Reactions of 1-[benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines with 1,3-dibromopropyne, 2-propynyl bromide, and allyl bromide

Article abstract of DOI:10.1023/B:RUJO.0000013127.32367.38

Reactions of 1-[benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines with 1,3-dibromopropyne in MeOH at 50°C afforded 2-phenyl(heteryl)-6- bromomethylidene-4,4-dimethyl-5H-1,3,4-oxadiazinium bromides. Reactions of 1-[benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines with

Full text of DOI:10.1023/B:RUJO.0000013127.32367.38

Russian Journal of Organic Chemistry, Vol. 39, No. 11, 2003, pp. 1561 1564. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 11, 2003,
pp. 1631 1634.
Original Russian Text Copyright
2003 by Nakhmanovich, Karnaukhova, Larina, Ushakov, Lopyrev.
Reactions of 1-[Benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines
with 1,3-Dibromopropyne, 2-Propynyl Bromide,
and Allyl Bromide
A. S. Nakhmanovich, R. V. Karnaukhova, L. I. Larina, P. E. Ushakov,
and V. A. Lopyrev
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Scienses, Irkutsk, 664033 Russia
Received October 9, 2002
Abstract Reactions of 1-[benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines with 1,3-dibromopropyne in MeOH at
50 C afforded 2-phenyl(heteryl)-6-bromomethylidene-4,4-dimethyl-5H-1,3,4-oxadiazinium bromides.
Reactions of 1-[benzoyl(2-hetaroyl)]-2,2-dimethyhydrazines with propargyl bromide and allyl bromide gave
rise to 1,1-dimethyl-1-(2-propyn-1-yl)- and 1,1-dimethyl-1-(2-propen-1-yl)-2-benzoyl(hetaroyl)hydrazinium
bromides. On treating these compounds with NaOH solution the corresponding imides were obtained.
Quaternization of 1,1-dimethylhydrazine and its
derivatives with alkynyl and alkenyl halides up till
now remains relatively poorly studied.
The known reactions of 1,1-dimethylhydrazine
with propargyl bromide [1] and propargyl chloride
[2] afford 1,1-dimethyl-1-(2-propynyl)hydrazinium
bromide or chloride. Aroylethynyl bromides with
1,1-dimethylhydrazine give rise to 1-(2-aroyl-1-
bromovinyl)-1,1-dimethylhydrazinium bromides [3].
In reactions of 1,1-dimethylhydrazones with proparg-
yl bromide and 1,3-dibromopropyne the correspond-
ing bromides of 1,1-dimethyl-1-(2-propynyl)hydr-
azonium and 1,1-dimethyl-1-(3-bromo-2-propynyl)-
hydrazonium were obtained in 30 72% yield [4].
R = Ph (a); thienyl-2 (b); furyl-1 (c).
As a result of amide-imide tautomerism bromides
We established that reactions of 1-benzoyl-, 1-(2-
thenoyl)-, and 1-(2-furoyl)-2,2-dimethylhydrazines
(Ia c) with 1,3-dibrompropyne carried out in an-
hydrous methanol at 50 C furnished 2-phenyl(heter-
yl)-6-bromomethylidene-4,4-dimethyl-5H-1,3,4-oxa-
diazinium bromides (IIa c) in 68 87% yield.
A in the methanol solution formed intermediates B
which under the synthesis conditions readily under-
went cyclization into 1,3,4-oxadiazinium bromides
IIa c.
1
The structure of the latter was proved by IR, H
and 13C NMR spectra.
In the first stage hydrazines Ia c were alkylated
with 1,3-dibrompropyne at the tertiary nitrogen giv-
ing 1-benzoyl(hetaroyl)-2-(3-bromo-2-propyn-1-yl)-
2,2-dimethylhydrazinium bromides (A) which we
failed to isolate.
1-Benzoyl(hetaroyl)-2,2-dimethylhydrazines Ia c
also actively reacted with propargyl bromide and allyl
We previously [4] proved in the study of reactions
between 1,1-dimethylhydrazones and 1,4-dibromo-
propyne or propargyl bromide that the tertiary nitro-
gen atom was alkylated exclusively by the CH2Br
group.
R= Ph, R = HC C (III); R= 2-thienyl, R = HC C
(IV); R = 2-furyl, R = HC C (V); R = Ph, R =
CH2=CH (VI); R= 2-thienyl, R = CH2=CH (VII);
R = 2-furyl, R
= CH2=CH (VIII).
