(Butylsulfanyl)ethanal and 3-(organylsulfanyl)butanal 1,1-dimethylhydrazones

Article abstract of DOI:10.1007/s11176-005-0341-8

Previously unknown (butylsulfanyl)ethanal and 3-(organylsulfanyl)butanal 1,1-dimethylhydrazones were synthesized. Their reactivity toward methyl iodide was studied.

Full text of DOI:10.1007/s11176-005-0341-8

Russian Journal of General Chemistry, Vol. 75, No. 6, 2005, pp. 891 900. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005,
pp. 945 953.
Original Russian Text Copyright
2005 by Sorokin, Lopyrev, Voronkov.
(Butylsulfanyl)ethanal
and 3-(Organylsulfanyl)butanal 1,1-Dimethylhydrazones
M. S. Sorokin, V. A. Lopyrev, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received January 12, 2004
Abstract Previously unknown (butylsulfanyl)ethanal and 3-(organylsulfanyl)butanal 1,1-dimethylhydra-
zones were synthesized. Their reactivity toward methyl iodide was studied.
Certain N-substituted hydrazones have exhibited
spasmolytic, hypotensive, and antitumor activity.
Their use for treatment of schizophrenia, leprosy, and
other diseases is being studied [1]. Over the past few
years much attention has been given to 1,1-dimethyl-
hydrazones, i.e. derivatives of 1,1-dimethylhydrazine,
a component of rocket fuels [2 4]. In particular,
certain 1,1-dimethylhydrazones serve as key starting
materials in the synthesis of azapeptides [5, 6], anti-
biotics, such as cirzathiomycin [7], anthrimycin [8],
azinothricyn [9], citropeptin [10], methamycin [11],
as well as biologically active pyrazole derivatives [12]
and muscarinic antagonists [13].
3-(Organylsulfanyl)butanal 1,1-dimethylhydrazones
V XII were synthesized by thiylation of the C=C
bond in crotonaldehyde 1,1-dimethylhydrazone (III)
with organic thiols, thiolcarboxylic acids, (sulfanyl-
alkyl)trialkoxysilanes, and 1-(sulfanylalkyl)silatranes
[scheme (2)]. The most vigorous reaction was ob-
served with thiolcarboxylic acids. Mixing of thiol-
acetic or thiolbenzoic acids with 1,1-dimethylhydra-
zone III gives rise to a vigorous exothermic reaction
that results in an almost quantitative formation of
hydrazones VII and VIII, respectively. The reaction
of hydrazone III with benzenethiol occurred less
vigorously but still with heat release. The latter reac-
tion involved an induction period of about 2 min and
then exothermal reaction developed to form hyd-
razone VI. Ethanethiol could be added to crotonal-
dehyde 1,1-dimethylhydrazone (III) only under pro-
longed reflux (reagent molar ratio 1:3) or UV irradia-
tion. However, the yield of product V in both cases
was no higher than 40%.
Proceeding with the research into aldehyde 1,1-di-
methylhydrazones [14], as well as trialkoxysilyl and
silatranyl derivatives of alkyl organyl sulfides [15 18],
we have synthesized previously unknown (butylsul-
fanyl)ethanal 1,1-dimethylhydrazone (II) and 3-(or-
ganylsulfanyl)butanal 1,1-dimethylhydrazones IV
XIV and studied their reactions with methyl iodide.
The yields, physicochemical properties, and elemental
analyses of compounds II XIV are listed in Table 1
and their structural formulas and spectral characteris-
tics, in Table 2.
RSH + MeCH=CH CH=NNMe
III
(2)
MeCH(SR)CH2CH=NNMe2,
V XII
R = Et (V), Ph (VI), MeCO (VII), PhCO (VIII),
CH2CH2OH (IX), CH2COOEt (X), CH2Si(OMe)3 (XI),
CH2CH2Si(OMe)3 (XII).
(Butylsulfanyl)ethanal 1,1-dimethylhydrazone (II)
was synthesized by reaction of (butylsulfanyl)ethanal
(I) with 1,1-dimethylhydrazine [scheme (1)].
Successful thiylation of crotonaldehyde 1,1-di-
methylhydrazone (III) with 2-sulfanylethanol, ethyl
sulfanylacetate, trimethoxy(sulfanylmethyl)silane,
trimethoxy(2-sulfanylethyl)silane, 1-(sulfanylmethyl)-
silatrane, and 1-(2-sulfanylethyl)silatrane could only
be effected by heating of a mixture of the correspond-
ing reagents at 135 140 C for 2.5 3 h. Under these
conditions, adducts IX XII formed in high yields
(Table 1). At the same time, the same reactions under
UV irradiation at 35 40 C for 6 h gave no more than
10 15% of adducts IX XII.
1
2
3
4
5
CH3CHCH2CH=NN(CH3)2
SH
BuSCH2CH=NNMe2 + H2O.
(1)
II
The reaction was accomplished by mixing equi-
molar reagent amounts in benzene or with no solvent.
It is accompanied by heat release and is complete
within 10 15 min. The yield of hydrazone II attains
85% in both cases.
1070-3632/05/7506-0891 2005 Pleiades Publishing, Inc.

892
Table 1. Physicochemical characterisitics and elemental analyses of hydrazones II and IV XIV
Found, % Calculated, %
SOROKIN et al.
