Phenylenediamine and 4,4′-diaminodiphenyls in cyclothiomethylation with CH2O and H2S

Article abstract of DOI:10.1134/S107036321404015X

Cyclothiomethylation of o-phenylenediamine with CH₂O and H ₂S gives rise to 1,2,4,5-tetrahydrobenzo[d][1,3,6]thiadiazepine and 1,2,6,7-tetrahydrobenzo[f][1,3,5,8]dithiadiazonine, whereas m-phenylenediamine forms benzothiaza macrohete

Full text of DOI:10.1134/S107036321404015X

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 4, pp. 693–699. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © G.R. Khabibullina, V.R. Akhmetova, R.V. Kunakova, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 4, pp. 614–
620.
Phenylenediamine and 4,4'-Diaminodiphenyls
in Cyclothiomethylation with СН2О and Н2S
G. R. Khabibullinaa, V. R. Akhmetovaa, and R. V. Kunakovab
a Institute of Petrochemistry and Catalysis, Russian Avademy of Sciences,
pr. Oktyabrya 141, Ufa, Bashkortostan, 450075 Russia
е-mail: ink@anrb.ru
b Ufa State Academy of Economy and Service, Ufa, Bashkortostan, Russia
Received July 15, 2013
Abstract―Cyclothiomethylation of о-phenylenediamine with CH2O and H2S gives rise to 1,2,4,5-
tetrahydrobenzo[d][1,3,6]thiadiazepine and 1,2,6,7-tetrahydrobenzo[f][1,3,5,8]dithiadiazonine, whereas m-phe-
nylenediamine forms benzothiaza macroheterocycles of various structure, comprising 4–8 molecules of the
starting diamine, formaldehyde, and hydrogen sulfide. 4,4'-Diaminodiphenyls give bis(1,3,5-dithiazinanes),
along with oligomeric hetero(N,S,O)atomic compounds.
Keywords: benzothiaza macroheterocycles, phenylenediamines, multicomponent condensation, thiomethyla-
tion, bisdithiazinanes
DOI: 10.1134/S107036321404015X
According to [1–4], cyclothiomethylation of
aliphatic and aromatic primary amines, as well as
amides of carboxylic acids [5, 6] with СН2О and Н2S
gives rise to the corresponding 1,3,5-dithiazinanes; but
with functionally substituted anilines, benzothiaza
macroheterocycles were obtained [3, 4]. Hydrazines
[7, 8] and aliphatic α,ω-diamines [9, 10] form con-
densed bicycles or bis(1,3,5-dithiazinanes), depending
on cyclothiomethylation conditions. As known, aryl-
containing hetero(N,S,O)atomic compounds, including
macrocycles, hold promise as photochromic molecular
sensors for metal analysis [11, 12].
With the aim to synthesize a new class of nitrogen-
and sulfur-containing heterocycles and explore the
possibility to involve in cyclothiomethylation the above-
mentioned aromatic amines, we have studied intra- and
intermolecular reactions of the latter with СН2О and Н2S.
It was found that о-phenylenediamine (I) enters
multicomponent intramolecular condensation with
СН2О and H2S to form a complex mixture of hetero-
atomic compounds, including 1,2,4,5-tetrahydrobenzo-
[d][1,3,6]thiadiazepine (II), 1,2,6,7-tetrahydrobenzo[f]-
[1,3,5,8]dithiadiazonine (III), 1Н-1,3-benzimidazole
(IV), N,N'-dimethylene-1,2-phenylenediamine (V), and
1,2,4-trithiolane (VI) (Scheme 1). The mixture of
compounds II–V was separated by column chromato-
graphy on SiO2. The structure of heterocycles II and
III was established by spectral methods.
Before our research, cyclothiomethylation of
isomeric phenylenediamines and 4,4'-diamino-
diphenyls and their derivatives with СН2О and Н2S has
never been reported.
Scheme 1.
H
N
CH2
HN
NH2
NH2
S
S
N
N
S
S
a
b
CH2O−H2S
f
d
S
a
+
+
+
+
CH2
(6 : 4)
S
e
N
H
c
HN
N
N
H
b
c
d
I
IV
V
II
III
VI
Сyclothiomethylation of o-phenylenediamine with CH2O and H2S.
693

694
KHABIBULLINA et al.
