenthesized are the reference RI values.
with sulfur (wiping with water followed by dichloro-
methane extraction. Of 14 components one have to
choose those that are unambiguously identified by
mass spectra. This relates first of all to such well-
known compounds as dimethyl disulfide (the mean RI
on standard nonpolar polydimethylsiloxane phases is
730 ± 9) and dimethyl trisulfide (RI 952 ± 10). As the
third component we can choose the next polymer
homolog in this series (dimethyl tetrasulfide). For
quantitative analysis we added to this sample such a
readily detectable internal standard as naphthalene-d8
which could also be used as the reference component.
The mean retention index of naphthalene is 1163 ± 11.
Then for naphthalene-d8 we can take RI 1160, and the
RI of (CH3)2S4 (1191 ± 6) can be used for independent
control of the resulting data. The q value of –2.71,
calculated with the retention times of the reference
components, was used to calculate retention indices for
other components by Eq. (1).
which coincides, within error, with the reference RI
1191 ± 6 and provides evidence for the correctness of
the chosen algorithm of data treatment. The other
important issue to be commented upon is the extra-
polation of retention indices to the retention times
larger than the retention time of the last of the
reference components. Thus, the tR of naphthalene-d8
is 20.6 min (RI 1160) and the tR of (dimethylamino)
methyl tetrasulfide is 25.9 min, which corresponds to
RI 1338. The most reliable evidence for the reliability
of such data is the coincidence of the RIs of the same
components in different samples analyzed in different
conditions.
Table
2
shows analogous results of the
recalculation of retention times to retention indices for
the reaction products of compound I with sulfur in an
acetone solution, as well as the results of identification
of the products. For the reference compounds we chose
three dimethyl polysulfides (CH3)2Sn, 2 ≤ n ≤ 4 (q
–2.89). The main reference compound is acetone
dimethylhydrazone (RI 696 ± 4) formed by con-
densation of 1,1-dimethylhydrazine with acetone. The
table only shows the components with larger RI values.
Like in the previous case, the retention indices of
For each component in Table 1 we put retention
time, M/(m/z)100, and known reference retention
indices. Retention indices for seven identified
compounds are determined for the first time. The RI
value of dimethyl tetrasulfide was estimated at 1193,
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CHROMATOGRAPHIC COMPONENT OF IDENTIFICATION
1109
Table 2. Recalculation of retention times to retention indices for the reaction products of 1,1-dimethylhydrazine with sulfur
(acetone extract)a
tR, min
–
M/(m/z)100
100/56
94/94
Reaction product
Acetone dimethylhydrazone
Dimethyl disulfide
RIb (q –2.89)
(696±4)
5.8
730±9 (730±9)
751 (760±8)
777 (783±11)
814 (811±15)
822 (820±7)
862 (868±2)
900
6.8
92/91
Toluenec
7.9
98/55
4-Methylpent-3-en-2-onec
9.3
120/76
116/43
115/44
123/76
126/126
90/90
Bis(dimethylamino) sulfide
4-Hydroxy-4-methylpentan-2-onec
1,1,4,4-Tetramethylamidrazone
(Dimethylamino) methyl trisulfide
Dimethyl trisulfide
9.6
11.0
12.3
14.0
15.5
15.8
18.3
19.4
21.3
23.5
25.6
29.4
952±10 (952±10)
999
1,1-Dimethyl-2-thioxohydrazine
Dimethylthioformamide
89/89
1009 (1004±7)
1090
152/44
155/76
158/79
184/42
187/76
184/42
Bis(dimethylamino) disulfide
(Dimethylamino) methyl trisulfide
Dimethyl tetrasulfide
1127
1191±6 (1191±6)
1266
Bis(dimethylamino) trisulfide
Dimethylaminoacetaldehyde dimethylhydrazone
(Dimethylamino) methy tetrasulfide
1339
1472
a
The data for compounds chosen as reference components for calculation of the retention indices of the other components (no less than
three) are printed bold. b Parenthesized are the reference RI values. c Solvent admixtures and products of acetone condensation in the
presence of bases.
seven compounds are determined for the first time;
note that the resulting values are well consistent with
those in Table 1. Moreover, the results can be checked
out using the retention indices of admixtures,
specifically the products of intermolecular condensa-
tion of acetone in the presence of bases: 4-hydroxy-4-
methylpentan-2-one (diacetone alcohol, RI 822,
reference RI 820 ± 7) and 4-methylpent-3-en-2-one
(mesityl oxide, RI 777 and 783 ± 11, respectively). It is
noteworthy that the retention indices for 1,1-dimethyl-
2-thioxohydrazine in Tables 1 and 2 coincide with
each other (RI 999).
induces, we need not three but four reference com-
ponents and use in the calculations two triads of
reference compounds (Table 3).