bp,
C
n2D0
Formula
(p, mm Hg)
C
H
N
S
C
H
N
S
II
IV
V
VI
VII
VIII
IX
X
XI
85 80 81(1.5) 1.4960 54.93 10.43
83 85 86(9.0) 1.4990 49.37 9.21
37 70 71(1.5) 1.4965 54.81 10.18
15.85 18.03 C8H18N2S
19.01 21.56 C6H14N2S
15.88 18.02 C8H18N2S
12.47 14.22 C12H18N2S
14.47 16.78 C8H16N2OS
10.87 12.65 C13H18N2OS
14.28 16.37 C8H18N2OS
11.88 13.62 C10H20N2O2S
55.13 10.41
49.27 9.64
55.13 10.41
16.07 18.39
19.15 21.92
16.07 18.39
12.60 14.42
14.88 17.02
11.19 12.81
14.72 16.85
12.06 13.80
9.99 11.41
9.51 10.89
12.60 9.61
12.09 9.22
78 117 119(2.5) 1.5657 64.31
90 95 96(1.5) 1.5018 50.78
92 115 116(1.5) 1.5675 61.86
87 120 121(1.5) 1.5180 50.02
85 115 116(1.0) 1.4920 51.36
78 135 136(1.5) 1.4760 42.31
70 147 148(1.5) 1.4730 44.31
7.88
8.23
6.94
9.14
8.43
8.27
8.41
7.87
8.17
64.82
51.03
62.37
50.49
51.69
8.16
8.56
7.25
9.53
8.68
8.63
8.90
8.16
8.41
9.62 11.09 C10H24N2O3SSi 42.82
9.36 10.39 C11H26N2O3SSi 44.86
XII
XIII
XIV
96 80 82a
94
46.38
48.01
12.36
11.87
9.36 C13H27N3O3SSi 46.82
9.06 C14H29N3O3SSi 48.38
b
a
b
Melting point.
Viscous oil.
3-[2-(Trimethoxysilyl)ethylsulfanyl]butanal 1,1-
dimethylhydrazone (XII) was also synthesized by
addition of 3-sulfanylbutanal 1,1-dimethylhydrazone
(IV) to trimethoxy(vinyl)silane [scheme (3)].
whereas its homolog XIV was obtained as a thick
light yellow syrup that could not be crystallized even
upon prolonged handling in the cold.
1
The H and 13C NMR spectra of silatranyl deriva-
tive XIV show that it contains a small admixture of
the starting compounds. On attempted purification by
vacuum distillation hydrazone XIV decomposed to
form 1-(2-sulfanylethyl)silatrane (XV) [scheme (5)
(7)].
IV + CH2=CHSi(OMe)3
XII.
(3)
The reaction was accomplished by heating of
equimolar reagent mixture at 135 140 C. However,
the yield of thus obtained adduct XII after 3 h was no
higher 35%.
XIV
MeCHCH2CH=NNMe2
Previously unknown 3-sulfanylbutanal 1,1-di-
methylhydrazone (IV) was synthesized from acetyl-
sulfanyl derivative VII in methanol under reflux in
the presence of a catalytic amount of sodium
methylate.
+ S(CH2)2Si(OCH2CH2)3N,
(5)
MeCHCH2CH=NNMe2
[MeCH=CHCH=NNMe2] + H , (6)
III
H + S(CH2)2Si(OCH2CH2)3N
XV.
(7)
Hydrazones II and IV XII are viscous colorless or
light yellow liquids with a characteristic strong un-
pleasant odor.
This reaction occurs above 200 C, probably, by a
free-radical mechanism. Along with 1-(2-sulfanyl-
ethyl)silatrane (XV), crotonaldehyde 1,1-dimethyl-
hydrazone (III) is formed and undergoes tarring under
the reaction conditions.
Silatranes XIII and XIV were synthesized by
transetherification of 3-(trimethoxysilyl)methylsul-
fanyl)- and 3-[2-(trimethoxysilyl)ethylsulfanyl]buta-
nals (XII, XIII) with tris(2-hydroxyethyl)amine
[scheme (4)]. The reaction was accomplished by heat-
ing (120 130 C) of equimolar reagent mixture of the
corresponding reagents in the presence of a catalytic
amount of sodium methylate.
Because of the thermal instability of 1,1-dimethyl-
hydrazone XIV, we failed to synthesize it by adding
(2-sulfanylethyl)silatrane (XV) to the C=C bond in
hydrazone III. Heating of equimolar reagent mixture
at 145 150 C for 3 h resulted in no adduct XIV for-
mation, and at 180 200 C tarring of the reaction
mixture was observed. For qualitative assessment of
the ability of the S and N atoms in organic (II, V X)
and organosilicon (XI XIV) 3-sulfanylbutanal 1,1-
XI, XII + (HOCH2CH2)3N
XIII, XIV + 3MeOH. (4)
3-(Silatranylmethylsulfanyl)butanal 1,1-dimethyl-
hydrazone (XIII) is a colorless crystalline substance,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

(BUTYLSULFANYL)ETHANAL AND 3-(ORGANYLSULFANYL)BUTANAL
Table 2. 1H, 13C, and 29Si NMR spectra of hydrazones II XIV
893
Structure
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
1
2
3
4
5
6
7
II
CH3CH2CH2CH2SCH2CH=NN(CH3)2 0.82 t (3H, C1H3), 1.33 sextet (2H, 13.74 (C1), 21.99 (C2), 30.51 (C3),
C2H2), 1.48 sextet (2H, C3H2), 2.42 t 31.64 (C4), 34.05 (C5), 43.71 (C7),