Effect of reaction temperature and starting reagent ratio on
the yield and composition of о-phenylenediamine (I) cyclo-
thiomethylation products
methylation reaction of compound I involves both its
NH2 groups. As seen from the table, in our experi-
mental conditions the main reaction was, as a rule,
heterocycle II, and, therewith, its yield increased to
40% as the reaction temperature was increased (40–
70°С). At higher temperatures, along with compounds
II and III, we observed formation of poorly soluble
oligomeric heteroatomic compounds. The nine-
membered N,S-heterocycle III could be prepared in
low yield, and the best yield (16%) was obtained at a
1 : 3 : 2 reagent ratio (see table).
Yield of reaction products (wt %)
T,
I : CH2O : H2S
ratio
°С
II
III
IV
V
VI
0
20
40
0
20
40
20
70
1 : 2 : 1
1 : 2 : 1
1 : 2 : 1
1 : 3 : 2
1 : 3 : 2
1 : 3 : 2
1 : 6 : 4
1 : 6 : 4
35
32
40
18
26
41
35
42
4
4
3
16
12
16
10
7
10
13
19
27
23
11
13
14
16
18
10
10
8
11
15
18
3
3
7
2
2
1
6
6
Cyclothiomethylation of m-phenylenediamine (VII)
with СН2О and H2S at a 1 : 3 : 2 reagent ratio and 0°С
gave macroheterocycle VIII (yield 99%) as the result
of intermolecular heterocyclization with the oligomeri-
zation degree nav = 8. As the temperature was increased
(20–70°С), an exclusive reaction product was three-
membered oligomer IX with nav = 4–5 (yield 91–99%)
(Scheme 2).
The mass spectra of compounds II and III contain
strong molecular ion peaks [М]+ at m/z 166 and 212,
respectively. The 1Н and 13С NMR spectra of
compound II show, in view of the symmetric
molecular structure, by three aromatic proton and
carbon signals, as well as by one upfield signal at δН
4.40 и δС 55.16 ppm, characteristic of the methylene
1
The Н NMR spectra of suspensions of poorly
soluble cyclic oligomers VIII and IX in DMSO-d6
display aromatic proton signals at δН 6.60–8.05 ppm,
as well as proton signals of the SCH2N and NCH2N
groups at δН 4.39 and 4.63 ppm, respectively, in a 2 : 1
ratio (for compound VIII). The SCH2S and NCH2S
methylene proton signals in the spectrum of compound
IX are observed at δН 3.84 and 4.40 ppm, respectively
(integral intensity ration 1 : 2). It should be noted that
the oligomer IX produced by the reaction of m-
phenylenediamine with excess СН2О–Н2S (6 : 4) at
temperatures above 20°С contains more –CH2S− units
(m = 2), and, as a result, the signal at δН 3.84 ppm in
1
groups bridging the N and S atoms. The Н and 13С
NMR spectra of compound III contains, along with
aromatic proton and carbon signals, by two methylene
signals at δН 3.95 and δС 36.92 ppm (SСН2S) and δН
4.63 and δС 54.93 ppm (NСН2S). The IR spectra of
products II and III show an NH deformation vibration
band at 1618 cm–1.
Aiming at developing a selective cyclothio-
methylation procedure for о-phenylenediamine (I), we
have studied the effect of temperature and starting
reagent ratio on the yield and composition of this
compound with СН2О and H2S. The cyclothio-
1
its Н NMR spectrum has a higher intensity. The
absorption band at 720 cm–1 in the IR spectra of
Scheme 2.
S
S
9S
10
8
67N
11
N 12
S
S
N
N
S
S
N
N
NH2
NH2
13
m
m
5
23
CH2O−H2S
CH2O−H2S
22 24
14
15
3 : 2, 0oC
3 : 2, 6 : 4
20−70oC
4
3
2
21
16
N
N
n
n
17
18
1
VII
20
19S
VIII, nav = 8
S
S
IX, nav = 4−5
CH2O−H2S, 3 : 2, m = 1; 6 : 4, m = 2
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PHENYLENEDIAMINE AND 4,4'-DIAMINODIPHENYLS
695
compounds VIII and IX provides evidence for the
presence of a С–S bond. The band at 1460 cm–1 relates
to the CAr–N bond and that at 1600 cm–1 is assignable
basicity of one the NH2 groups (Kb 110 × 10–10 and
0.035 × 10–10) [17, 18]. p-Phenylenediamine hydro-
chloride, too, could not be involved in thiomethylation.
