Products of the Reactions of 1-Aroyl-2,2-dimethylhydrazines with Propargyl and Allyl Bromides

Article abstract of DOI:10.1023/A:1025644620981

1-Aroyl-2,2-dimethylhydrazines react with propargyl and allyl bromides to form, respectively, 1,1-dimethy1-1-(2-propyn-1-y1)- and 1,1-dimethy1-1-(2- propen-1-y1)-2-aroylhydrazinium bromides. Treatment of these compounds with an NaOH solution yielded, resp

Full text of DOI:10.1023/A:1025644620981

Russian Journal of General Chemistry, Vol. 73, No. 4, 2003, pp. 583 585. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 4, 2003,
pp. 617 619.
Original Russian Text Copyright
2003 by Nakhmanovich, Nizovtseva, Karnaukhova, Komarova, Albanov, Lopyrev.
Products of the Reactions of 1-Aroyl-2,2-dimethylhydrazines
with Propargyl and Allyl Bromides
A. S. Nakhmanovich, T. V. Nizovtseva, R. V. Karnaukhova,
T. N. Komarova, A. I. Albanov, and V. A. Lopyrev
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received April 4, 2001
Abstract 1-Aroyl-2,2-dimethylhydrazines react with propargyl and allyl bromides to form, respectively,
1,1-dimethyl-1-(2-propyn-1-yl)- and 1,1-dimethyl-1-(2-propen-1-yl)-2-aroylhydrazinium bromides. Treatment
of these compounds with an NaOH solution yielded, respectively, N-[dimethyl(2-propyn-1-yl)ammonio]- and
N-[dimethyl(2-propen-1-yl)ammonio]aroylimides.
Among diverse transformations of 1,1-dimethyl-
hydrazine and its derivatives, quaternization with
alkenyl and alkynyl halides is still poorly studied.
The reaction of 1,1-dimethylhydrazine with propargyl
bromide in diethyl ether gave 1,1-dimethyl-1-(2-prop-
yn-1-yl)hydrazinium bromide in 59% yield [1]. The
reactions of 1,1-dimethylhydrazine with allyl and
propargyl chlorides in MeCN gave, respectively, 1,1-
dimethyl-1-allylhydrazinium chloride (yield 90%) and
1,1-dimethyl-1-(2-propyn-1-yl)hydrazinium chloride
(yield 55%) [2]. 1-Aroyl-2-bromoacetylenes react
with 1,1-dimethylhydrazine in MeCN at 20 C to form
1-(1-bromo-2-aroylvinyl)-1,1-dimethylhydrazinium
bromides [3]. The reactions of 1,1-dimethylhydra-
zones with propargyl bromide and 1,3-dibromoprop-
yne in diethyl ether, MeCN, or benzene at 20 C gave
the bromides of the corresponding 1,1-dimethyl-
1-(2-propyn-1-yl)hydrazones and 1,1-dimethyl-1-(3-
bromo-2-propyn-1-yl)hydrazones [4] in 30 72%
yields [4].
zinium bromides IIa IIc in 30 59% yield, i.e., alkyla-
tion occurs at the tertiary nitrogen atom.
+
R CH2Br
Me2N NH C R
Me2N NH C R
Br
CH2R
O
O
Ia Ic
IIa IIf
+
NaOH
HBr
Me2N
N C R
CH2R
O
IIIa IIIf
R = Ph, R = HC C (a); R = 4-BrC6H4, R = HC C (b);
R = 2-ClC6H4, R = HC C (c); R = Ph, R = CH2=CH (d);
R = 4-BrC6H4, R = CH2=CH (e); R = 2-ClC6H4, R =
CH2=CH (f).
We have studied the reaction of 1-aroyl-2,2-di-
methylhydrazines Ia Ic with allyl bromide in MeCN
at 20 C. As in the reaction with propargyl bromide,
alkylation occurred at the tertiary nitrogen atom and
yielded 1-aroyl-2,2-dimethyl-2-(2-propen-1-yl)hydra-
zinium bromides IId IIf.
With the aim to further study alkylation of 1,1-di-
methylhydrazine derivatives, we examined the reac-
tion of 1-benzoyl-2,2-dimethylhydrazine Ia, 1-(4-bro-
mobenzoyl)-2,2-dimethylhydrazine Ib, and 1-(2-chlo-
robenzoyl)-2,2-dimethylhydrazine Ic with propargyl
and allyl bromides.