(2H, C4H2), 2.70 s (6H, 2C7H3), 3.19, 133.30 (C6)
3.2
d
[2H, C5H2, J(C5H2 C6H)
(1H, C6H)
6.5 Hz)], 6.44
t
1
2
3
4
5
III
CH3CH=CH CHNN(CH3)2
1.78, 1.79 d (3H, C1H3, J 6.80 Hz), 18.15 (C1), 42.90 (C5), 130.11
2.78 s (6H, 2C5H3), 5.78 m [1H, C2H3, (C2), 130.38 (C3), 136.83 (C4)
J(C1H3 C2H) 6.8, Jgem 15.5 Hz],
6.18 m (1H, C3H), 6.97, 6.99 d (1H,
C4H, J 8.85 Hz)
1
2
3
4
5
IV
V
1.19, 1.20 (d, 3H, C1H3), 1.52, 1.54 d 24.71 (C1), 33.80 (C2), 43.51 (C3),
(1H, SH), 2.29 (A), 2.32 (B) m (2H, 42.83 (C5), 134.49 (C4)
AB), C3H2), 2.59 s (6H, 2C5H3),
CH3CHCH2CH=NN(CH3)2
SH
2.97 sextet (1H, C2H), 6.45 t (1H, C4H)
1
2
3
4
5
1.24 t (3H, C7H3), 1.28, 1.29 d (3H, 14.68 (C7), 19.49 (C1), 24.12 (C3),
C1H3), 2.42 (A), 2.46 (B) m (2H, AB), 38.28 (C2), 39.86 (C6), 43.02 (C5),
C3H2), 2.56 q (2H, C6H2), 2.73 s (6H, 135.41 (C4)
2C5H3), 2.94 sextet (1H, C2H), 6.65 t
CH3CHCH2CH=NN(CH3)2
6
7
SCH2CH3
(1H, C4H)
1
2
3
4
5
VI
1.33, 1.35 d (3H, C1H3), 2.44 (A), 2.52 20.78 (C1), 39.82 (C3), 42.10 (C2),
(B) m (2H, AB), C3H2), 2.71 s (6H, 43.02 (C5), 126.80 (C9), 128.72
2C5H3), 3.38 sextet (1H, C2H), 6.62 t (C7, C11), 132.13 (C8, C10), 134.79
(1H, C4H), 7.19 7.41 m (5H, C6H5) (C6), 135.02 (C4)
CH3CHCH2CH=NN(CH3)2
7
S
6
8
11
9
10
1
2
3
4
5
VII
VIII
1.30, 1.31 d (3H, C1H3), 2.28 s (3H, 20.71 (C1), 30.62 (C2), 37.98 (C3),
C7H2), 2.47 pseudotriplet (2H, C3H2), 39.78 (C7), 43.04 (C5), 134.20
2.72 s (6H, 2C5H3), 3.71 sextet (1H, (C4), 195.31 (C6)
C2H), 6.52 t (1H, C4H)
CH3CHCH2CH=NN(CH3)2
6
7
SCOCH3
1
2
3
4
5
1.39, 1.41 d (3H, C1H3), 2.59 pseodo- 20.73 (C1), 37.89 (C2), 39.80 (C3),
triplet (2H, C3H2), 2.70 s (6H, 2C5H3), 42.91 (C5), 126.96 (C9, C11),
3.95 m (1H, C2H), 6.60 t (1H, C4H), 128.36 (C8, C12), 133.08 (C10),
CH3CHCH2CH=NN(CH3)2
6
C
8
S
7
9
10
12
11
O
7.38 7.91 m (5H, C6H5)
134.51 (C4), 136.96 (C7), 191.34
(C6)
1
2
3
4
5
IX
1.29, 1.30 d (3H, C1H3), 2.44 (A), 2.47 21.41 (C1), 33.24 (C3), 38.81 (C2),
(B) m (4H, AB), C3H2 and C6H2), 39.91 (C6H2), 43.21 (C5), 61.40
CH3CHCH2CH=NN(CH3)2
6
7
SCH2CH2OH
2.73 s (6H, 2C5H3), 2.99 m (1H, C2H), (C7), 135.88 (C4)
3.69 t (2H, C7H2), 6.65 t (1H, C4H)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

894
SOROKIN et al.
Table 2. (Contd.)
Structure
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
1
2
3
4
5
X
1.26 t (3H, C9H3), 1.29, 1.30, d (3H, 14.23 (C9), 20.73 (C1), 32.56 (C3),
C1H3), 2.44 (A), 2.51 (B) m (2H, AB, 39.48 (C2), 43.23 (C5), 60.35 (C8),
C3H2), 2.74 s (6H, 2C5H3), 3.12 pse- 134.84 (C4), 170.69 (C7), 39.64
udo-sextet (1H, C2H), 3.26 s (2H, (C6)
CH3CHCH2CH=NN(CH3)2
6
7
8
9
SCH2COOCH2CH3
C6H2), 4.18 q (2H, C8H2), 6.62 t (1H,
C4H)
1
2
3
4
5
XIa
1.28, 1.29 d (3H, C1H3), 1.88 s (2H, 8.60 (C6), 20.16 (C1), 39.14 (C3),
C6H2), 2.41 (A), 2.48 (B) m (2H, AB, 41.36 (C2), 43.26 (C5), 51.08 (C7),
C3H2), 2.74 s (6H, 2C5H3), 2.87 m 135.52 (C4)
CH3CHCH2CH=NN(CH3)2
6
7
SCH2Si(OCH3)3
(1H, C2H), 3.60 s (9H, 3C7H3), 6.65 t
(1H, C4H)
1
2
3
4
5
XIIb
0.96 m (2H, C7H2), 1.28, 1.29 d (3H, 10.31 (C7), 20.78 (C1), 24.14 (C3),
C1H3), 2.43 (A), 2.47 (B) m (2H, AB, 38.50 (C2), 39.75 (C6), 42.90 (C5),
C3H2), 2.64 m (2H, C6H2), 2.73 s 50.27 (C8), 135.19 (C4)
(6H, 2C5H3), 2.95 pseudo-sextet (1H,
CH3CHCH2CH=NN(CH3)2
6
7
8
SCH2CH2Si(OCH3)3
C2H), 3.58 s (9H, 3C8H3), 6.65 t (1H,
C4H)
1
2
3
4
5
XIIIc
XIVd
1.25, 1.28 d (3H, C1H3), 1.76 s (2H, 16.05 (C6), 19.62 (C1), 39.06 (C3),
C6H2), 2.35 (A), 2.42 (B) m (2H, AB, 40.84 (C2), 43.07 (C5), 50.65 (C7),
C3H2), 2.74 s (6H, 2C5H3), 2.80 m 57.25 (C8), 136.99 (C4)
CH3CHCH2CH=NN(CH3)2
6
7
8
SCH2Si(OCH2CH2)3N
(1H, C2H), 2.85 t (6H, 3C8H2), 3.85 t
(6H, 3C7H2), 6.72 t (1H, C4H)
1
2
3
4
5
0.67 m (2H, C2H2), 1.21, 1.24 d (3H, 17.42 (C7), 20.88 (C1), 27.45 (C3),
C1H3), 2.35 (A), 2.42 (B) m (2H, AB, 38.01 (C2), 39.99 (C6), 43.15 (C5),
C3H2), 2.61 m (2H, C6H2), 2.65, 50.94 (C8), 57.46 (C9), 137.03
2.67 d (6H, C5H3), 2.87 pseudo-sextet (C4)
CH3CHCH2CH=NN(CH3)2
6
7
8
9
SCH2CH2Si(OCH2CH2)3N
(1H, C2H), 6.65 t (1H, C4H)
a
b
c
d
48.7 ppm.