As a result, p-phenylenediamine catalyzes polycon-
densation of formaldehyde with Н2S to form poly
(methylene sulfide) [19]. At the same time, о- and m-
phenylenediamines, the basicities of the amino groups
in which are 3.3 × 10–10 and 7.6 × 10–10, undergo
cyclothiomethylation. Thus, the 1,3,5-dithiazinane
cycles we previously prepared by cyclothiomethylation
of aliphatic and aromatic amines, and aliphatic α,ω-
diamines could not be prepared from о-, m-, and p-
phenylenediamines. At the same time, 4-(1,3,5-
dithiazinan-5-yl)aniline was selectively synthesized by
the transamination of 5-methyl-1,3,5-dithiazinane with
p-phenylenediamine in the presence of a FeCl3·6Н2О
catalyst in 60% [20], аnd о-phenylenediamine under
the same conditions formed 1,2,6,7-tetrahydrobenzo[f]-
[1,3,5,8]dithiadiazonine (III) in 67% yield.
1
to the aromatic ring (CAr–N, С=СAr). The IR and Н
NMR spectra contain no terminal NH2, OH, or SH
signals, which is obviously explained by the formation
of cyclic oligomers. The cryoscopic molecular weights
Мcr [13] of benzothiaza macrocycle VIII and cross-
linked cyclic oligomer IX are 1598 ± 10 (nav 8) and
1570–2207 ± 10 (nav 4–5), respectively. The mass
spectra of compounds VIII and IX have low
information content because of the instability of these
products.
A
low-intensity
peak
of
the
[CH2NC6H4NCH2S]+ ion at m/z 164 is present, and the
most intense peaks belong to the [C6H6]+ and [CH2S]+
ions (m/z 78 and 46, respectively).
The obtained evidence allowed compounds VIII
and IX to be assigned cyclic oligomeric structures built
of units containing m-phenylenediamine fragments
linked by methylene sulfide CH2SCH2 groups. The
reaction at 0°С involves initial formation of an NCH2N
bonds followed by cyclization under the action of
СН2О–Н2S to form a 1,3,5-thiadiazine cycle. The same
products are also formed at 0°С from anilines [14–16]
and aliphatic diamines [9, 10]. In should be mentioned
that cyclothiomethylation of m-aminophenol [4] with
СН2О and H2S, too, involves intermolecular cyclo-
condensation to form macroheterocycles, whereas о-
and p-aminophenols undergo intramolecular hetero-
cyclization to form the corresponding 1,3,5-
dithiazinanes. Furthermore, the intermolecular thio-
methylation by two functional groups of the substrates,
yielding benzothiaza macrocycles is also characteristic
of m-aminothiophenol [3].
Cyclothiomethylation of 4,4'-diaminodiphenyl (X),
4,4'-diamonidiphenyl
oxide
(XI),
and
4,4'-
diaminodiphenylmethane (XII) with CH2O and H2S
(1 : 6 : 4, 40–80°С) in chloroform gives rise to bis-
(1,3,5-dithiazinanes) XIII–XV in yields of 62–99%.
The highest yields of compounds XIII–XV is observed
at 40–45°С. Along with bis(1,3,5-dithiazinane) XV,
the reaction with 4,4'-diaminodiphenylmethane (XII)
forms oligomeric products. The yield of compounds
XIII–XV decreases in the order: XIV (99%) > XIII
(69%) > XV (62%) (Scheme 3).
Cyclothiomethylation of 4,4'-diaminodiphenyls at
0–30°С or above 80°С gives poorly soluble oligomeric
products as the result of thee-component condensation
of diamines X–XII with CH2O and H2S. The reaction
products contain –CH2S– (XVI) and –CH2O–
fragments (XVII). Bisdithiazinanes XIII–XV were
extracted with chloroform. In the reaction with
p-Phenylenediamine fails to enter the thio-
methylation reaction at any reagent ratios and
temperature conditions, probably, because of the high
Scheme 3.
H2N
S
S
S
S
2
N
N
N
N
X
6 : 4
XIII
CH2O−H2S
40−60oC
H2N
Y
S
S
S
2
Y
Y = O (XI, X, IV)
CH2 (XII, XV)
S
XIV, XV
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696
KHABIBULLINA et al.
diamine XII, we made use of fractional crystallization
to isolate cyclic oligomers XVI and XVII is a total
yield of about 30%; therewith, oligomer XVII
precipitated immediately upon formation (Scheme 4).
