Reaction of 2-(2-cyanoethyl)-1,1-dimethylhydrazine with prop-2-ynyl bromide, 1,3-dibromopropyne, and allyl bromide

Article abstract of DOI:10.1023/A:1021634130964

The reactions of 2-(2-cyanoethyl)-1,1-dimethylhydrazine with prop-2-ynyl bromide, 1,3-dibromopropyne, and allyl bromide involve alkylation by a tertiary nitrogen atom to form 2-(2-cyanoethyl)-1,1-dimethyl-1-(prop-2-ynyl)-, 1-(3-bromoprop-1-ynyl)-2-(2-cyanoethyl)-1,1-dimethyl-, and 1-allyl-2-(2-cyanoethyl)-1,1-dimethylhydrazinium bromides.

Full text of DOI:10.1023/A:1021634130964

Russian Journal of General Chemistry, Vol. 72, No. 9, 2002, pp. 1433 1434. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 9, 2002,
pp. 1520 1522.
Original Russian Text Copyright
2002 by Karnaukhova, Nakhmanovich, Larina, Lopyrev.
Reaction of 2-(2-Cyanoethyl)-1,1-dimethylhydrazine
with Prop-2-ynyl Bromide, 1,3-Dibromopropyne,
and Allyl Bromide
R. V. Karnaukhova, A. S. Nakhmanovich, L. I. Larina, and V. A. Lopyrev
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received December 18, 2000
Abstract The reactions of 2-(2-cyanoethyl)-1,1-dimethylhydrazine with prop-2-ynyl bromide, 1,3-dibro-
mopropyne, and allyl bromide involve alkylation by a tertiary nitrogen atom to form 2-(2-cyanoethyl)-1,1-
dimethyl-1-(prop-2-ynyl)-, 1-(3-bromoprop-1-ynyl)-2-(2-cyanoethyl)-1,1-dimethyl-, and 1-allyl-2-(2-cyano-
ethyl)-1,1-dimethylhydrazinium bromides.
Among diverse transformations of 1,1-dimethyl-
hydrazine and its derivatives, quaternization reactions
with alkenyl and alkynyl halides have not yet received
sufficient study.
absolute methanol at room temperature we obtained
2-(2-cyanoethyl)-1,1-dimethyl-1-(prop-2-ynyl)hyd-
1
razinium bromide (IIIa) in 63% yield. The H and
13C NMR spectra showed that the quaternization has
occurred by a tertiary nitrogen atom.
The reaction of 1,1-dimethylhydrazine with prop-2-
ynyl bromide in diethyl ether, leading to 1,1-dimethyl-
1-(prop-2-ynyl)hydrazinium bromide (yield 59%) has
been reported [1]. The reactions of 1,1-dimethylhyd-
razine with allyl chloride and prop-2-ynyl chloride in
MeCN have been used to obtain 1-allyl-1,1-dimethyl-
hydrazinium chloride (yield 90%) and 1,1-dimethyl-1-
(prop-2-ynyl)hydrazinium chloride (yield 55%) [2].
1-Ethynyl-1,1-dimethylhydrazinium chloride has been
prepared by the reaction of chloroethyne with 1,1-di-
methylhydrazine (70 80 C) [3]. 1-Aroyl-2-bromo-
ethynes have been reported to react with 1,1-dimethyl-
hydrazine at 20 C in MeCN to give 1-(1-bromo-2-
aroylvinyl)-1,1-dimethylhydrazinium bromide [4].
The reaction of compound I with 1,3-dibromopro-
pyne (IIb) in absolute ethanol at 20 C gave 1-(3-
bromoprop-2-ynyl)-2-(2-cyanoethyl)-1,1-dimethyl-
hydrazinium bromide (IIIb) in 75% yield. Here, too,
the alkylation involves a tertiary nitrogen atom and
the CH2Br group of 1,3-dibromopropyne (IIb). This
reaction might be expected to provide the isomeric
1-(3-bromoprop-2-ynyl)-2-(2-cyanoethyl)-1,1-di-
1
methylhydrazinium bromide (IV), but in the H NMR
spectra of compounds IIIa and IIIb we observed
identical proton signals of the N+CH2 group at 4.65
and 4.72 ppm, and in the 13C NMR spectra, indentical
carbon signals of the N+CH2 group at
57.35 and
58.32 ppm. Consequently, in the reactiCon of com-
pound I with dibromopropyne IIb, like in the reaction
with prop-2-ynyl bromide, the tertiary nitrogen atom
is alkylated by the BrCH2 group, yielding bromide
IIIb.
Proceeding with studies on alkylation of 1,1-di-
methylhydrazine derivatives with haloalkynes and
haloalkenes [5, 6], we reacted 2-(2-cyanoethyl)-1,1-
dimethylhydrazine (I) with prop-2-ynyl bromide,
1,3-dibromopropyne, and allyl bromide (IIa IIc).
The reaction of allyl bromide (IIb) with compound
I in acetonitrile at 20 C gave 1-allyl-2-cyanoethyl-1,1-
dimethylhydrazinium bromide, too, via alkylation by
a tertiary nitrogen atom (yield 66%).
Me2NNHCH2CH2CN + RCH2Br
I
IIa IIc
+
+
Me2NNHCH2CH2CN
Me2NNHCH2CH2CN
CH2R Br
IIIa IIIc
1
C CCH2Br
Br
The CH signal in the H NMR spectrum of com-
pound IIIa overlaps with a strong signal of the N+Me2
IV
group, as evidenced by the enhanced integral intensity
1
of this signal. The H NMR spectra of compounds
R = HC C (a), BrC C (b), CH2=CH (c).
IIIa IIIc in DMSO-d6 show a characteristic triplet
NH proton signal in the region of 6.94 7.04 ppm,
split by coupling with protons of the neighboring CH2
By the reaction of 2-(2-cyanoethyl)-1,1-dimethyl-
hydrazine (I) with prop-2-ynyl bromide (IIa) in
1070-3632/02/7209-1433$27.00 2002 MAIK Nauka/Interperiodica