The first set of references includes acetaldehyde
dimethylhydrazone (RI 675 ± 9), mesityl oxide (RI 783 ±
11), and tetramethyltetrazene (RI 831 ± 4), which
correspond to q 10.98. The second set includes two last
components of the first set and naphthalene-d8 (RI
1160, q –5.62). Such different q values (including their
different signs), do not, however, only slightly affect
RIs. As seen in the middle part of Table 3, the RI
values calculated with two different sets of reference
compounds differ from each other by as little as 1–2.
The transformation products of unsymmetrical
dimethylhydrazine, extracted from the shungite surface
with acetone (Table 3) are more diverse. In this case to
recalculate the retention times varying over a fairly
broad range (from 4.6 to 25.0 min) to retention
The resulting data allowed us to exclude wrong
variants of mass spectral identification and to correct
the other data. Thus, for example, the component with
tR 18.1 min (RI 990) was identified as acetaldehyde
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1110
ZENKEVICH et al.
Table 3. Recalculation of retention times to retention indices for the transformation products of 1,1-dimethylhydrazine on the
surface of shungite (acetone extract)a
RIb
tR, min
M/(m/z)100
Reaction product
Reference RI
q 10.98
q –5.62
4.6
6.0
88/88
86/42
100/56
74/74
73/73
–/43
Tetramethylhydrazine
Acetaldehyde dimethylhydrazone
Acetone dimethylhydrazone
Dimethyl-N-nitrosamine
Dimethylformamide
Not identified
627
675±9
696
–
614±21
–
–
675±9
696±4
708±5
749±16
–
6.7
–
–
–
7.8
726
9.5
769
9.7
774
10.1
10.4
10.8
11.2
11.6
11.9
12.0
12.3
13.7
18.1
18.7
19.2
19.6
21.4
22.2
23.4
24.8
25.0
98/83
97/97
96/96
97/96
96/96
116/43
112/56
116/116
115/44
–/99
4-Methyl-3-penten-2-onec
783±11
790
783±11
789
783±11
–
C5H7N3
1,3-Dmethyl-1Н-pyrazole, C4H8N2
C5H7N3
799
797
805±6
–
–
808
806
Dimethylpyrazole, C4H8N2
4-Hydroxy-4-methylpentan-2-onec
Acetone azine
816
815
823
822
820±7
828±7
825
824
Tetramethyltetrazene
Tetramethylamidrazone
Not identified
831±4
831±4
866
831±4
–
868±2
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
990
–/59
The same
1009
1024
1037
1094
1120
1160
1207
1214
–/43
''
–/43
''
–/43
''
–/58
''
136/136
142/44
–/97
Naphthalene-d8
1160
–
Ethanedial bis(dimethylhydrazone)
Not identified
–
a
The data for compounds chosen as reference components for calculation of the retention indices of the other components (no less than
three) are printed bold. b Calculated by two sets of reference compounds. c Solvent admixtures.
diethylhydrazone [4]. However, taking account of the
chromatographic invariants, we cannot accept this
assignment, because the reference RI of this compound
is 822 ± 5. The three components with tR 10.4–11.6
min (RI 790–816) have molecular masses of 96 and 97,
which allows these compounds to be assigned the
structures of dimethylpyrazoles and dimethyltriazoles
(the latter of these components was identified as 1,3-
dimethyl-1Н-pyrazole). However, the reference RI 805 ±
6 is better consistent with 1,3-dimethylpyrazole (RI
799, tR 10.8 min), whereas the peak at tR 11.6 min
probably belongs to 1,5-dimethylpyrazole. In view of
the lack of reference retention indices for dimethyl-
triazoles, we can do nothing more than specify their
molecular formulas С4H7N3.