EXPERIMENTAL
The purity of the starting compounds was no less
than 95%. The 1Н and 13С NMR spectra of compounds
II–VI, VIII, IX, and XIII were registered on a Jeol
FX-90Q spectrometer [22.5 (13C), 90 МHz (1H)] and
those of compounds XIV–XV, on a Bruker Avance
400 spectrometer [100.62 (13C), 400.13 МHz (1H)],
solvents CDCl3 and DMSO-d6, internal standard TMS.
The IR spectra were measured on a Specord 75 IR
spectrometer for suspensions in mineral oil. The mass
spectra of compounds II–IX were registered on a
Finnigan 4021 GCMS system (glass capillary column
50000×0.25 mm, stationary phase НР-5, carrier gas
helium, temperature programming from 50 to 300°С at
a rate of 5 deg/min, injector temperature 280°С, ion
source temperature 250°С, 70 eV). The mass spectra
of compounds XIII–XVII were obtained on a Bruker
Autoflex III MALDI TOF/TOF instrument (dried
droplet sample preparation technique, matrices α-
cyano-4-hydroxycinnamic and 2,5-dihydrobenzoic
acids). The elemental compositions were determined
on a Carlo Erba instrument. The melting points were
measured on an RNMK 80/2617 apparatus. Thin-layer
chromatography was performed on Silufol W-254
plates, development in an iodine chamber. Column
chromatography was performed on a KSK silica (100–
200 µm).
The MALDI-TOF mass spectra of bisdithiazianes
XIII and XIV show molecular ion peaks [M]+ at m/z
392 and 408, and the spectrum of compound ХV
contains an [M – H]+ ion peak at m/z 405. In the
spectra of oligomers XVI and XVII, molecular ion
peaks at m/z 549 [М – H]+ and 583 [М + H + Na]+ are
1
observed. The Н and 13С NMR spectra of bisdithia-
zianes XIII–ХV contain, along with aromatic proton
and carbon signals, signals at δH 4.98–5.11 and δС
53.53–55.37 ppm, corresponding to two magnetically
equivalent NCH2S methylene carbons in the dithiazine
ring, and the SCH2S methylene signals are observed at
δH 4.29–4.36 and δс 34.04–34.94 ppm. The 1Н and 13С
NMR signals of compound ХV also contain signals at
δН 3.92 and δС 46.78 ppm, which can be assigned to
the methylene bridge between the two benzene rings.
It should be noted that the cyclothiomethylation of
diphenyldiamines X–XI in ethanol results in
preferential formation of various cyclic dimers formed
by two-component intermolecular condensation of
diamines X–XI with CH2O and three-component
intermolecular condensation of X–XII with СH2O and
H2S.
Thus, aromatic diamines in the cyclothiomethyla-
tion reaction with formaldehyde and H2S tend to form
benzothiaza macroheterocycles. 1,3,5-Dithiazinanes
can only be synthesized from diamines with the amino
groups separated by a diphenyl bridge, whereas in
phenylenediamines, where the NH2 groups mutually
influence each other, the cyclothiomethylation results
are not so definite. The p-isomer fails to react, whereas
the о- and m-isomers undergo cyclothiomethylation by
the two NH2 groups simultaneous. With the о-isomer,
the reaction involves intramolecular cyclization, while
with m-isomer, intermolecular cyclization takes place.
Thiomethylation of o-, m-, and p-phenylene-
diamines (general procedure). A solution of 37%
formaldehyde (2.2 mL, 0.03 mol) was saturated with
H2S (0.02 mol, prepared from Na2S·9H2O and HCl) for
30 min at 20°С. A solution of 1.08 g (0.01mol) of о-
phenylenediamine (I) in 50 mL of СНСl3 [m- and p-
phenylenediamines were dissolved in 50 mL of EtOH
(95%)] was added dropwise to the resulting solution.
The mixture was stirred for 3 h at a preset temperature
(0–70°С) and then extracted with chloroform. The
extract was dried over СаCl2, the solvent was
evaporated, and the residue was subjected to column
Scheme 4.
N
N
N
N
N
N
N
N
O
O
O
O
O
O
S
XVI
XVII
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PHENYLENEDIAMINE AND 4,4'-DIAMINODIPHENYLS
697
chromatography on SiO2 (eluent hexane–ethyl acetate,
3 : 1) to obtain a mixture of compounds II–VI. The
product obtained from p-phenylenediamine was
filtered off and washed with EtOH.
