Transformations of N-ethylamines into amide derivatives under the action of sulfur monochloride

Article abstract of DOI:10.1007/s11172-007-0179-9

Tertiary N-ethylamines were converted into amide derivatives by reactions with sulfur monochloride and DABCO at 0 °C. Depending on the nature of the substituents in the amine, the reaction can be accompanied by unexpected transformations.

Full text of DOI:10.1007/s11172-007-0179-9

Russian Chemical Bulletin, International Edition, Vol. 56, No. 6, pp. 1178—1183, June, 2007
1178
Transformations of Nꢀethylamines into amide derivatives
under the action of sulfur monochloride
L. S. Konstantinova, A. A. Berezin, and O. A. Rakitinꢀ
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5328. Eꢀmail: orakitin@ioc.ac.ru
Tertiary Nꢀethylamines were converted into amide derivatives by reactions with sulfur
monochloride and DABCO at 0 °C. Depending on the nature of the substituents in the amine,
the reaction can be accompanied by unexpected transformations.
Key words: sulfur monochloride, tertiary amines, dichloroacetamides, 1,2ꢀdithiolꢀ3ꢀones.
Reactions of Nꢀsubstituted diisopropylamines, espeꢀ
cially commercial and inexpensive NꢀethylꢀN,Nꢀdiisoꢀ
propylamine (1a) (Hünig base), with sulfur monochloride
have been intensively studied by us for more than 10 years.
It was believed for a long period of time that such reacꢀ
tions involve only the isopropyl groups of these comꢀ
pounds, which allowed the synthesis of complex S,Nꢀconꢀ
taining heterocycles, e.g., bis[1,2]dithiolo[1,4]thiazines,1
bis[1,2]dithiolopyrroles,2 and bis[1,2]dithiolylamines.3 In
our further investigations in this field, we found the conꢀ
ditions for the reaction to stop at the formation of monoꢀ
cyclic 1,2ꢀdithioles.4 Tests of these compounds for antiꢀ
cancer activity at the US National Cancer Institute have
revealed their appreciable effects against certain types of
cancer.5
Recently,6 we have demonstrated that the pathway of
the reaction of Hünig base 1a with S2Cl2 and 1,4ꢀdiꢀ
azabicyclo[2.2.2]octane (DABCO) dramatically changes
at a lower temperature (0 °C) so that the transformation
selectively occurs at the Nꢀethyl group to give N,Nꢀdiꢀ
isopropyldichloroacetamide (2), the isopropyl groups reꢀ
maining intact (Scheme 1).
Here we studied reactions of tertiary amines containꢀ
ing ethyl or βꢀsubstituted ethyl groups with sulfur monoꢀ
chloride and the influence of the structures of the starting
reagents on the reaction outcome.
Results and Discussion
A study of a reaction of NꢀethylꢀN,Nꢀdiisopropylamine
(1a) with S2Cl2 and DABCO in chloroform (Scheme 2)
and an analysis of the previous results (Table 1) showed
that amide 2 is formed on keeping the reaction mixꢀ
ture at 0 °C. At room temperature, tricyclic bis[1,2]diꢀ
thiolo[1,4]thiazines 4 were the major reaction products,
while at –20 °C, the reaction proceeded slowly to give
dithiolothiazines 5 and 6 in low yields. The amounts of
S2Cl2 and DABCO have no substantial effect on the reacꢀ
tion pathway; with an increase in their amounts, the yield
of amide 2 decreased only slightly. Selected data on optiꢀ
mization of the synthesis of amide 2 from the Hünig base
are given in Table 1.
Scheme 2
Scheme 1
i. 1) S2Cl2, DABCO; 2) HCO2H.
The discovered transformation of the Nꢀethyl group
into a dichloroacetamido one has not been documented
hitherto and opens up new possibilities for functionalizaꢀ
tion of Nꢀalkyl groups in compounds that can be of interꢀ
est for fine organic synthesis.
X = Y = O (4); X = S, Y = O (5); X = Y = S (6)
The best conditions for the synthesis of amide 2 are as
follows: chloroform as a solvent, 0 °C, 3 days, further
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1135—1140, June, 2007.