Treatment of IIa IIe with 6 N NaOH at 20 C re-
sulted in elimination of HBr and formation of N-[di-
methyl(2-propyn-1-yl)ammonio]aroylimides IIIa IIIc
and N-[dimethyl(2-propen-1-yl)ammonio]aroylimides
IIId IIIf; their compositions and structures were con-
The starting compounds Ia Ic were prepared by
the reactions of the corresponding acid chlorides with
1,1-dimethylhydrazine in absolute diethyl ether, ben-
zene, and THF at 20 C or with weak heating (35
40 C), following the procedure described in [5].
1
firmed by elemental analysis and by H and 15N NMR
and IR spectroscopy.
EXPERIMENTAL
We found that hydrazines Ia Ic react with propar-
gyl bromide in absolute methanol on heating (50 C)
to form 1-aroyl-2,2-dimethyl-2-(2-propyn-1-yl)hydra-
The IR spectra were taken on a Specord IR-75
1
spectrometer in KBr. The H, 13C, and 15N NMR
spectra were recorded at 20 C on a Bruker DPX-400
1070-3632/03/7304-0583$25.00 2003 MAIK Nauka/Interperiodica

584
NAKHMANOVICH et al.
spectrometer (400.13, 100.62, and 40.54 MHz, respec-
tively); HMDS was used as internal reference.
40.10; H 4.21; Br 44.42; N 7.80. C12H14Br2N2O.
Calculated, %: C 39.81; H 3.89; Br 44.14; N 7.74.
All the compounds are colorless crystals or pow-
ders.
1-(2-Chlorobenzoyl)-2,2-dimethyl-2-(2-propyn-
1-yl)hydrazinium bromide IIc was prepared similarly
to IIa from 3 g of Ic and 1.8 g of propargyl bromide
in absolute methanol at 60 C. Yield 1.42 g (30%),
1-Benzoyl-2,2-dimethylhydrazine Ia was prepared
according to [5] from 3 g of 1,1-dimethylhydrazine
and 7.1 g of benzoyl chloride in benzene at 20 C.
Yield 1.7 g (21%), mp 106 107 C (from CCl4). IR
mp 142 144 C (from chloroform). IR spectrum,
,
1
cm : 3275 (NH), 3082 (N+CH2), 2130 (C C), 1675
(C=O). 1H NMR spectrum (DMSO-d6), , ppm:
3.72 s (6H, 2CH3), 4.18 m (1H, CH), 5.12 d (2H,
CH2), 7.48 7.61 m (4H, C6H4), 8.12 t (1H, NH).
Found, %: C 45.51; H 4.72; Br 25.32; Cl 11.23; N
8.74. C12H14BrClN2O. Calculated, %: C 45.38; H
4.44; Br 25.16; Cl 11.16; N 8.82.
1
spectrum, , cm : 3190 (NH), 1640 (C=O). Found,
%: C 65.63; H 7.31; N 16.95. C9H12N2O. Calculated,
%: C 65.83; H 7.37; N 17.06.
1-(4-Bromobenzoyl)-2,2-dimethylhydrazine Ib
was prepared from 4.4 g of 4-bromobenzoyl chloride
and 2.4 g of 1,1-dimethylhydrazine in THF at 40 C.
Yield 3.7 g (77%), mp 148 150 C (from MeCN). IR
1-Benzoyl-2,2-dimethyl-2-(2-propen-1-yl)hydra-
zinium bromide IId was prepared similarly from
1.53 g of Ia and 1.21 g of allyl bromide. Yield 1.86 g
(68%), mp 133 134 C (from MeCN). IR spectrum, ,
1
spectrum, , cm : 3200 (NH), 1640 (C=O). Found,
%: C 44.12; H 4.82; Br 32.74; N 11.23. C9H11BrN2O.
Calculated, %: C 44.47; H 4.56; Br 32.87; N 11.52.
1
cm : 3445 (NH), 3020, 2945 (CH2), 1684 (C=O),
1
1-(2-Chlorobenzoyl)-2,2-dimethylhydrazine Ic
was prepared from 7.2 g of 1,1-dimethylhydrazine and
10 g of 2-chlorobenzoyl chloride in THF at 40 C.
Yield 6.9 g (58%), mp 150 152 C (from CCl4). IR
1582 (C=C). H NMR spectrum (CDCl3), , ppm:
3.91 s (6H, 2CH3), 4.97 d (2H, CH2), 5.74 t (2H,
=CH2), 6.02 m (1H, CH), 7.26 8.05 m (5H, C6H5),
11.82 t (1H, NH). Found, %: C 50.88; H 5.65; Br
28.32; N 10.12. C12H17BrN2O. Calculated, %: C
50.52; H 5.96; Br 28.07; N 9.82.
1
spectrum, , cm : 3180 (NH), 1640 (C=O). Found,
%: C 54.30; H 6.01; Cl 18.20; N 14.52. C9H11ClN2O.
Calculated, %: C 54.42; H 5.58; Cl 17.85; N 14.10.