45.2 ppm.
75.3 ppm.
69.9 ppm.
Si
Si
Si
Si
dimethylhydrazones to form the corresponding onium
derivatives, we studied their reaction with methyl
iodide in a 1:1 molar ratio [schemes (8) and (9)]. It
was found that the most active reaction center in
organylsulfanyl derivatives II and V X is the terminal
nitrogen atom. (Butylsulfanyl)ethanal hydrazone II
fairly fast reacts with methyl iodide already at room
temperature both in the absence of solvents and in
ether or methanol. However, reaction (8) fails to come
to completion. The yield of 1,1,1-trimethylhydrazi-
nium iodide XVI is no higher than 50%, even though
the reaction time is increased from 1 to 6 h. Under
similar conditions, hydrazones VI VIII much faster
react with methyl iodide ( 10 min). Therewith, res-
pective 1,1,1-trimethylhydrazonium iodides XVIII
XX are formed in an almost quantitative yeild. Even
though hydrazones V and IX XII slowly reacted with
methyl iodide under the same conditions (8 10 h), the
yields of 1,1,1-trimethylhydrazinium iodides XVII
and XXI XXIV were no higher than 70%. The yields,
physicochemical properties, and elemental analyses
of compounds XVI XXXIII are listed in Table 3 and
their structural formulas and spectral characteristics,
in Table 4.
II + MeI
XVI,
XVII XXIV.
(8)
(9)
V XII, XIV + MeI
With hydrazones V and XII, both the nitrogen and
sulfur atoms could be iodomethylated at a hydrazone:
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

(BUTYLSULFANYL)ETHANAL AND 3-(ORGANYLSULFANYL)BUTANAL
895
Table 3. Physicochemical characteristics and elemental analyses of 1,1,1-trimethylhydrazinium iodides XVI XXIV,
XXXI, and XXXIII and diiodomethylates XXV, XXVI, and XXX
Found, %
I
Calculated, %
mp,
C
Formula
C
H
N
S
C
H
I
N
S
XVI
42 117 119 33.76 6.42 39.63 8.81 9.74 C9H21IN2S
(decomp.)
34.16
6.69
40.11 8.85 10.13
XVII
XVIII
72 84 85
87 74 76
33.95 6.51 40.11 8.79 9.93 C9H21IN2S
42.51 5.58 34.87 7.89 8.86 C13H21IN2S
34.16
42.86
6.69
5.81
40.11 8.85 10.13
34.84 7.68 8.80
(decomp.)
XIX
XX
XXI
XXII
XXIII
XXIV
XXV
XXVI
XXX
96 147 148 32.14 5.63 37.90 8.04 9.34 C9H19IN2OS
32.73
42.86
32.53
35.28
31.26
33.03
26.19
5.80
7.14
6.37
6.19
6.44
6.70
5.28
5.58
5.38
38.42 8.48 9.71
32.36 5.40 8.17
38.19 8.43 9.65
33.89 7.48 8.56
30.03 6.63 7.58
29.31 6.42 7.34
55.35 6.11 6.99
43.87 7.27 5.54
41.08 6.80 5.18
91 148 149 42.43 6.88 31.79 5.16 7.78 C14H21IN2OS
a
72
75
78
81
32.35 6.12 37.75 8.18 9.16 C9H21IN2OS
35.24 6.10 33.18 7.56 9.34 C11H23IN2O2S
30.91 6.11 29.73 6.33 7.39 C11H27IN2O3SSi
32.89 6.32 25.94 6.13 7.11 C12H29IN2O3SSi
a
a
a
89 140 142 26.01 5.62 54.97 6.03 6.83 C10H24I2N2S
a
96
26.49 5.78 42.18 7.12 5.08 C13H32I2N2O3SSi 26.99
95 145 146 29.62 6.05 40.25 6.32 4.87 C15H33I2N3O3SSi 29.16
(decomp.)
a
XXXI
97
36.32 6.18 25.18 8.17 6.14 C15H32IN3O3SSi
36.81
33.08
6.59
5.95
25.92 8.58 6.55
49.94 11.02
XXXIII 98 185 187 33.15 6.17 49.24 10.87
C7H15IN2
a
Oily material.
MeI molar ratio of 1:2 [scheme (10)]. The reaction
was accomplished under short reflux in methanol.
Therefore, it might be expected that the reaction of
hydrazone XIII with MeI at a 1:1 molar ratio would
lead to methylsulfonium iodide XXVIII rather than
1,1,1-trimethylhydrazinium iodide XXIX.
V, XII + 2MeI
[MeCH(Me+SR)CH2CH=NNMe3]2 I ,
(10)
+
MeCHCH2CH=NNMe2 MeCHCH2CH=NNMe2 I
XXV, XXVI
+
SCH2Si(OCH2CH2)3N
I
MeSCH2Si(OCH2CH2)3N
R = Et (XXV), CH2CH2Si(OMe)3 (XXVI).
XXVIII
XXIX
At the same time, hydrazones IX and X react by
the terminal nitrogen atom even with excess MeI.
After 6-h refluxing in methanol, 1,1,1-trimethylhydra-
However, we failed to obtain unambiguous ex-
perimental evidence for this suggestion. The reaction
in chloroform gave a hardly separable mixture of
sodides XXVIII XXX. The reaction in methanol at a
1: 2 XIII:CH3I molar ratio gave bisiodomethylate
XXX.
zinium iodides XXI and XXII, as well as 1,1,1-tri-
+
methylhydrazinium iodide Me3NNH2 (XXVII) were
isolated. The latter product (yield 20%) is probably
formed by partial hydrolysis or methanolysis of 1,1,1-
trimethylhydrazinium iodides XXI and XXII.