1066ꢀ5285/07/5606ꢀ1178 © 2007 Springer Science+Business Media, Inc.

Dichloroacetamides from tertiary Nꢀethylamines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
1179
Table 1. Conditions (amounts of the reagents and the reaction
temperature) and the yields of the products for the reaction of
Hünig base 1a with S2Cl2 and DABCO
and inert to electrophilic species. For instance, N,Nꢀdiꢀ
isopropyldichloroacetamide (2) is inert in the reaction
with S2Cl2 and DABCO even at room temperature. Earꢀ
lier,1 we have shown that neither Nꢀacetylꢀ nor Nꢀcyaꢀ
no(diisopropyl)amines reacts with S2Cl2 under analogous
conditions.
Entry
Amounts of the
reagents*/mmol
T
Yields of the reaction
products (%)
/°C
Possible selective formation of iminium ion 7 rather
than its isomer 8 has been illustrated7 with oxidation of
Hünig base 1a with trifluoroacetic anhydride in CH2Cl2
at 0 °C; no products of the oxidation of the isopropyl
group were detected.
Thus, our study revealed that the reaction of the Hünig
base with S2Cl2 and DABCO at 0 °C involves the ethyl
group to give dichloroacetyl derivative 2, while at room
temperature, the isopropyl group transformation leads to
1,2ꢀdithioles.
S2Cl2 DABCO
2
3
4
5
6
1 1
2 3
3
4
5
10
8
10
6
20
20
20
0
0
0
—
—
19
41
34
—
10
—
—
—
42
8
—
—
—
—
—
20
—
—
—
11
—
—
—
—
—
—
6
5
5
5
5
7
7
6
7
10
5
5
5
12 17 20
—
–20
—
—
* Per millimole of compound 1a.
Since analogous transformations of the Nꢀethyl group
have not been documented, in a search for an area of
their application we studied reactions of a number of
Nꢀ(2ꢀRꢀethyl)ꢀN,Nꢀdiisopropylamines with S2Cl2 and
DABCO under the conditions of the synthesis of amide 2.
It turned out that the reaction outcomes substantially
depend on the nature of the substituent R and that the
reactions can be complicated by unexpected rearrangeꢀ
ments.
A reaction of Nꢀ(2ꢀchloroethyl)ꢀN,Nꢀdiisopropylꢀ
amine (1b) with S2Cl2 and DABCO at 0 °C followed by
treatment with formic acid gave two products: dichloroꢀ
acetyl derivative 2 and 1,2ꢀdithiolꢀ3ꢀone 11b (Scheme 4).
Note that the corresponding dithiolone 11a was not deꢀ
tected among the products obtained from Hünig base 1a
under analogous conditions.
treatment with formic acid. The yield of product 2
was 41%.
Apparently, the key step of the reaction is oxidation of
the tertiary amine with S2Cl2 into iminium ion 7 or 8
(Scheme 3). The final reaction outcome (formation of
compounds 3—6 or amide 2) depends on which of the
ions (7 or 8) will have a higher concentration under the
reaction conditions. At 0 °C, the conditions seem to be
more favorable for oxidative abstraction of the sterically
less blocked αꢀH atom of the ethyl group rather than the
proton of the isopropyl group; this process yields kinetiꢀ
cally controlled iminium ion 7 rather than more stable
ion 8. Ion 7 probably undergoes a transformation into
enamine 9, which then oxidizes to give tetrachloride 10.
The latter is transformed in the presence of formic acid
into the final amide 2 (see Scheme 3). Apparently, the
isopropyl groups in intermediates 7—10 are deactivated
Obviously, the chloroethyl group in amine 1b oxidizes
like the ethyl group but the oxidation rate is lower, which
Scheme 3

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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Konstantinova et al.
Scheme 4
the presence of palladium catalysts or bromine trifluoride.
However, no transformation of the azidoethyl group into
a C(O)CN group has been observed hitherto. The formaꢀ
tion of this compound can be explained in terms of the
general mechanism (see Scheme 3) by elimination of a
nitrogen molecule from an intermediate (most likely, 14)
followed by formation of a triple CN bond (see Scheme 6).