1-(4-Bromobenzoyl)-2,2-dimethyl-2-(2-propen-1-
yl)hydrazinium bromide IIe was prepared similarly
from 2.13 g of Ib and 1.6 g of allyl bromide in MeCN
at 20 C. Yield 2.42 g (65%), mp 138 140 C (from
1-Benzoyl-2,2-dimethyl-2-(2-propyn-1-yl)hydra-
zinium bromide IIa. A solution of 0.7 g of propargyl
bromide in 10 ml of absolute methanol was added
slowly with stirring to a solution of 1 g of 1-benzoyl-
2,2-dimethylhydrazine Ia in 15 ml of absolute meth-
anol. The mixture was stirred at 50 C for 6 h. The
solvent was vacuum-evaporated, and the remaining
oily residue was dissolved in a small amount of meth-
anol. Bromide IIa was precipitated by adding cold
diethyl ether. The precipitate was filtered off and
vacuum-dried. Yield 1.1 g (59%), mp 125 126 C
1
acetone). IR spectrum, , cm : 3452 (NH), 3019,
2951 (CH2), 1695 (C=O), 1590 (C=C), 748 (C Br).
1H NMR spectrum (CDCl3), , ppm: 3.91 s (6H,
2CH3), 4.97 d (2H, NCH2), 5.74 t (2H, CH2), 5.99 m
(1H, CH), 7.55 7.90 m (4H, C6H4), 7.94 t (1H, NH).
Found, %: C 39.31; H 4.28; Br 43.93; N 8.05.
C12H16Br2N2O. Calculated, %: C 39.69; H 4.42; Br
43.89; N 7.69.
1
(from MeCN). IR spectrum, , cm : 3280 (NH),
1
2920 (N+CH2), 2140 (C C), 1680 (C=O). H NMR
1-(2-Chlorobenzoyl)-2,2-dimethyl-2-(2-propen-
1-yl)hydrazinium bromide IIf was prepared similarly
from 3.3 g of Ic and 2.42 g of allyl bromide in
MeCN at 20 C. Yield 4.29 g (75%), mp 104 106 C.
spectrum (CDCl3), , ppm: 2.95 s (6H, 2CH3), 4.04 m
(1H, CH), 5.37 d (2H, CH2), 7.29 7.52 m (5H,
C6H5), 8.13 t (1H, NH). Found, %: C 50.68; H 5.51;
Br 28.09; N 9.75. C12H15BrN2O. Calculated, %:
C 50.90; H 5.34; Br 28.22; N 9.89.
1
IR spectrum, , cm : 3440 (NH), 3080, 2940 (CH2),
1
1680 (C=O), 1620 (C=C), 620 (C Cl). H NMR spec-
trum (CDCl3), , ppm: 3.64 s (6H, 2CH3), 4.68 d
(2H, NCH2), 5.72 t (2H, CH2), 6.07 m (1H, CH),
7.47 7.60 m (4H, C6H4), 12.24 t (1H, NH). Found,
%: C 45.20; H 5.24; Br 25.31; Cl 11.32; N 8.86.
C12H16BrClN2O. Calculated, %: C 45.09; H 5.04;
Br 25.00; Cl 11.09; N 8.76.
1-(4-Bromobenzoyl)-2,2-dimethyl-2-(2-propyn-
1-yl)hydrazinium bromide IIb was prepared similarly
to IIa from 5.81 g of Ib and 2.38 g of propargyl bro-
mide in absolute methanol at 80 C. Yield 2.1 g (29%),
1
mp 158 160 C (from MeOH). IR spectrum, , cm :
3190 (NH), 2921 (N+CH2), 2130 (C C), 1680 (C=O).
1H NMR spectrum (DMSO-d6), , ppm: 3.80 s (6H,
2CH3), 4.15 m (1H, CH), 5.21 d (2H, CH2), 7.81
7.86 m (4H, C6H4), 7.95 t (1H, NH). Found, %: C
N-[Dimethyl(2-propyn-1-yl)ammonio]benzoyl-
imide IIIa. To 0.57 g of IIa we added 2.5 ml of 6 N
NaOH and stirred at 20 C for 2 h. The light yellow
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003

PRODUCTS OF THE REACTIONS OF 1-AROYL-2,2-DIMETHYLHYDRAZINES
585
oily precipitate was extracted with chloroform, and Yield 0.75 g (37%), mp 84 85 C. IR spectrum,
,
1
the extract was dried over MgSO4. The solvent was
evaporated to dryness in a vacuum, and the white
solid residue was ground in a mortar. Yield 0.21 g
cm : 3040, 2980 (CH2), 1640 (C=O), 1590 (C=C),
1
no NH absorption band. H NMR spectrum (DMSO-
d6), , ppm: 3.33 s (6H, 2CH3), 4.35 d (2H, N+CH2),
5.43 m (2H, =CH2), 6.04 m (1H, CH=), 7.24 7.83 m
(5H, C6H5). Found, %: C 70.74; H 8.66; N 13.68.