1070-4280/03/3911-1561$25.00 2003 MAIK Nauka/Interperiodica

1562
NAKHMANOVICH et al.
bromide in anhydrous MeOH at 50 C affording in
good yield (55 72%) bromides III VIII.
and 3.0 g (0.05) mol of 1,1-dimethylhydrazine in
30 ml of anhydrous THF at 40 C. Yield of compound
Ic 3.7 g (60%). Colorless crystals, mp 110 112 C
In contrast to intermediates B bromides III VIII
under the same conditions did not undergo intra
molecular cyclization into substituted 1,3,4-oxadi-
azinium bromides. This fact is apparently due to the
lack of polarization of the triple bond in compounds
III V and double bond in compounds VI VIII unlike
the triple bond in the CH2 C CBr moiety of inter-
mediates B, and the nucleophilic addition of OH
group to the C C and C=C bonds in compounds III
VIII failed to occur.
1
(from MeCN). IR spectrum, , cm : 3230 (NH);
1658 (C=O). Found, %: C 54.66; H 6.35; N 18.46.
C7H10N2O2. Calculated, %: C 54.55; H 6.49;
N 18.18.
2-Phenyl-6-bromomethylidene-4,4-dimethyl-5H-
1,3,4-oxadiazinium bromide (IIa). To a solution of
1.64 g (0.01 mol) of 1-benzoyl-2,2-dimethylhydr-
azine (Ia) in 30 ml of anhydrous methanol was added
at stirring a solution of 3.58 g (0.01 mol) of 1,3-di-
bromopropyne in 20 ml of anhydrous methanol, the
mixture was heated to 50 C, and stirred at this
temperature for 4 h. On cooling the reaction mixture
to 0 C the separated precipitate was filtered off,
washed on the filter with cold ether, and dried in a
vacuum. Yield of compound IIa 3.81 g (73%), color-
Thus the reaction of 1-[benzoyl(2-hetaroyl)]-2,2-
dimethyhydrazines (Ia c) with 1,3-dibromopropyne
opens up new way to the synthesis of substituted
1,3,4-oxadiazinium bromides IIa c.
EXPERIMENTAL
1
less crystals, mp 148 149 C. IR spectrum, , cm :
Compounds synthesized were studied by the use of
multidimensional (1D, 2D) multinuclear (1H, 13C)
NMR spectroscopy. The spectra were registered at
20 C from solutions in DMSO-d6 on spectrometer
Bruker DPX-400 at operating frequencies 400.13 (1H)
and 100.62 (13C) MHz with accuracy of chemical
shifts measurements of 0.01 and 0.02 ppm respective-
ly, the coupling constants determined with accuracy
of 0.1 Hz. HMDS was used as internal reference. The
signals assignment in the spectra was made using
two-dimensional 1H 13C spectra (XH-CORR).
2955 (CH2), 1612 (C=N), 1570 (C=C), 695 (C Br).
1H NMR spectrum (DMSO-d6), , ppm: 3.58 s (6H,
2CH3), 4.95 s (2H, CH2), 6.82 s (1H, =CHBr), 7.68
8.02 m (5H, Ph). 13C NMR spectrum (DMSO-d6), ,
ppm: 55.9 (CH3), 57.4 (CH2), 94.8 (CHBr),
124.8 134.5 (Ph), 139.4 (C=CHBr), 157.8 (C=N).
Found, %: C 39.70; H 3.66; Br 44.38; N 8.12.
C12H14Br2N2O. Calculated, %: C 39.78; H 3.87;
Br 44.20; N 7.93.
2-(2-Thienyl)-6-bromomethylidene-4,4-dimethyl-
5H-1,3,4-oxadiazinium bromide (IIb) was prepared
in the similar way as compound IIa from 1.7 g
(0.01 mol) of 1-(2-thenoyl)-2,2-dimethylhydrazine
(Ib) and 3.58 g (0.01 mol) of 1,3-dibromopropyne.
Yield of compound IIb 3.59 g (68%). Colorless
IR spectra were recorded on Specord 75IR instru-
ment from samples pelletized with KBr.