Scheme 6
i. 1) S2Cl2, DABCO, 0 °C; 2) HCO2H.
allows the isopropyl group to participate in a competitive
reaction leading to dithiolone 11b. Based on the reaction
mechanism (see Scheme 3) and the results summarized in
Table 1, we concluded that the transformation of the
isopropyl group should be favored by an increased reacꢀ
tion temperature, while the formation of dichloroacetꢀ
amide, by the lowered temperature. This was additionꢀ
ally confirmed by the reaction of amine 1b with S2Cl2
and DABCO in boiling chloroform, giving a mixture
of bis[1,2]dithiolo[1,4]thiazines8 (although in low
yields), while compound 2 was detected only in trace
amounts (TLC). An analogous reaction at –20 °C selecꢀ
tively afforded dichloroacetamide 2; however, its yield
was low (12%).
Nꢀ(2ꢀPhthalimidoethyl)diisopropylamine (1c) reacted
like chloro analog 1b to give chloroacetamide 12 and
dithiolone 11c, respectively, in virtually the same yields
(Scheme 5).
i. 1) S2Cl2, DABCO, 0 °C; 2) HCO2H.
The formation of cyanoformamide 13 from azidoethyl
derivative 1d prompted us to use NꢀcyanomethylꢀN,Nꢀ
diisopropylamine 15 in the reaction with S2Cl2 and
DABCO. We expected that the same compound 13 would
be obtained, possibly in a higher yield. However, along
with dithiolone 17 (20%), we isolated from the reaction
mixture cyanothioformamide 16 (24%). The formation of
compound 16 instead of carboxamide 13 suggested an
alternative mechanism of the reaction with S2Cl2, probꢀ
ably, because of the presence of the cyano group in the
starting amine 15. Apparently, in this case, S2Cl2 adds to
the activated methylene group to give S—S—Cl derivaꢀ
tive 18 (analogous addition has been described earlier10),
which is followed by elimination of an S atom and an HCl
molecule (Scheme 7).
Scheme 5
The possibility of this reaction pathway for acetoniꢀ
trile derivatives was indirectly confirmed by a reaction of
Nꢀ(2ꢀcyanoethyl)ꢀN,Nꢀdiisopropylamine (1e) with S2Cl2
and DABCO at 0 °C. Apart from chlorodithiolone 11e
(24%), we isolated a yellow crystalline product. Its moꢀ
lecular formula (C18H30N4S4) was assigned from elemenꢀ
tal analysis data and mass spectra; 1H and 13C NMR
spectra provide evidence for dimer 19 (Scheme 8).
Alternative structure 19´ is possible for compound 19;
however, the calculated data of the 13C NMR spectra are
closer to the parameters of structure 19. A plausible route
i. 1) S2Cl2, DABCO, 0 °C; 2) HCO2H.
Reactions of Nꢀ(2ꢀazidoethyl)diisopropylamine (1d)
with S2Cl2 and DABCO at 0 °C also gave dithiolone 11d
as the result of a transformation at the isopropyl group.
The ethyl group is also involved but the product was
cyanoformyl derivative 13 rather than the expected
azidoacetyl one (Scheme 6). It is known9 that the azidoꢀ
methyl group can be transformed into a cyano group in

Dichloroacetamides from tertiary Nꢀethylamines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
1181
Scheme 7
Scheme 9
i. 1) S2Cl2, DABCO, 0 °C; 2) HCO2H.
Scheme 8
R = CO2Et (f), SPh (g), SO2Ph (h)
In summary, we found that the reactions of
Nꢀ(2ꢀRꢀethyl)ꢀN,Nꢀdiisopropylamines with S2Cl2 and
DABCO at 0 °C, in contrast to an analogous reaction of
the Hünig base, not always yield dichloroacetamides; in
some cases, the isopropyl group also undergoes a transꢀ
formation leading to 1,2ꢀdithiolones. That is why we tried
to use in the reactions with S2Cl2 other tertiary diꢀ
ethylamines: N,NꢀdiethylꢀNꢀisopropylamine (20) and triꢀ
ethylamine. Under appropriate conditions, dichloroꢀ
acetamide 21 was obtained from N,NꢀdiethylꢀNꢀisoꢀ
propylamine in 34% yield. Moreover, even if the reaction
was carried out at room temperature for three days, only
the ethyl group was involved and the yield of acetamide
21 increased to 54% (Scheme 10).