C12H16N2O. Calculated, %: C 70.59; H 7.84; N 13.72.
1
(51%), mp 94 95 C. IR spectrum, , cm : 2980
(N+CH2), 2120 (C C). 1620 (C=O), no NH absorp-
1
tion band. H NMR spectrum (DMSO-d6), , ppm:
3.32 s (6H, 2CH3), 3.68 t (1H, CH), 4.74 d (2H,
CH2), 7.24 7.87 m (5H, C6H5). Found, %: C 70.71;
H 7.04; N 13.44. C12H14N2O. Calculated, %: C
71.29; H 6.93; N 13.86.
N-[Dimethyl(2-propen-1-yl)ammonio](4-bromo-
benzoyl)imide IIIe was prepared similarly from
2.17 g of IIe. Yield 0.28 g (17%), mp 43 45 C. IR
1
spectrum, , cm : 3040, 2960 (CH2), 1590 (C=O),
N-[Dimethyl(2-propyn-1-yl)ammonio](4-bromo-
benzoyl)imide IIIb was prepared similarly to IIIa
from 0.4 g of IIb. Yield 0.24 g (77%), mp 104
1
1550 (C=C), 760 (C Br), no NH absorption band. H
NMR spectrum (acetone-d6), , ppm: 3.36 s (6H,
2CH3), 4.41 d (2H, N+CH2), 5.45 m (2H, =CH2),
1
106 C. IR spectrum, , cm : 3120 (N+CH2), 2110
6.11 m (1H, CH=), 7.39 7.89 m (4H, C6H4). 15N
NMR spectrum (DMSO-d6), N, ppm: 94.1 (Me2N+),
244.6 (N CO). Found, %: C 50.54; H 5.62; Br 28.32;
N 9.68. C12H15BrN2O. Calculated, %: C 50.90; H
5.33; Br 28.22; N 9.89.
(C C), 1580 (C=O), 760 (C Br), no NH absorption
1
band. H NMR spectrum (CDCl3), , ppm: 2.67 t (1H,
CH), 3.52 s (6H, 2CH3), 4.71 d (2H, CH2), 7.25
8.01 m (4H, C6H4). 15N NMR spectrum (DMSO-d6),
N, ppm: 93.8 (Me2N+), 247.0 (N CO). Found, %:
C 51.45; H 5.04; Br 27.99; N 9.59. C12H13BrN2O.
Calculated, %: C 51.27; H 4.66; Br 28.42; N 9.96.
REFERENCES
N-[Dimethyl(2-propyn-1-yl)ammonio](2-chloro-
benzoyl)imide IIIc was prepared similarly from
1.13 g of IIc. Yield 0.22 g (24%), mp 118 120 C. IR
1. Smith, R.F. and Coffman, K.I., Synth. Commun., 1982,
vol. 12, no. 10, p. 801.
2. Konig, K.H. and Zeeh, B., Chem. Ber., 1970, vol. 103,
1
spectrum, , cm : 2980 (N+CH2), 2110 (C C), 1580
no. 7, p. 2052.
1
(C=O), 650 (C Cl), no NH absorption band. H NMR
3. Elokhina, V.N., Nakhmanovich, A.S., Larina, L.I.,
Shishkin, O.V., Baumer, V.N., and Lopyrev, V.A., Izv.
Ross. Akad. Nauk, Ser. Khim., 1999, no. 8, p. 1536.
spectrum (acetone-d6), , ppm: 3.28 t (1H, CH),
3.48 s (6H, 2CH3), 4.80 d (2H, CH2), 7.17 7.38 m
(4H, C6H4). 15N NMR spectrum (DMSO-d6),
,
N
ppm: 94.5 (Me2N+), 248.5 (N CO). Found, %: C
60.46; H 5.86; Cl 14.97; N 11.62. C12H13ClN2O.
Calculated, %: C 60.89; H 5.53; Cl 14.98; N 11.84.
4. Elokhina, V.N., Nakhmanovich, A.S., Karnaukho-
va, R.V., and Lopyrev, V.A., Zh. Org. Khim., 2000,
vol. 36, no. 4, p. 502.
N-[Dimethyl(2-propen-1-yl)ammonio]benzoyl-
imide IIId was prepared similarly from 2.85 g of IId.
5. Hinman, R.L., J. Am. Chem. Soc., 1956, vol. 78, no. 8,
p. 1645.
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