1-Benzoyl-2,2-dimethylhydrazine
(Ia)
was
prepared by previously described procedure [5] from
3.0 g (0.05 mol) of 1,1-dimethylhydrazine and 7.05 g
(0.05 mol) of benzoyl chloride in 30 ml of benzene at
20 C. Yield 2.27 g (28%). Colorless crystals, mp
1
crystals, mp 136 138 C. IR spectrum, , cm : 2950
(CH2), 1600 (C=N), 1565 (C=C), 730 (C Br), 690
(C S). 1H NMR spectrum (DMSO-d6), , ppm:
3.50 s (6H, 2CH3), 4.89 d (2H, CH2), 6.78 s (1H,
1
106 107 C (from CCl4). IR spectrum, , cm : 3205
3
3
(NH), 1645 (C=O). Found, %: C 65.72; H 7.22;
N 17.11. C9H12N2O. Calculated, %: C 65.83;
H 7.37; N 17.06.
=CHBr), 7.32 d.d (1H, H3, J 5, J 3.4 Hz), 7.88
(1H, H4, 3J 3.4 Hz), 8.09 (1H, H2, 3J 5 Hz).
13C NMR spectrum (DMSO-d6), , ppm: 56.0 (CH3),
57.9 (CH2), 95.05 (=CHBr), 128.66 (C2), 128.80
(C5), 133.32 (C3), 135.04 (C4), 139.26 ( C=),
154.56 (C=N). Found, %: C 32.35; H 3.15; Br
43.65; N 7.82; S 8.73. C10H12Br2N2OS. Calculated,
%: C 32.61; H 3.26; Br 43.48; N 7.61; S 8.70.
1-(2-Thenoyl)-2,2-dimethylhydrazine (Ib) was
prepared from 4.41 g (0.03 mol) of 2-thenoyl
chloride and 3.0 g (0.05) mol of 1,1-dimethylhydr-
azine in 30 ml of anhydrous THF at 40 C. Yield of
compound Ib 4.43 g (87%). Light-yellow crystals,
1
mp 122 123 C (from MeCN). IR spectrum, , cm :
2-(2-Furyl)-6-bromomethylidene-4,4-dimethyl-
5H-1,3,4-oxadiazinium bromide (IIc) was prepared
in the similar way as compound IIa from 1.54 g
(0.01 mol) of 1-(2-furoyl)-2,2-dimethylhydrazine (Ib)
and 3.58 g (0.01 mol) of 1,3-dibromopropyne. Yield
of compound IIc 4.45 g (87%). Colorless crystals,
3220 (NH), 1655 (C=O), 680 (C S). Found, %:
C 49.35; H 6.06; N 16.41; S 18.70. C7H10N2OS.
Calculated, %: C 49.41; H 5.88; N 16.47; S 18.82.
1-(2-Furoyl)-2,2-dimethylhydrazine (Ic) was
prepared from 5.24 g (0.04 mol) of 2-furoyl chloride
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003

REACTIONS OF 1-[BENZOYL(2-HETAROYL)]-2,2-DIMETHYHYDRAZINES
1563
1
mp 141 142 C. IR spectrum, , cm : 2920 (CH2),
1-(2-Furoyl)-2,2-dimethyl-2-(2-propyn-1-yl)-2-
hydrazinium bromide (V) was prepared in the same
way as compound III from 1.54 g (0.01 mol) of 1-(2-
1
1610 (C=N), 1560 (C=C), 710 (C Br). H NMR
spectrum (DMSO-d6), , ppm: 3.44 s (6H, 2CH3),
4.84 d (2H, CH2), 6.77 t (1H, CH), 6.84 d.d (1H, H4, furoyl)-2,2-dimethylhydrazine (Ic) and 1.99
g
(0.01 mol) of propargyl bromide. Yield of bromide
V 1.98 g (56 %). Colorless crystals, mp 129 130 C.
3J 3.7, J 1.8 Hz), 7.41 d.d (1H, H3, 3J 3.7, J
0.7 Hz), 8.14 d.d (1H, H5, 3J 1.8, 4J 0.7 Hz).
13C NMR spectrum (DMSO-d6), , ppm: 56.09
(CH3), 58.08 (CH2), 95.12 (CH), 113.13 (C3),
118.84 (C4), 139.00 (C2), 140.53 ( C=CHBr),
148.93 (C5), 150.61 (C=N). Found, %: C 34.37;
H 3.33; Br 45.65; N 8.02. C10H12Br2N2O2. Calculat-
ed, %: C 34.09; H 3.41; Br 45.45; N 7.95.