12(13),14(15),16(24)-hexaene (VIII) was synthesize
by the above-described procedure at 0°С from 0.18 g
(0.001 mol) of m-phe-nylenediamine dihydrochloride,
0.22 mL (0.003 mol) of 37% formaldehyde, and
0.02 mol of H2S under stirring for 3 h. The reaction
mixture was neutralized with 50% KOH, the
precipitate that formed was filtered off, washed with
distilled water, and dried. Yield 0.18 g (99%), mp 290°С
(decomp.), Мcr 1598 ± 10 (nav = 9). IR spectrum, ν,
cm–1: 720 (С–S), 1370, 1450 (Ar), 1600 (Ar), 2900
(CH2). 1Н NMR spectrum (DMSO-d6), δ, ppm: 4.39
br.s (4Н, NСН2S), 4.63 br.s (2Н, NСН2N), 6.75 s (1Н,
НСAr), 7.40 br.s (2Н, НСAr), 8.05 s (1Н, НСAr). UV
spectrum (DMSO), λmax, nm (ε): 311.7 (0.75). Mass
spectrum, m/z (Irel, %):164 (6) [CH2NC6H4NCH2S]+, 78
(59) [C6H6]+, 46 (100) [CHS]+. Found, %: С 60.68; Н
5.46; N 15.18; S 18.43. С9Н10N2S. Calculated, %: С
60.64; Н 5.65; N 15.72; S 17.99.
1,2,4,5-Tetrahydrobenzo[d][1,3,6]thiadiazepine
(II). Yield 0.55 g (26% at 20°С), mp 137–139°С, Rf
0.52 (hexane–ethyl acetate, 3 : 1). IR spectrum, ν, cm–1:
750 (С–S), 1480 (Ar), 1600 (Ar), 1618 (NH), 2900
(CH2), 3300 (N–H). 1Н NMR spectrum (DMF-d6), δ,
ppm: 4.27 br.s (2H, NH), 4.40 br.s (2Н, Н2С2,7), 6.90–
7.30 m (4Н, НС8–11). 13С NMR spectrum (DMF-d6),
δС, ppm: 55.16 (С2,7), 114.46 (С8,11), 122.92 (С9,10),
135.23 (С4,5). Mass spectrum, m/z (Irel, %): 166 (28)
[М]+, 120 (100) [М – СН2S]+, 105 (45) [М –
СН2SСН3]+, 92 (55) [С6Н4NН2]+, 77 (79) [М – С6Н5]+.
Found, %: С 57.88; Н 6.64; N 16.53; S 20.30.
С8Н10N2S. Calculated, %: С 57.80; Н 6.06; N 16.85; S
19.29.
In a similar way, from 0.18 g of m-phenylene-
diamine dihydrochloride at 20°С we obtained 0.20 g of
compound IX [63%, Мcr 1570 ± 10 (nav = 5, m = 1)]; at
40°С: 0.28 g [89%, Мcr 2207 ± 10 (nav = 6, m = 1)].
1,2,6,7-Tetrahydrobenzo[f][1,3,5,8]dithiadiazonine
(III). Yield 0.25 g (12% at 20°С), mp 147–148°С, Rf
0.65 (hexane–ethyl acetate, 3 : 1). IR spectrum, ν, cm–1:
750 (С–S), 1500 (Ar), 1600 (Ar), 1618 (NH), 2900
(CH2), 3300 (N–H). 1Н NMR spectrum (СDCl3), δ,
ppm: 3.95 br.s (2Н, Н2С2), 4.25 br.s (2H, NH), 4.63
br.s (4Н, Н2С4,9), 7.00–7.30 m (4Н, НС10–13). 13С NMR
spec-trum (СDCl3), δС, ppm: 36.92 (С2), 54.93 (С4,9),
115.39 (С10,13), 129.39 (С11,12), 133.37 (С6,7). Mass
spectrum, m/z (Irel, %): 212 (20) [М]+, 149 (100) [М –
NH2SСН3]+, 133 (20) [М – SСН2SН]+, 120 (33) [М –
СН2SСН2SН]+, 105 (27) [СНSСН2SСН2]+, 92 (40)
[СН2SСН2S]+, 77 (20) [С6Н5]+. Found, %: С 50.82; Н
5.67; N 13.20; S 30.71. С9Н12N2S2. Calculated, %: С
50.91; Н 5.70; N 13.19; S 30.20.