Unlike compound XIII, the reaction of hydrazone
XIV with MeI at a 1:1 molar ratio in ether gave
primarily 1,1,1-trimethylhydrazinim iodide XXXI
(yield 90%).
3-(Silatranylmethylsulfanyl)butanal and 3-[2-(sila-
tranylethylsulfanyl)butanal] 1,1-dimethylhydrazones
(XIII, XIV) in which the sulfur and silicon atoms are
intervened by one (XIII) or two (XIV) methylene
units were of particular interest in view of the pre-
sence in their molecules of a superelectron-donor
group Si(OCH2CH2)3N ( * 3.49 [19]). Previously
we found that 1-(organylsulfanylmethyl)silatranes
extremely easily react with methyl iodide to form
+
MeCHCH2CH=NNMe2 I
+
I
MeSCH2CH2Si(OCH2CH2)3N
XXXI
Attempted synthesis of bisiodomethylate XXXII
by reaction of hydrazone XIV with excess methyl
dimethylsilatranylmethylsulfonium
iodides
[20].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

896
SOROKIN et al.
1
Table 4. H, 13C, and 29Si NMR spectra of 1,1,1-trimethylhydrazinium iodides XVI XXIV, XXXI, and XXXIII and
diiodomethylate XXX
Structure
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
1
2
3
4
5
6
7
XVI
CH3CH2CH2CH2SCH2CH=NN+ (CH3)3 I 0.94 t (3H, C1H3), 1.43 sextet (2H, 14.29 (C1), 23.07 (C2), 32.28
C3H2), 1.56 m (2H, C2H2), 2.55 t (2H, (C3), 32.54 (C4), 32.80 (C5),
C4H2), 3.43, 3.45 d [2H, C5H2, 56.28 (C6), 165.67 (C7)
3J(CH2=CH) 6.14 Hz], 3.47 s (9H,
3C7H3), 8.35 t (1H, C6H)
1
2
3
4
5
+
XVII
XVIII
XIX
1.24 t (3H, C7H3), 1.35, 1.38 d (3H, 14.60 (C7), 21.68 (C1), 23.79
C1H3), 2.55 (A), 2.58 (B) m (4H, AB, (C3), 35.90 (C6), 38.24 (C8),
C3H2 and C6H2), 3.35 sextet (1H, C2H), 55.68 (C5), 168.40 (C4)
3.72 s (9H, 3C5H3), 8.99 t (1H, C4H)
CH3CHCH2CH=NN(CH3)3I
SCH2CH3
1
2
3
4
+ 5
1.37, 1.39 d (3H, C1H3), 2.69 (A), 2.82 21.43 (C1), 39.20 (C3), 39.57
(B) m (2H, AB, C3H2), 3.67 s (9H, (C2), 55.75 (C5), 127.57 (C9),
3C5H3), 3.81 sextet (1H, C2H), 7.24 129.08 (C7, C11), 132.69 (C8,
7.48 m (5H, C6H5), 9.06 t (1H, C4H) C10), 133.12 (C6), 168.52 (C4)
CH3CHCH2CH=NN(CH3)3I
7
S
6
8
11
9
10
1
2
3
4
+ 5
1.42, 1.44 d (3H, C1H3), 2.32 s (3H, 20.97 (C1), 30.98 (C2), 36.19
C7H3), 2.73 (A), 2.89 (B) m (2H, AB, (C3), 39.80 (C7), 55.73 (C5),
C3H2), 3.74 s (9H, 3C5H3), 3.84 sextet 167.64 (C4), 196.06 (C6)
CH3CHCH2CH=NN(CH3)3I
6
7
SCOCH3
(1H, C2H), 8.85
t
(1H, C4H)
1
2
3
4
5
+
XX
1.53, 1.55 d (3H, C1H3), 2.76 (A), 3.08 21.14 $(C1), 36.28 (C3), 40.33
(B) m (2H, AB, C3H2), 3.66 s (9H, (C2), 55.45 (C5), 127.21 (C9,
3C5H3), 4.07 pseudo-sextet (1H, C2H), C11), 128.97 (C8, C12), 134.05
7.44 7.87 m (5H, C6H5), 8.84 t (1H, (C10), 136.38 (C7), 166.91 (C4),
CH3CHCH2CH=NN(CH3)3I
6
C
8
S
7
9
10
12
11
O
C4H)
192.13 (C6)
1
2
3
4
+ 5
XXI
1.37, 1.39 d (3H, C1H3), 2.75 m (4H, 22.24 (C1), 26.50 (C3), 37.72
C6H2 and C3H2), 3.35 pseudo-sextet (C2), 39.84 (C6), 56.05 (C5),
(1H, C2H), 3.52 s (9H, 3C5H3), 3.70 t 62.43 (C7), 169.00 (C4)
CH3CHCH2CH=NN(CH3)3I
6
7
SCH2CH2OH
(2H, C7H2), 8.85 t (1H, C4H)
1
2
3
4
+ 5
XXII
1.28 t (3H, C9H3), 1.41 d (3H, C1H3), 13.81 (C9), 21.42 (C1), 32.15
2.70 (A), 2.85 (B) m (2H, AB, C3H2), (C6), 37.28 (C2), 37.86 (C3),
3.34 s (2H, C6H2), 3.43 m (1H, C2H), 55.50 (C5), 61.23 (C8), 161.71
3.74 s (9H, 3C5H3), 9.00, 8.99 d.d (C4), 170.00 (1H, C4H) (C7)
CH3CHCH2CH=NN(CH3)3I
6
7
8
9
SCH2COOCH2CH3
1
2
3
4
+ 5
XXIIIa
1.22, 1.25 d (3H, C1H3), 1.71 s 6.61 (C6), 20.08 (C1), 36.75
(2H, C6H2), 2.65 (A), 2.75 (B) m (2H, (C3), 37.53 (C2), 50.46 (C7),
AB, C3H2), 3.25 m (1H, C2H), 3.44 s 55.21 (C5), 167.54 (C4)
(9H, 3 C5H3), 3.58 s (9H, 3C7H3),
CH3CHCH2CH=NN(CH3)3I
6
7
SCH2Si(OCH3)3
8.80 t (1H, C4H)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

(BUTYLSULFANYL)ETHANAL AND 3-(ORGANYLSULFANYL)BUTANAL
Table 4. (Contd.)