1434
KARNAUKHOVA et al.
group. In the spectra of compounds IIIa and IIIb we
found no NH proton signals because of the fast proton
exchange with the solvent.
1.98 g of 1,3-dibromopropyne (IIb) in 20 ml of ab-
solute ethanol was slowly added with stirring to a
solution of 1.13 g of compound I in 15 ml of absolute
ethanol. The mixture was stirred at 20 C for 5 h and
cooled to 0 C. The precipitate that formed was filtered
off and washed on the filter with cold ethanol to ob-
tain 2.32 g (75%) of compound IIIb as yellow crys-
EXPERIMENTAL
The IR spectra were obtained on a Specord IR-75H
1
1
spectrometer in KBr. The H and 13C NMR spectra
tals, mp 137 138 C. IR spectrum, , cm : 1070
were measured on a Bruker DPX-400 spectrometer
(400 and 100 MHz, respectively), internal reference
(C N), 2210 (C C), 2250 (CN), 2950 (CH2), 3010
(CH3), 3140 (NH). H NMR spectrum (DMSO-d6), ,
1
1
HMDS. The H and 13C chemical shifts were mea-
ppm (J, Hz): 2.73 t (2H, CH2CN, J 6.4), 3.24 d.t (2H,
CH2NH, J 7.5, J 6.4), 3.36 s [6H, N+(CH3)2], 4.72 s
(2H, N+CH2), 7.04 t (1H, NH, J 7.5); (CD3OD):
2.74 t (2H, CH2CN, J 6.3), 3.33 t (2H, CH2NH, J 6.3),
3.43 s [6H, N+(CH3)2], 4.73 s (2H, N+CH2). 13C NMR
spectrum (CD3OD), C, ppm: 17.39 (CH2CN), 40.79
(CH2NH), 53.62 [N+(CH3)2], 56.66 ( CBr), 58.32
(N+CH2), 68.87 (C ), 119.11 (CN). Found, %: C
31.14; H 4.30; Br 51.31; N 13.58. C8H13Br2N3. Cal-
culated, %: C 30.89; H 4.21; Br 51.39; N 13.51.
sured accurate to within 0.01 and 0.02 ppm, respec-
tively, and the J values, to within 0.1 Hz. The spectra
of compounds IIIa and IIIb were assigned using two-
dimensional 1H 13C spectra (XH CORR) and 13C
NMR spectra without proton decoupling and with
DEPT-45 editing.
2-(2-Cyanoethyl)-1,1-dimethylhydrazine (I).
Acrylonitrile, 8.7 g, was slowly added to a stirred
solution of 15 g of 1,1-dimethylhydrazine in 30 ml of
water. The mixture was stirred for 2 h at 20 C and
vacuum-sublimed collecting a fraction with bp 78
80 C (3 mm), yield 15.2 g (54%), n2D5 1.4380 {bp
2-(2-Cyanoethyl)-1,1-dimethyl-1-(prop-2-ynyl)-
hydrazinium bromide (IIIc). A solution of allyl
bromide (IIc) in 15 ml of acetonitrile was slowly
80 90 C (3 mm), n2D5 1.4410 [5]}. Found, %: C 52.92; added with stirring to a solution of 3 g of compound I
H 9.80; N 37.30. C5H11N3. Calculated, %: C 53.07;