Scheme 10
to product 19 involves an attack of S2Cl2 on the αꢀC atom
with respect to the cyano group in compound 1e (as shown
in Scheme 7) followed by addition of another amine molꢀ
ecule and formation of a dimer via an S—S bridge. Then
two thiocarbonyl groups will form according to the mechaꢀ
nism described for compound 16.
Reactions of S2Cl2 with other substituted diisopropylꢀ
amines containing ethoxycarbonylethyl (1f), phenylthioꢀ
ethyl (1g), and phenylsulfonylethyl groups (1h) gave unꢀ
der analogous conditions 1,2ꢀdithiole derivatives in yields
up to 70% (Scheme 9).
To obtain dithiolone 11h from phenylsulfonyl derivaꢀ
tive 1h, a fivefold excess of formic acid is quite sufficient
for the conversion of a dithiolium salt into dithiolone and
quenching of the excess of S2Cl2. A greater excess of
HCO2H leads to nucleophilic displacement of the sulfoꢀ
nyl group to give formyloxy dithiolone 11i.
Room temperature was also an optimum for a reaction
of S2Cl2 and DABCO with triethylamine, which contains
no isopropyl groups; the yield of dichloroacetamide 22
was 51%. However, with a decrease in the reaction temꢀ
perature, the yield of amide 22 gradually declined to trace
amounts. At –10 °C, the major product was trichloroacetyl
derivative 23 (23%) (Scheme 11). The transformation of
the Nꢀethyl group into the N—C(O)CCl3 group has not
been documented hitherto, as well. The formation of
trichloroacetamide 23 in the chlorination of the ethyl
group in triethylamine can be explained by diminꢀ

1182
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Konstantinova et al.
J = 6.6 Hz); 3.35 (sept, 1 H, CHMe2, J = 6.6 Hz); 3.35, 3.70
(both t, 2 H each, 2 CH2, J = 6.6 Hz); 7.70, 7.83 (both m,
2 H each, Ar). 13C NMR (CDCl3), δ: 21.33 (2 Me); 37.54,
54.27 (2 CH2); 42.54 (CHMe2); 123.13, 133.89 (4 CHAr);
132.17, 137.28, 153.08, 168.17, 187.66 (5 C quaternary). MS (EI,
70 eV), m/z (Irel (%)): 382 [M]+ (11), 222 (91), 180 (100),
130 (46). IR (KBr), ν/cm–1: 2908 (C—H); 1768, 1652 (C=O);
720 (C—Cl).
ished steric hindrances compared to the Hünig base and
N,NꢀdiethylꢀNꢀisopropylamine.
Scheme 11
5ꢀChloroꢀ4ꢀ{NꢀisopropylꢀNꢀ[2ꢀ(phenylthio)ethyl]amino}ꢀ
3Hꢀ1,2ꢀdithiolꢀ3ꢀone (11g). The yield was 72%, a yellow oil.
Found (%): C, 48.23; H, 4.52; N, 4.32. C14H16ClNOS3. Calcuꢀ
lated (%): C, 48.61; H, 4.66; N, 4.05. 1H NMR (CDCl3), δ: 1.10
(d, 6 H, (CH3)2CH, J = 6.6 Hz); 2.89, 3.34 (both t, 2 H each,
2 CH2, J = 6.6 Hz); 3.39 (sept, 1 H, CHMe2, J = 6.6 Hz); 7.20
(m, 3 H, Ph); 7.29 (m, 2 H, Ph). 13C NMR (CDCl3), δ: 21.72
(2 Me); 33.45, 45.64 (2 CH2); 53.69 (CHMe2); 126.05 (CHPh);
128.99 (2 CHPh); 129.19 (2 CHPh); 130.99, 136.21, 154.19,
187.70 (4 C quaternary). MS (EI, 70 eV), m/z (Irel (%)): 345
i. 1) S2Cl2, DABCO, ~20 °C; 2) HCO2H.
ii. 1) S2Cl2, DABCO, –10 °C; 2) HCO2H.