897
Structure
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
1
2
3
4
+ 5
XXIVb
1.30, 1.32 d (3H, C1H3), 0.89 m (2H, 10.04 (C7), 21.51 (C1), 23.73
C7H2), 2.60, 2.73 centers of two over- (C3), 36.18 (C2), 38.27 (C6),
lapping multiplets (4H, C3H2 and 50.41 (C8), 55.64 (C5), 168.31
C6H2), 3.28 m (1H, C2H), 3.49 s (9H, (C5)
CH3CHCH2CH=NN(CH3)3I
6
7
8
SCH2CH2Si(OCH3)3
3C5H3), 3.68 s (9H, 3C8H3), 8.94 t
(1H, C4H)
1
2
3
4
+ 5
XXX
1.47 d. d. (3H, C1H3), 1.95 (A), 2.10 21.33 (C1), 27.82 (C7), 29.07
CH3CHCH2CH=NN(CH3)3I
2
(B) (2H, AB, C7H2, JAB 7.6 Hz), 2.76, (C6), 42.16 (C2), 43.92 (C6),
6
7
8
CH3+SCH2Si(OCH2CH2)3N
I
2.82 d (3H, C3H3), 3.00 t (6H, C8H2), 50.01 (C9), 54.44 (C5), 56.90
3.49 s (9H, 3C5H3), 3.81 t (6H, C9H2), (C8), 167.59 (C4)
4.02 pseudo-sextet (1H, C2H), 8.60 t
(1H, C4H)
1
2
3
4
+ 5
XXXI
0.90 m (2H, C7H2), 1.08 center of a 17.54 (C5), 21.84 (C1), 26.77
CH3CHCH2CH=NN(CH3)3I
doublet (3H, C1H3)
(C3), 35.86 (C2), 38.60 (C6),
50.54 (C8), 55.46 (C5), 57.09
(C9), 167.55 (C4)
6
7
8
9
+SCH2CH2Si(OCH2CH2)3N
1
2
3
4
+ 5
XXXIII CH3CH=CHCH=NN(CH3)3 I
2.00 d (3H, C1H]3), 3.47 s (9H, 19.59 (C1), 56.59 (C5), 126.66
3C5H3), 6.31 m (1H, C2H), 6.94 m (C2), 153.34 (C3), 166.61 (C4)
(1H, C3H), 8.72 d (1H, C4H)
iodide in methanol or by transetherification of tri-
methoxysilyl derivative XXVI with tris(2-hydroxy-
ethyl)amine proved unsuccessful. In both cases, com-
plex product mixtures formed. In the first case we
could only isolate (2-hydroxyethyl)amine hydroiodide
and in the second, tris(2-hydroxyethyl)amine hydro-
iodide and 2-(but-2-enylidene)-1,1,1-trimethylhydra-
zinium iodide (XXXIII).
tively). Most compounds were studied as 10 15%
solutions in CDCl3. The NMR spectra of iodides XVI,
XXI, and XXVII, as well as of bisiodomethylate
XXX were obtained for 10 15% solutions in CD3OD.
(Butylsulfanyl)ethanal 1,1-dimethylhydrazone
(II). To a stirred solution of 9.0 g of (butylsulfanyl)-
ethanal (I) in 25 ml of benzene, 6.0 g of 1,1-dime-
thylhydrazine was added dropwise. Therewith, the
temperature of the reaction mixture was maintained at
20 25 C. The mixture was stirred for 1 h at that
temperature, transferred into a separatory funnel, left
to stand for 1 h, and the aqueous layer was separated.
The organic layer was freed of water admixture (by
azeotropic distillation with benzene), after which
benzene was distilled off at atmospheric pressure. The
residue was fractionated in a vacuum to obtain 10.1 g
(85%) of compound II as a colorless oily liquid with a
characteristic unpleasant odor of aminosulfide. IR
Attempted quaternization of the nitrogen atom in
hydrazones VII and VIII with 1-(iodomethyl)silatrane
in methanol under reflux or in DMF also failed.
The composition and structure of the synthesized
1
compounds were proved by H, 13C, and 29Si NMR
and IR spectroscopy and elemental analysis (Tables 3
and 4).
EXPERIMENTAL
1
spectrum, , cm : 1590 (C=N).
The IR spectra were recorded on a Specord IR-75
1
instrument. The H, 13C, and 29Si NMR spectra were
A similar simplified procedure was used to prepare
the starting (known) crotonaldehyde 1,1-dimethyl-
hydrazone (III). From 14.0 g of crotonaldehyde and
obtained on a Bruker DPX-400 instrument at 400.13,
100.61, and 79.49 MHz (1H, 13C, and 29Si, respec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

898
SOROKIN et al.
1
12.0 g of 1,1-dimethylhydrazine in 25 ml of benzene
we obtained 11.5 g (51%) of compound III as a color-
less oily liquid with a strong unpleasant odor, bp 62
63 C (20 mm Hg), n2D0 1.5120 {published data [21]:
bp 65 68 C (16 mm Hg)}.
1,1-dimethylhydrazone (X) [IR spectrum, , cm :
950, 1050 (C?O), 1610 (C=N), 1720 (C=O)], and
from 5.0 g of hydrazone III and 7.5 g of trimethoxy-
(sulfanylmethyl)silane, 9.7 g (78%) of 3-[(trimeth-
oxysilyl)methylsulfanyl]butanal 1,1-dimethylhyd-
1
razone (XI) [IR spectrum, , cm : 790, 810, 1090,
3-(Ethylsulfanyl)butanal 1,1-dimethylhydra-
zone (V). A mixture of 8.3 g of crotonaldehyde 1,1-
dimethylhydrazone (III) and 7.0 ml of ethanethiol was
heated under reflux for 6 h. Excess ethanethiol was
removed from the reaction mixture by distillation. The
residue was fractionated in a vacuum to isolate 4.7 g
(37%) of compound V as a colorless oily liquid. IR
1190 (Si O C), 1600 (C=N)].