The use of retention indices not only allows them to
be compared with reference data, but also makes
possible “secondary” control of the results, which is
especially important with new compounds. Among the
transformation products of unsymmetrical dimethyl-
hydrazine in the presence of sulfur we found three
series of compounds: dimethyl polysulfides СН3SnСН3,
(dimethylamino) methyl polysulfides (CH3)2NSnCH3,
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CHROMATOGRAPHIC COMPONENT OF IDENTIFICATION
1111
Table 4. Comparison of the increments to retention indices ΔRI(S) for dialkyl polysulfides СН3SnСН3, (dimethylamino)
methyl polysulfides (CH3)2NSnCH3, and bis (dimethylamino) polysulfides (CH3)2NSnN(CH3)2
n
СН3SnСН3
(CH3)2NSnCH3
(CH3)2NSnN(CH3)2
RI
ΔRI(S)
RI
ΔRI(S)
RI
ΔRI(S)
1
2
3
4
5
506±14а
661±12а
902±3
1127
1338
–
814±1
1092±4
1265±2
1472
730±9
224
222
241
225
211
–
279
173
207
–
952±10
1191±6
1408±11
239
217
–
Average ΔRI(S)
226±9
226±15
220±54
a Not detected in the samples. The data are given to calculate ΔRI(S).
and bis(dimethylamino) polysulfides (CH3)2NSnN(CH3)2
with 2 ≤ n ≤ 4. Previously [40] such polysulfides were
identified among the products of chemical destruction
of O-isobutyl S-(2-diethylaminoethyl)phosphono-
thioate. In all analogous cases, further evidence for the
correctness of structural assessment of analytes should
be provided. In our example, the variable structural
characteristic is the number of sulfur atoms in the
polysulfide bridge Sn; consequently, as the criterion of
correct structural assessment of such homologous
polymers we can take the increments of retention
indices, corresponding to one sulfur atom. As a result,
we obtain a data set (Table 4).
polydimethylsoloxane stationary phases is 998 ± 2; the
base peak in its mass spectrum belong to the molecular
ion [(m/z)100 90], which allows fairly reliable
interpretation of the isotope signals m/z 91 and 92 and
thus confirm the presence of sulfur in the molecule.
The fragment ions [M – (CH3)2N], m/z 90–44 = 46, are
assignable to the fragment [NS]+, which is evidence
for the presence of the dimethylamino group.
Consequently, the molecular formula C2H6N2S can be
considered established even without resorting to high-
resolution mass spectrometry. However, all the above
reasoning could be considered sufficient for
unambiguous structural assessment, provided among
the whole set of possible C2H6N2S isomers no other
structure meeting the same criteria is found. Therefore,
it is necessary to compare the characteristics of
C2H6N2S isomers, ten of which are presented in Table 5.
The mean increment ΔRI(S) for the series of
dimethyl polysulfides is 226 ± 9, which ideally
coincides with the value (226 ± 8) estimated
previously for any dialkyl polysulfide [41]. The value
of this increment for (dimethylamino) methyl poly-
sulfides is the same but its standard deviation is larger
(226 ± 15). And, finally, bis(dimethylamino) poly-
sulfides naturally have close ΔRI(S) values but the
scatter of data is even larger (220 ± 54). The coin-
cidence of ΔRI(S) implies that the three series of
compounds all correspond to the same type of
structural transformations of the molecules, namely
–S2– → –S3– → –S4– →… .
CAS numbers are known for six C2H6N2S isomers.
This fact implies not a high degree of knowledge of
these compounds but the research interest in them. Four
compounds (including dimethylthioxohydrazine) are
characterized by mass spectra. Some physicochemical
characteristics are known for only one C2H6N2S
isomer: N-methylthiourea. However, only four of the
ten isomers contain N–N or N=N bonds, and the
(CH3)2N fragment is present in dimethylthioxohyd-
razine and absent from the other isomers.