Polymer IX. mp 290–320°С (decomp.). IR
spectrum, ν, cm–1: 730 (С–S), 1460 (Ar), 1620 (Ar),
2930 (CH2). UV spectrum (DMSO), λmax, nm (ε):
1
311.7 (0.75). Н NMR spectrum (DMSO-d6), δ, ppm:
3.84 s (4Н, SСН2S), 4.40 s (8Н, NСН2S), 6.62 s (2Н,
НСAr), 7.27 s (4Н, НСAr), 7.93 s (2Н, НСAr). Found,
%: С 46.35; Н 5.05; N 8.68; S 40.50. С12Н16N2S4.
Calculated, %: С 45.53; Н 5.09; N 8.85; S 40.52.
Thiomethylation of 4,4'-diaminodiphenyls (general
procedure). A solution of 0.184 g (0.001 mol) of 4,4'-
diaminodiphenyl (X) in 10 mL of СНСl3 was added
dropwise at 40°С to a solution of 37% formaldehyde
(0.5 mL, 0.006 mol) saturated with H2S (0.01 mol) for
30 min at 20°С. Before adding 4,4'-diaminodiphenyl
the H2S-saturated formaldehyde solution was heated to
40°С, and H2S was further bubbled at that temperature
under stirring for 1 h. After bubbling was stopped, the
reaction mixture was stirred for an additional 2 h and
then extracted with chloroform, dried over СаCl2, and
evaporated in a vacuum to obtain bis-4-(1,3,5-
dithiazinan-5-yl)phenyl (XIII).
1Н-1,3-Benzimidazole (IV). Yield 0.27 g (23% at
20°С), mp 164–166°С, Rf 0.34 (hexane–ethyl acetate,
3 : 1). Mass spectrum, m/z (Irel, %): 118 (100) [М]+, 91
(33) [С6Н4NH]+. The NMR spectra are identical to
those in [21].
N,N'-Dimethylene-1,2-phenylenediamine
(V).
Yield 0.11 g (8% at 20°С), mp 154–156°С, Rf 0.30
(hexane–ethyl acetate, 3 : 1). Mass spectrum, m/z (Irel,
%): 132 (100) [М]+, 104 (27) [С6Н5NN]+, 77 (17)
[С6Н5]+. The NMR spectra are identical to those in
[20].
Bis[4-(1,3,5-dithiazinan-5-yl)phenyl] (XIII). Yield
0.27 g (69%), light yellow crystals, mp 170–171°С. IR
spectrum, ν, cm–1: 700 (С–S), 1200 (C–N), 1480
1,3,4-Trithiolane (VI). The physicochemical
characteristics are identical to those in [15].
1
(CH2), 1600 (Ar), 2900 (CH2). Н NMR spectrum
(DMSO-d6), δ, ppm: 4.36 br.s (2Н, Н2С2,2'), 5.11 br.s
(4Н, Н2С4,6,4',6'), 6.65–6.80 br.s (4Н, НС8,12,8',12'), 7.41
1,7,11,17-Tеtraaza-9,19-dithiapenta-cyclo-
[15,3,1,12,6,17,11,112,16]tetracosa-2(22),3(4),5(6),-
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KHABIBULLINA et al.
br.s (4Н, НС9,11,9',11'). 13С NMR spectrum (DMSO-d6),
δС, ppm: 33.41 (С2,2'), 53.53 (С4,6,4',6'), 117.41
(С8,12,8',12'), 126.53 (С9,11,9',11'), 130.86 (С10,10'), 143.76
(С7,7'). Mass spectrum, m/z (Irel, %): 392 (28) [М]+, 315
(100) [М – СН2S2 + Н], 301 (45) [М – (СН2)2S2 + Н],
288 (55) [М – (СН2)3S2 + 2Н], 255 (79) [М – (СН2S)3 +
Н], 223 (79) [Ph2N2(CН2)3 + Н], 209 (79) [Ph2N2(CН2)2 +
Н]. Found, %: С 55.45; H 5.40; N 7.62; S 32.82.
С18Н20N2S4. Calculated, %: С 55.06; H 5.13; N 7.14; S
32.67.
С19Н22N2S4. Calculated %: С 56.12; H 5.45; N 6.89; S
31.54.
Oligomer XVI. Yield 15%. Mass spectrum, m/z
(Irel, %): 549 (100) [М – H], 457 (4) [М – PhNH2].
С33Н34N4SO2.