3-[2-(Trimethoxysilyl)ethylsulfanyl]butanal
1,1-dimethylhydrazone (XII). a. Compound XII was
obtained similarly to compound XI from 5.0 g of
hydrazone III and 8.1 g of trimethoxy(2-sulfanyl-
1
ethyl)silane. Yield 9.2 g (70%). IR spectrum, , cm :
1
spectrum, , cm : 1610 (C=N).
800, 1090, 1190 (Si O C), 1600 (C=N).
3-(Phenylsulfanyl)butanal 1,1-dimethylhydra-
zone (VI). Benzenethiol, 2.2 g, was added to 2.3 of
crotonaldehyde 1,1-dimethylhydrazone (III). Within
1 2 min, the temperature of the reaction mixture
raised from 20 to 50 C. The mixture was heated for
1 h at 100 C and fractionated in a vacuum to obtain
3.4 g (78%) of compound VI as a colorless oily liquid.
b. A mixture of 2.5 g of hydrazone IV and 2.2 g of
trimethoxy(vinyl)silane was heated at 140 145 C for
3 h and then fractionated in a vacuum to isolate 1.5 g
(35%) of compound XII.
3-(Silatranylmethylsulfanyl)butanal 1,1-di-
methylhydrazone (XIII). A solution of 2.3 g of tris-
(2-hydroxyethyl)amine in 5 ml of methanol and
2 drops of 10% methanolic MeONa were added to a
solution of 4.1 g of compound XI in 5 ml of methanol.
The reaction mixture was refluxed for 2 h. Methanol
was distilled off at atmospheric pressure. The syrupy
residue crystallized within 1 day in a refrigerator.
3-(Acetylsulfanyl)butanal 1,1-dimethylhydra-
zone (VII). Thiolacetic acid, 4.0 g, was added drop-
wise to 5.5 g of hydrazone III. Therewith, the tem-
perature of the reaction mixture was maintained at 20
25 C. The mixture was fractionated in a vacuum to
obtain 8.3 g (90%) of compound VII as a colorless
1
Yield 4.8 g (96%). IR spectrum, , cm : 780, 800,
1
oily liquid. IR spectrum, , cm : 1595 (C=N), 1680
1090, 1120 (Si O C), 1600 (C=N).
(C=O).
In a similar way, from 5.0 g of compound XII and
2.5 g of tris(2-hydroxyethyl)amine we obtained 5.5 g
(94%) of 3-(2-silatranylethylsulfanyl)butanal 1,1-
dimethylhydrazone (XIV) as a thick light yellow
syrup.
A similar procedure was used to obtain 3-(benzoyl-
sulfanyl)butanal 1,1-dimethylhydrazone (VIII)
from 5.5 g of hydrazone III and 7.0 g of thiolbenzoic
1
acid. Yield 10.1 g (82%). IR spectrum, , cm : 1580
(C Carom), 1590 (C=N), 1650 (C=O).
2-[2-(Butylsulfanyl)ethylidene]-1,1,1-trimethyl-
hydrazinium iodide (XVI). A mixture of 1.55 g of
hydrazone II and 1.26 g of methyl iodide was allowed
to stand at room temperature for 24 h. Colorless
crystals formed and were filtered off, washed with
ether, and dried in a vacuum to obtain 1.18 g (42%)
3-Sulfanylbutanal 1,1-dimethylhydrazone (IV).
Methanolic MeONa, 5 6 drops, was added to a solu-
tion of 5.4 g of 3-(acetylsulfanyl)butanal 1,1-dime-
thylhydrazone (VII) in 50 ml of CH3OH, and the mix-
ture was refluxed for 6 h. The solvent was distilled
off at atmospheric pressure, and the residue was frac-
tionated in a vacuum to obtain 3.5 g (83%) of com-
pound IV as a colorless oily liquid. IR spectrum, ,
1
of iodide XVI. IR spectrum, , cm : 1630 (C=C).
2-[3-(Ethylsulfanyl)butylidene]-1,1,1-trimethyl-
hydrazinium iodide (XVII). A solution of 1.3 g of
methyl iodide in 5 ml of ether was added to 1.6 g of
hydrazone II. The mixture was allowed to stand at
room temperature in the dark for 24 h. A precipitate
formed and was filtered off, washed with ether, and
dried in a vacuum to obtain 2.4 g (83%) of iodide
1
cm : 1600 (C=N), 2550 (SH).
3-[(2-Hydroxyethyl)sulfanyl]butanal (IX).
Equimolar mixture of 4.8 g of hydrazone III and 3.4 g
of 2-sulfanylethanol was heated for 3 h at 140 150 C
and then fractionated in a vacuum to isolate 7.1 g
(87%) of compound IX as a colorless oily liquid. IR
1
XVII as light yellow flakes. IR spectrum, , cm :
1
spectrum, , cm : 1600 (C=N), 3400 (OH).
1620 (C=N).
In a similar way, from 5.5 g of hydrazone III and
6.0 g of (ethoxycarbonyl)methanethiol we obtained
9.9 g (85%) of 3-(ethoxycarbonylsulfanyl)butanal
2-[3-(Phenylsulfanyl)butylidene]-1,1,1-trime-
thylhydrazinium iodide (XVIII). Hydrazone VI,
1.5 g, and 1.5 g were mixed at room temperature.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

(BUTYLSULFANYL)ETHANAL AND 3-(ORGANYLSULFANYL)BUTANAL
899
After 5 min the mixture warmed up from 25 to 40 C.
It was cooled to room temperature and allowed to
stand for 2 h in the dark. A precipitate formed and
was filtered off, washed with ether, and dried in a
vacuum to obtain 2.14 g (87%) of compound XVIII.
ground, washed with ether, and dried in a vacuum to
obtain 4.9 g (89%) of diiodomethylate XXV as light
1
yellow fine crystals. IR spectrum, , cm : 1630
(C=N).
3-[2-(Trimethoxysilyl)ethylsulfanyl]butanal
1,1-dimethylhydrazone diiodomethylate (XXVI).