The above reasoning concerning the necessity of
providing further evidence for the structure of new
compounds relates in full measure to such trans-
formation product of unsymmetrical hydrazine in the
presence of sulfur and sulfur-containing materials as
1,1-dimethyl-2-thioxohydrazine. The mean retention
index of this compound on standard nonpolar
The retention index of dimethylthioxohydrazine is
impossible to estimate using additive schemes, because
until now no retention indices have been reported for
N=S compounds. However, to confirm the assignment
to the compound with RI 998 ± 2 and М/(m/z)100
=
90/90 of the (CH3)2NNS structure, we can consider
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ZENKEVICH et al.
Table 5. Comparison of the availability of data for certain possible С2Н6N2S isomers and presence of N–N and (CH3)2N
structural fragments in the molecules
Mass spectrum;
m/z (Irel, %)
Presence of
fragment
С2Н6N2S isomer
CAS number
598-52-7
Other data
N–N
(CH3)2N
–
–
–
–
–
–
N-Methylthiourea
90(100), 30
mp 118–121°С; рKа 0.83
Methyl carbamidothioate
N,N'-Dimethylsulfur diimide
Methyl(methylsulfanyl)diimide
(2-Aminoethane)thioamide
(2-Sulfanylethane)imidate
1,3,4-Thiadiazoline
2986-19-8 43(100), 90
–
–
–
–
–
–
–
13849-02-0 28(100), 61, 30, 62
–
–
–
–
–
–
+
–
–
–
–
–
105301-27-7
50433-21-1
39517-32-3
36712-81-9
–
+
–
–
–
1,2,4-Thiadiazoline
1,1-Dimethyl-2-thioxohydrazinea
90(100), 46, 42
–
+
+
+
–
Dimethyldiazene thioxide
–
–
a The melting point is higher than room temperature.
Table 6. Comparison of the retention indices of compounds with varied N−CH fragment
Structure
(CH3)2N−N=S
(CH3)2N−CH=S
ΔRI(N → CH)
RI
Structure
(CH3)2N−N=O
(CH3)2N−CH=O
RI
ΔRI(O → S)
+290
998±2а
1004±7
+6
708±5
749±16
+41
+255
a Checked value.
how the retention indices vary in going from dimethyl-
thioxohydrazine to dimethylthioformamide, dimethyl-
N-nitrosamine, and dimethylformamide. One can see
without calculations that the retention indices of
compounds with varied CH–N fragment are fairly
close to each other (Table 6).
The chromatographic retention indices of new
compounds, determined for the first time, can be
included into the corresponding databases and used for
identification of these compounds.
EXPERIMENTAL
Such analogy allows the retention index of dimethyl-
thionitrosamine to be estimated by the following
scheme.
Spiking soils with unsymmetrical dimethylhyd-
razine, preparation of the reaction mixtures, and
sample preparation for analysis were performed as
described in [1, 3, 4]. The GCMS analysis was
performed on a JMS-D300 mass spectrometer coupled
with a НР 5890 gas chromatograph. Chromatography
conditions: DB-5 quartz capillary column (30 m ×
0.5 mm × 0.25 µm); temperature program: initial 30°С
(hold 4 min), ramp rate 5–12 deg/min, final 300°С
(hold 5–10 min); injector temperature 280°С, split
ratio 1 : 6, carrier gas helium (5 mL/min). Mass
(CH3)2N–N=O + (CH3)2N–CH=S – (CH3)2N–CH=O
= (CH3)2N–N=S,
(708 ± 5) + (1004 ± 7) – (749 ± 16) = 963 ± 18.
This estimate coincides, even though not very
exactly (within two standard deviations), with the
experimental RI value of 998 ± 2, which is quite
acceptable for previously unknown compounds.
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CHROMATOGRAPHIC COMPONENT OF IDENTIFICATION
1113
spectrometry conditions: ionizing energy 70 eV,
accelerating voltage 3 kV, mass range from m/z 10–40
to 450–650, ion source temperature 130–170°С.
Identification was performed using WILEY275,
NBS75K, and NIST98 databases or considering the
principal regularities of mass spectral fragmentation of
organic compounds [42].
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(30) [М – СН3]+, 58 (4), 56 (6), 47 (4), 46 (16) [М –
(CH3)2N]+, 44 (10) [C2H6N]+, 43 (25), 42 (39), 41 (6).
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