H 9.80; N 37.13.
in 20 ml of acetonitrile. The mixture was stirred at
20 C for 4 h and cooled to 0 C. The precipitate that
formed was filtered off and washed on the filter with
cold acetonitrile to obtain 4 g (66%) of compound
IIIc as yellow crystals, mp 114 116 C. IR spectrum,
2-(2-Cyanoethyl)-1,1-dimethyl-1-(prop-2-ynyl)-
hydrazinium bromide (IIIa). A solution of 3.1 g of
prop-2-ynyl bromide (IIa) in 20 ml of absolute me-
thanol was slowly added to a solution of 3 g of com-
pound I in 20 ml of absolute methanol. The mixture
was stirred at 20 C for 0.5 h and cooled (0 C). The
precipitate that formed was filtered off, washed on the
filter with cold methanol, and dried in a vacuum to
obtain 3.9 g (63%) of compound IIIa as rose crystals,
1
, cm : 1020 (C N), 1590 (C=C), 2950 (CH2), 3020
1
(CH3), 3150 (NH). H NMR spectrum (DMSO-d6), ,
ppm (J, Hz): 2.79 t (2H, CH2CN, J 6.4), 3.22 d.t (2H,
CH2NH, J 7.5, J 6.4), 3.31 s [6H, N+(CH3)2], 4.30 s
(2H, N+CH2), 6.94 t (1H, NH, J 7.5). Found, %: C
41.02; H 6.84; Br 34.27; N 17.88. C8H16BrN3. Cal-
culated, %: C 41.04; H 6.89; Br 34.13; N 17.95.
1
mp 150 151 C. IR spectrum, , cm : 1020 (C N),
2140 (C C), 2260 (CN), 2940 (CH2), 2970 (CH3),
3180 (NH). H NMR spectrum (DMSO-d6), , ppm
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1
(J, Hz): 2.73 t (2H, CH2CN, J 6.4), 3.24 d.t (2H,
CH2NH, J 7.5, J 6.5), 3.35 s [6H, N+(CH3)2], 3.36 m
(1H, CH), 4.65 d (2H, N+CH2, J 2.4), 6.99 t (1H,
NH, J 7.5); (CD3OD): 2.74 t (2H, CH2CN, J 6.3),
3.35 t (2H, CH2NH, J 6.3), 3.45 s [6H, N+(CH3)2],
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3.46 m (1H, CH), 4.63 d (2H, N+CH2, J 2.4). 13C
NMR spectrum (CD3OD), C, ppm (J, Hz): 17.38
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1
1
(CH2CN, J 134.0), 40.79 (CH2NH, J 137.3), 53.59
[N+(CH3)2, J 145.82], 57.35 (N+CH2, 1J 147.61),
72.16 (C ), 83.82 ( CH, J 257.3), 119.12 (CN).
1
1
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Found, %: C 41.23; H 6.14; Br 34.35; N 18.03.
C8H14BrN3. Calculated, %: C 41.39; H 6.08; Br 34.43;
N 18.11.
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1-(3-Bromoprop-2-ynyl)-2-(2-cyanoethyl)-1,1-
dimethylhydrazinium bromide (IIIb). A solution of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002