Oligomer XVII. Yield 15% Mass spectrum, m/z
(Irel, %): 583 (19) [М + H + Na], 381 (100) [М –
NСH2OН]. С34Н36N4O4.
ACKNOWLEDGMENTS
Сyclothiomethylation of 4,4'-diaminodiphenyl oxide
(XI) (0.1 g, 0.0005 mol) with СН2О and Н2S by the
above-described procedure gave bis[4-(1,3,5-dithia-
zinan-5-yl)phenyl] oxide (XIV) (0.202 g, 99%), and
from 4,4'-diaminodiphenylmethane (XII) (0.1 g,
0.0005 mol) we obtained a mixture of compounds
XV–XVII. Oligomer XVII insoluble in organic
solvents was filtered off from the reaction mixture, and
the filtrate was evaporated. Chloroform, 50 mL, was
added to the residue, and the precipitate that formed
was filtered off (oligomer XVI). The chloroform
filtrate was evaporated to obtain product XV.
The authors are grateful to U.M. Dzhemilev for
discussion of the obatined data.
REFERENCES
1. FR Patent 1341792, 1963; Chem. Abstr. , 1964, vol. 60,
p. P5528d.
2. Akhmetova, V.R., Nadyrgulova, G.R., Niatshina Z.T.,
and Dzhemilev, U.M., Chem. Heterocycl. Comp., 2009,
p. 1155.
3. Akhmetova, V.R., Khabibullina, G.R., Rakhimova, E.B.,
Vagapov, R.A., Khairullina, R.R., Niatshina, Z.T., and
Murzakova N.N., Mol. Divers., 2010, vol. 14, p. 463.
4. Akhmetova, V.R., Nadyrgulova, G.R., Khafizova, S.R.,
Tyumkina, T.V., Yakovenko, A.A., Antipin, M.Yu.,
Khalilov, L.M., Kunakova, R.V., and Dzhemilev, U.M.,
Russ. Chem. Bull., 2006, no. 2, p. 312.
5. Akhmetova, V.R., Khayrullina, R.R., Nadyrgulova, G.R.,
Kunakova, R.V., and Dzhemilev, U.M., Russ. J. Org.
Chem.., 2008, vol. 44, no. 2, p. 190.
6. Akhmetova V.R., Khairullina R.R., Tyumkina T.V.,
Nelyubina, Yu.V., Smolyakov, A.F., Bushmarinov, I.S.,
Starikova, Z.A., Abdullin, M.F., and Kunakova R.V.,
Russ. Chem. Bull., 2010, no. 2, p. 425.
7. Akhmetova, V.R., Nadyrgulova, G.R., Khafizova, S.R.,
Khairullina, R.R., Paramonov, E.A., Kunakova, R.V.,
and Dzhemilev, U.M., Russ. J. Org. Chem.., 2006,
vol. 42, no. 1, p. 145.
8. Khafizova, S.R., Akhmetova, V.R., Tyumkina, T.V.,
Khalilov, L.M., Kunakova, R.V., and Dzhemilev, U.M.,
Russ. Chem. Bull., 2004, no. 8, p. 1717.
9. Akhmetova, V.R., Vagapov, R.A., Nadyrgulova, G.R.,
Kunakova, R.V., and Dzhemilev, U.M., Russ. J. Org.
Chem.., 2007, vol. 43, no. 6, p. 918.
Bis[4-(1,3,5-dithiazinan-5-yl)phenyl] oxide (XIV).
Yield 0.2 g (99%), light yellow crystals, mp 186–190°С.
IR spectrum, ν, cm–1: 750 (С–S), 1050 (C–O–C), 1600
(Ar), 2900 (CH2). 1Н NMR spectrum (DMSO-d6), δ,
ppm: 4.33 s (4Н, Н2С2,2'), 5.06 s (8Н, Н2С4,6,4',6'), 7.01
d. d (8Н, НС8,9,11,12,8',9',11',12', J1 9.0, J2 21.7 Hz). 13С
NMR spectrum (DMSO-d6), δС, ppm: 34.04 (С2,2'),
54.46 (С4,6,4',6'), 118.86 (С8,12,8',12'), 119.46 (С9,11,9',11'),
141.19 (С7,7'), 150.67 (С10,10'). Mass spectrum, m/z (Irel,
%): 408 (28) [М], 331 (26) [М – SСН2S + Н], 239 (10)
[М – (СН2S)3СН2N + 3Н], 163 (100) [М– СН2S(СН2)
NPh]. Found, %: С 52.93; Н 4.55; N 6.67; S 31.30.