Experimental
[M]+ (15), 222 (100), 180 (98), 109 (50). IR (KBr), ν/cm–1
:
1
H NMR spectra were recorded on Bruker WMꢀ250 and
2968, 2924 (C—H); 1728, 1664 (C=O); 740 (C—Cl).
Bruker AMꢀ300 instruments (250 and 300 MHz, respectively) in
CDCl3. Chemical shifts are given on the δ scale with reference
to Me4Si. Melting points were determined on a Kofler instruꢀ
ment and are given uncorrected. Mass spectra were recorded on
a Finnigan MAT INCOS 50 instrument (EI).
5ꢀChloroꢀ4ꢀ{NꢀisopropylꢀNꢀ[2ꢀ(phenylsulfonyl)ethyl]amiꢀ
no}ꢀ3Hꢀ1,2ꢀdithiolꢀ3ꢀone (11h). The yield was 67%, a yellow
oil. Found (%): C, 44.26; H, 4.14; N, 3.98. C14H16ClNO3S3.
Calculated (%): C, 44.49; H, 4.27; N, 3.71. 1H NMR (CDCl3),
δ: 1.04 (d, 6 H, (CH3)2CH, J = 6.6 Hz); 3.18, 3.39 (both t,
2 H each, 2 CH2, J = 6.6 Hz); 3.49 (sept, 1 H, CHMe2, J =
6.6 Hz); 7.63 (m, 3 H, Ph); 7.88 (d, 2 H, Ph, J = 7.9 Hz).
13C NMR (CDCl3), δ: 21.61 (2 Me); 45.78, 54.00 (2 CH2);
63.58 (CHMe2); 125.17 (2 CHPh); 129.02 (2 CHPh); 132.17
(CHPh); 133.84, 137.54, 154.28, 187.55 (4 C quaternary).
MS (EI, 70 eV), m/z (Irel (%)): 377 [M]+ (4), 262 (3), 235 (13),
222 (47), 180 (74), 125 (49), 97 (30), 77 (100), 51 (64), 43
(100). IR (KBr), ν/cm–1: 2968, 2928 (C—H); 1660 (C=O);
756 (C—Cl).
The starting substituted diisopropylamines 1c,11 1d,4 1e,12
1f,13 and 1g 8 were prepared as described earlier.
N,NꢀDiisopropylꢀNꢀ[2ꢀ(phenylsulfonyl)ethyl]amine (1h) was
prepared from Nꢀ(2ꢀchloroethyl)ꢀN,Nꢀdiisopropylamine and
sodium benzenesulfinate in THF at ~20 °C. The yield was 86%,
a yellow oil. Found (%): C, 62.74; H, 8.72; N, 5.03.
C14H23NO2S. Calculated (%): C, 62.42; H, 8.61; N, 5.20.
1H NMR (CDCl3), δ: 0.93 (d, 12 H, 4 Me, J = 6.6 Hz); 2.63 (t,
2 H, CH2, J = 5.9 Hz); 2.92 (sept, 2 H, 2 CHMe2, J = 6.6 Hz);
3.56, 3.90 (both m, 1 H each, CH2S); 7.54 (m, 3 H, Ph); 7.73
(m, 2 H, Ph). 13C NMR (CDCl3), δ: 20.97 (4 Me); 35.21, 45.37
(2 CH2); 49.17 (2 CH); 125.75 (CHPh); 128.86 (2 CHPh); 129.12
(2 CHPh); 139.94 (CSPh). MS (EI, 70 eV), m/z (Irel (%)):
5ꢀChloroꢀ4ꢀ{Nꢀ[2ꢀ(formyloxy)ethyl]ꢀNꢀisopropylamino}ꢀ
3Hꢀ1,2ꢀdithiolꢀ3ꢀone (11i). The yield was 45%, a yellow oil.