Methyl iodide, 3.5 g, was added to a solution of 3.0 g
of hydrazone XII in 5 ml of CH3OH. The mixture was
allowed to stand for 24 h in the dark. The solvent and
excess methyl iodide were removed in a vacuum. The
residue was washed with ether and then subjected to
a vacuum (1 2 mm Hg) for 1 h to obtain 5.6 g
(96%) of diiodomethylate XXVI as a light yellow
syrup.
In a similar way, from 1.9 g of hydrazone VII and
2.0 g of methyl iodide we obtained 3.2 g (96%) of
2-[3-(acetylsulfanyl)butylidene]-1,1,1-trimethyl-
hydrazinium iodide (XIX) [IR spectrum,
,
1
cm : 1630 (C=N), 1680 (C=O)] and from 2.5 g of
hydrazone VIII and 2.5 g of methyl iodide, 3.6 g
(91%) of 2-[3-(benzoylsulfanyl)butylidene]-1,1,1-
trimethylhydrazinium iodide (XX) [IR spectum, ,
1
cm : 1580 (C=Carom), 1600 (C=N), 1660 (C=O)].
2-[3-[2-(Hydroxyethyl)sulfanyl]butylidene]-
1,1,1-trimethylhydrazinium iodide (XXI). A solu-
tion of 2.0 g of hydrazone IX in 5 ml of ether was
mixed with a solution of 1.5 g of methyl iodide in
5 ml of ether. The reaction mixture was allowed to
stand in the dark for 24 h. The ether layer was
decanted, and the syrupy residue was treated with
ether (3.5 ml) and exposed to a vacuum of 1
2 mm Hg for 1 h to obtain 2.5 g (72%) of com-
pound XXI as a viscous yellowish oil.
Reaction of 3-[2-(trimethoxysilyl)ethylsulfa-
nyl]butanal 1,1-dimethylhydrazone diiodome-
thylate (XXVI) with tris(2-hydroxyethyl)amine. A
solution of 0.8 g of tris(2-hydroxyethyl)amine in 2 ml
of CH3OH was added to a stirred solution of 3.0 g of
diiodomethylate XXVI in 3 ml of CH3OH. When
slight heat release ceased ( 5 min), the mixture was
cooled to 0 C. White fine crystals formed and were
filtered off, washed with ether, and dried in a vacuum
to obtain 1.3 g of tris(2-hydroxyethyl)amine hydro-
iodide (mp 166 167 C). The mother liquor was
diluted with ether to isolate 0.9 g of 2-(but-2-enyl-
idene)-1,1,1-trimethylhydrazinium iodide (XXXIII).
In a similar way, from 2.0 g of hydrazone X and
1.2 g of methyl iodide we synthesized 2.1 g (75%) of
2-[3-(ethoxycarbonylmethylsulfanyl)butylidene]-
1,1,1-trimethylhydrazinium iodide (XXII) (viscous
yellowish oil), from 2.0 g of hydrazone XI and 1.3 g
of methyl iodide, 3.9 g (78%) of 2-[3-[(trimethoxy-
silyl)methylsulfanyl]butylidene]-1,1,1-trimethyl-
hydrazinium iodide (XXIII) (viscous yellowish oil),
and from 2.5 g of hydrazone XII and 1.2 g of methyl
iodide, 2.8 g (76%) of 2-[3-[2-(trimethoxysilyl)ethyl-
sulfanyl]butylidene]-1,1,1-trimethylhydrazinium
iodide (XXIV) (viscous yellowish oil).
2-(But-2-enylidene)-1,1,1-trimethylhydrazinium
iodide (XXXIII). Methyl iodide, 7.1 g, was added to
a stirred solution of 5.6 g of hydrazone III in 5 ml of
isopropanol. When slight heat release ceased ( 5 min),
fine crystals formed and were washed with ether and
dried in a vacuum to obtain 12.4 g (98%) of iodide
XXXIII.
Reaction of 1,1,1-trimethylhydrazonium iodide
(XXI) with methyl iodide. Methyl iodide, 2.5 g, was
added to a solution of 2.5 g of iodide XXI in 3 ml of
CH3OH. The mixture was allowed to stand for 72 h
in the dark. Fine crystals formed and were separated,
washed with ether, and dried in a vacuum to obtain
0.7 g (46%) of 1,1,1-trimethylhydrazinium iodide
(XXVII), mp 236 C (decomp.). Found, %: C 18.08;
H 5.12; I 62.30; N 13.27. C3H11IN2. Calculated, %: C
2-[3-(2-Silatranylethylsulfanyl)butylidene]-1,1,1-
trimethylhydrazinium iodide (XXXI). Methyl
iodide, 0.5 g, was added at 20 C to a stirred solution
of 1.2 g of hydrazone XIV in 5 ml of chloroform. The
mixture was allowed to stand at room temperature in
the dark for 2 h, after which the solvent was removed
in a vacuum to obtain 1.55 g (97%) of compound
XXXI as a viscous yellowish oil.
1
17.83; H 5.48; I 62.80; N 13.86. H NMR spectrum
(CD3OD), , ppm: 3.38 s (9H, 3CH3).
3-(Ethylsulfanyl)butanal 1,1-dimethylhydrazone
diiodomethylate (XXV). Methyl iodide, 3.5 g, was
added to a stirred solution of 2.1 g of hydrazone V in
5 ml of CH3OH. The mixture was allowed to stand
for 24 h in the dark, and the solvent and excess
methyl iodide were removed. The syrupy residue was
subjected to a vacuum (2 mm) at 50 C until it crys-
tallized. The solid reaction product was thoroughly
ACKNOWLEDGMENTS
The authors express their gratitude to N.A. Keiko
for providing (butylsulfanyl)ethanal (I).
The work was financially supported by the Inter-
national Science and Technology Center (grant
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

900
SOROKIN et al.
no. 427) and Council for Grants of the President of
the Russian Federation (grant no. NSh-1129-2003.3).
Agric. Biol. Chem., 1990, vol. 54, no. 4, p. 1007.
11. Shibahara, S., Kondo, S., Maeda, K., and Umeza-
wa, H., J. Am. Chem. Soc., 1972, vol. 94, no. 12,
p. 4353.
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