С18Н20N2S4О. Calculated, %: С52.91; Н 4.93; N 6.86;
S 31.39.
Bis[4-(1,3,5-dithiazinan-5-yl)phenyl]methane (XV).
Yield 0.13 g (62%), light yellow crystals, mp 167–
170°С. IR spectrum, ν, cm–1: 800 (С–S), 1250 (C–N),
1
1600 (Ar), 2900 (CH2). Н NMR spectrum (DMSO-
d6), δ, ppm: 3.92 s (2Н, Н2С13), 4.29 s (4Н, Н2С2,2'),
4.98 s (8Н, Н2С4,6,4',6'), 7.01 d (4Н, НС8,12,8',12', J 8.6 Hz),
7.19 d (4Н, НС9,11,9',11', J 8.6 Hz). 13С NMR spectrum
(DMSO-d6), δС, ppm: 34.94 (С2,2'), 46.78 (С13), 55.37
(С4,6,4',6'), 117.65 (С8,12,8',12'), 129.95 (С9,11,9',11'), 133.54
(С10,10'), 142.97 (С7,7'). Mass spectrum, m/z (Irel, %):
405 (100) [М H], 381 (82) [М – NС + Н], 329 (59)
[М – SСН2S + Н], 315 (36) [М – (СН2S)2СН2N + Н].
Found, %: С 55.98; H 5.45; N 6.74; S 31.32.
10. Akhmetova, V.R., Vagapov, R.A., Nadyrgulova, G.R.,
Tyumkina, T.V., Starikova, Z.A., Antipin, M.Yu.,
Kunakova, R.V., and Dzhemilev, U.M., Tetrahedron,
2007, vol. 47, p. 11702.
11. Tulyakova, E.V., Delbaere, S., Fedorov, Yu.V.,
Jonusauskas, G., and Fedorova, O.A., Eur. J. Chem.,
2011, vol. 17, p. 10752.
12. Gulakova, E.N., Sitin, A.G., Kuz’mina, L.G., and
Fedorova, O.A., Russ. J. Org. Chem., 2011, vol. 47,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

PHENYLENEDIAMINE AND 4,4'-DIAMINODIPHENYLS
699
17. Lindsay, R.J., Comprehensive Organic Chemistry,
Barton, S.D. and Ollis, W.D., Eds., Oxford: Pergamon,
1979, vol. 2, p. 159; Тranslated under the title
no. 2, p. 245.
13. Rybak, B.M., Analiz nefti i nefteproduktov (Analysis of
Oil and Oil products), Moscow: Gostoptekhizdat, 1962,
vol. 5, p. 66.
Obshchaya
organicheskaya
khimiya,
Moscow:
Khimiya, 1982, vol. 3, p. 168.
14. Akhmetova, V.R., Nadyrgulova, G.R., Niatshina, Z.T.,
Khairullina, R.R., Starikova, Z.A., Borisova, A.O.,
Antipin, M.Yu., Kunakova, R.V., and Dzhemilev, U.M.,
Heterocycles, 2009, vol. 1, p. 45.
15. Akhmetova, V.R., Niatshina, Z.T., Khabibullina, G.R.,
Bushmarinov, I.S., Borisova, A.O., Starikova, Z.A.,
Korzhova, L.F., and Kunakova, R.V., Russ. Chem.
Bull., 2010, no. 5, p. 1002.
18. Nikol’skii, B.N., Spravochnik khimika (Chemist’s
Handbook), Leningrad: Khimiya, 1964, vol. 3, p. 1008.
19. Aleev, R.S., Dal’nova, Yu.S., Popova, Yu.I.,
Masagutov, R.M., and Rafikov, S.R., Dokl. Akad. Nauk
SSSR, 1988, vol. 303, p. 873.
20. Rakhimova, E.B., Vasil’eva, I.V., Khalilov, L.M.,
Ibragimov, A.G., and Dzhemilev, U.M., Russ. J. Org.
Chem., 2011, vol. 47, no. 9, p. 1300.
16. Khafizova, S.R., Akhmetova, V.R., Kunakova, R.V.,
and Dzhemilev, U.M., Russ. Chem. Bull., 2003, no. 8,
p. 1817.
21. Aridoss, G. and Laali, K.K., Eur. J. Org. Chem., 2011,
vol. 15, p. 2827.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014