Found (%): C, 38.18; H, 4.25; N, 4.73. C9H12ClNO3S2. Calcuꢀ
lated (%): C, 38.36; H, 4.29; N, 4.97. 1H NMR (CDCl3), δ: 1.11
(d, 6 H, (CH3)2CH, J = 6.6 Hz); 3.37 (sept, 1 H, CHMe2, J =
6.6 Hz); 3.39, 4.09 (both t, 2 H each, 2 CH2, J = 5.9 Hz); 8.00
(s, 1 H, C(O)H). 13C NMR (CDCl3), δ: 21.65 (2 Me); 44.77,
54.13 (2 CH2); 54.3 (CHMe2); 137.56, 154.72 (2 C quaternary);
160.86 (C(O)H); 187.66 (C=O). MS (EI, 70 eV), m/z (Irel (%)):
269 [M]+ (3), 254 (23), 212 (17), 114 (100). IR (KBr), ν/cm–1
:
2970 (C—H).
Reactions of substituted diisopropylamines 1 with S2Cl2 and
DABCO (general procedure). A solution of S2Cl2 (0.4 mL,
5 mmol) in chloroform (5 mL) was added dropwise at –40 to
–45 °C to a solution of amine 1 (1 mmol) and DABCO (0.55 g,
5 mmol) in chloroform (20 mL). The mixture was left at 0 °C for
72 h and then HCO2H (3.75 mL, 100 mmol) was added dropwise
at 0 °C. The mixture was slowly warmed to ~20 °C, refluxed
for 1 h, and filtered on cooling. The precipitate was washed with
CH2Cl2. The filtrate was concentrated under reduced pressure
and the residue was chromatographed on Merck 60 silica gel
with CH2Cl2—light petroleum as an eluent.
The spectroscopic characteristics of substituted 3Hꢀ1,2ꢀ
dithiolꢀ3ꢀones 11b,d,e,f are analogous to those cited earlier.4,11
The properties of dichloroacetamides 2,14 21,15 and 22,16
trichloroacetamide 23,17 and compounds 13 18 and 15 19 are
identical with the literature data.
281 [M]+ (18), 222 (18), 180 (41), 73 (100). IR (KBr), ν/cm–1
:
2986, 2928 (C—H); 1728, 1656 (C=O); 736 (C—Cl).
N,NꢀDiisopropylꢀ2ꢀchloroꢀ2ꢀ(1,3ꢀdioxoꢀ1,3ꢀdihydroꢀ
2Hꢀisoindolꢀ2ꢀyl)acetamide (12). The yield was 22%, m.p.
160—162 °C. Found (%): C, 59.36; H, 5.72; N, 8.88.
C16H19ClN2O3. Calculated (%): C, 59.54; H, 5.93; N, 8.68.
1H NMR (CDCl3), δ: 1.38, 1.41 (both d, 6 H each, 2 (CH3)2CH,
J = 5.9 Hz); 3.43, 3.98 (both sept, 1 H each, 2 CHMe2, J =
5.9 Hz); 6.61 (s, 1 H, CHCl); 7.76, 7.90 (both m, 2 H each, Ar).
13C NMR (CDCl3), δ: 19.87, 19.93 (4 Me); 46.88, 49.40
(2 CHMe2); 59.01 (CHCl); 124.08, 134.73 (2 CHAr); 131.52
(1 C quaternary); 160.59, 165.58 (2 C=O). MS (EI, 70 eV),
m/z (Irel (%)): 322 [M]+ (1), 287 (2), 222 (2), 194 (20), 128 (82),
86 (95), 43 (100). IR (KBr), ν/cm–1: 2930 (C—H); 1680 (C=O);
730 (C—Cl).
2ꢀ{2ꢀ[Nꢀ(5ꢀChloroꢀ3ꢀoxoꢀ3Hꢀ1,2ꢀdithiolꢀ4ꢀyl)ꢀNꢀisopropylꢀ
amino]ethyl}ꢀ1Hꢀisoindoleꢀ1,3(2H)ꢀdione (11c). The yield
was 33%, m.p. 104—106 °C. Found (%): C, 50.32; H, 4.06;
N, 7.13. C16H15ClN2O3S2. Calculated (%): C, 50.19; H, 3.95;
N, 7.32. 1H NMR (CDCl3), δ: 1.11 (d, 6 H, (CH3)2CH,
N,NꢀDiisopropylꢀ2ꢀcyanothioacetamide (16). The yield
was 24%, yellow crystals, m.p. 75—78 °C. Found (%): C, 62.28;
H, 9.23; N, 18.36. C8H14N2S. Calculated (%): C, 62.31; H, 9.15;

Dichloroacetamides from tertiary Nꢀethylamines
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
1183
1
N, 18.17. H NMR (CDCl3), δ: 1.35, 1.57 (both d, 6 H each,
N. V. Obruchnikova, O. A. Rakitin, C. W. Rees, and
T. Torroba, J. Chem. Soc., Perkin Trans. 1, 2000, 3421.
3. S. Barriga, L. S. Konstantinova, C. F. Marcos, O. A. Rakitin,
C. W. Rees, T. Torroba, A. J. P. White, and D. J. Williams,
J. Chem. Soc., Perkin Trans. 1, 1999, 2237.
4 Me, J = 6.2 Hz); 4.26 (br.s, 2 H, 2 CH). 13C NMR (CDCl3),
δ: 18.53, 21.42 (2 Me); 51.86 (CH); 113.02 (CN); 163.74 (C=S).
MS (EI, 70 eV), m/z (Irel (%)): 170 [M]+ (87), 127 (86), 113
(14), 101 (43). IR (KBr), ν/cm–1: 2980 (C—H); 2150 (CN).
Highꢀresolution MS, found: m/z 170.0879 [M]+. C8H14N2S.
Calculated: M = 170.0878.
4. L. S. Konstantinova, O. A. Rakitin, and C. W. Rees,
Mendeleev Commun., 2001, 165.
[Nꢀ(5ꢀChloroꢀ3ꢀoxoꢀ3Hꢀ1,2ꢀdithiolꢀ4ꢀyl)ꢀNꢀisopropylamiꢀ
no]acetonitrile (17). The yield was 20%, a yellow oil. Found (%):
C, 38.39; H, 3.42; N, 11.48. C8H9ClN2OS2. Calculated (%):
C, 38.63; H, 3.65; N, 11.26. 1H NMR (CDCl3), δ: 1.12 (d, 6 H,
2 Me, J = 6.6 Hz); 3.51 (q, 1 H, CH, J = 6.5 Hz); 4.01 (s, 2 H,
CH2). 13C NMR (CDCl3), δ: 21.17 (Me); 35.93 (CH2); 53.59
(CH); 117.15 (CN); 136.12, 155.97, 187.17 (C=O, 2 C quaterꢀ
nary). MS (EI, 70 eV), m/z (Irel (%)): 248 [M]+ (74), 233 (47),
206 (61), 179 (33). IR (KBr), ν/cm–1: 2980 (C—H); 2140 (CN);
1660 (C=O). Highꢀresolution MS, found: m/z 247.9864 [M]+.
C8H9ClN2OS2. Calculated: M = 247.9845.
Bis(1ꢀcyanoꢀ2ꢀdiisopropylaminoꢀ2ꢀthioxoethyl) disulfide (19).
The yield was 22%, yellow crystals, m.p. 124—126 °C.
Found (%): C, 49.95; H, 7.00; N, 12.75; S, 29.96. C18H30N4S4.
Calculated (%): C, 50.19; H, 7.02; N, 13.01; S, 29.78. 1H NMR
(CDCl3), δ: 1.28 (d, 24 H, (CH3)2CH, J = 6.6 Hz); 3.66, 4.79
(both br.s, 2 H each, CHMe2); 6.61 (s, 2 H, CHCN). 13C NMR
(CDCl3), δ: 20.72, 23.40 (2 Me); 47.61, 49.67 (2 CHMe2);
64.85 (CHCN); 120.57 (CN); 153.96 (C=S). MS (EI, 70 eV),
m/z (Irel (%)): 366 [M – S2]+ (22), 334 (20), 183 (100), 141
(100). IR (KBr), ν/cm–1: 2930 (C—H); 2180 (CN); 1580; 1300.
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Received April 24, 2007;
in revised form June 8, 2007