3
4
1
IR spectrum, , cm : 3310 (NH), 3020 (CH2), 2125
1
(C C), 1688 (C=O). H NMR spectrum (DMSO-d6),
3
, ppm: 3.71 s (6H, 2CH3), 4.11 t (1H, CH, J
3
2.2 Hz), 5.10 d (2H, CH2, J 2.2 Hz), 6.76 d.d (1H,
3
3
3
H4, J 3.5, J 1.7 Hz), 7.43 (1H, H3, J 3.5 Hz),
8.05 (1H, H5, 3J 1.7 Hz). 13C NMR spectrum
(DMSO-d6), , ppm: 55.04 (CH3), 57.45 (CH2),
71.83 ( C ), 83.72 ( CH), 112.56 (C4), 118.25
(C3), 143.82 (C2), 147.66 (C5), 156.26 (C=O).
Found, %: C 44.15; H 4.55; Br 29.26; N 10.05.
C10H13BrN2O2. Calculated, %: C 43.96; H 4.76;
Br 29.30; N 10.26.
1-Benzoyl-2,2-dimethyl-2-(2-propyn-1-yl)-2-hydr-
azinium bromide (III). To a solution of 1.64 g
(0.01 mol) of 1-benzoyl-2,2-dimethylhydrazine (Ia)
in 25 ml of anhydrous methanol was slowly added at
stirring a solution of 1.99 g (0.01 mol) of propargyl
bromide in 15 ml of anhydrous methanol, the mixture
was heated to 50 C, and stirred at this temperature
for 4 h. The solvent was evaporated in a vacuum, the
oily residue was dissolved in a little of methanol and
bromide III was precipitated from solution by adding
cold ethyl ether. The precipitate was filtered off and
dried in a vacuum. Yield 2.14 g (59%). Colorless
crystals, mp 125 126 C (from MeCN). IR spectrum,
1-Benzoyl-2, 2-dimethyl-2-(2-propen-1-yl)-2-
hydrazinium bromide (VI) was prepared in the same
way as compound III from 1.64 g (0.01 mol) of
hydrazine Ia and 1.68 g (0.01 mol) of allyl bromide.
Yield of bromide VI 2.26 g (68 %). Colorless
crystals, mp 133 134 C (from MeCN). IR spectrum,
1
, cm : 3445 (NH); 3020, 2945 (CH2), 1684
, cm : 3280 (NH), 2920 (N+ CH2), 2140 (C C),
1680 (C=O). H NMR 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.
(C=O), 1582 (C=C). H NMR spectrum (CDCl3),
1
1
1
, 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. Calculat-
ed, %: C 50.52; H 5.96; Br 28.07; N 9.82.
1-(2-Thenoyl)-2,2-dimethyl-2-(2-propen-1-yl)-2-
hydrazinium bromide (VII) was prepared in the
same way as compound III from 1.7 g (0.01 mol) of
1-(2-thenoyl)-2,2-dimethylhydrazine (Ib) and 1.68 g
(0.01 mol) of propargyl bromide. Yield of bromide
VII 2.43 g (72 %). Colorless crystals, mp 134
1-(2-Thenoyl)-2,2-dimethyl-2-(2-propyn-1-yl)-2-
hydrazinium bromide (IV) was prepared in the same
way as compound III from 1.7 g (0.01 mol) of 1-(2-
thenoyl)-2,2-dimethylhydrazine (Ib) and 1.99
(0.01 mol) of propargyl bromide. Yield of bromide
g
1
IV 2.03 g (55 %). Light-yellow crystals, mp 127
129 C (from MeCN). IR spectrum, , cm ): 3295
136 C (from MeCN). IR spectrum, , cm : 3450
1
(NH), 3042, 2975 (CH2), 1670 (C=O), 1548 (C=C),
1
(NH), 2940 (CH2), 2140 (C C), 1680 (C=O), 685
685 (C S). H NMR spectrum (DMSO-d6), , ppm:
(C S). 1H NMR spectrum (DMSO-d6), , ppm:
3.68 m (6H, 2CH3), 4.69 s (2H, CH2, J 7.3 Hz),
3
3
3
3.73 m (6H, 2CH3), 4.09 s (1H, CH, J 2.1 Hz),
5.66 d.d (2H, CH2, J 16.6, J 9.9 Hz), 6.03 (1H,
5.12 d (2H, CH2, J 2.1 Hz), 7.25 d.d (1H, H4, J 5,
3
3
CH), 7.25 d.d (1H, H4, J 5, J 3.8 Hz), 7.91 d.d
3
3
3J 3.2 Hz), 7.94 (1H, H3, J 3.2 Hz), 8.01 d (1H,
3
(1H, H3, J 3.8, J 1 Hz), 8.01 d.d (1H, H5, J 5,
4J 1 Hz). 13C NMR spectrum (DMSO-d6), , ppm:
54.75 (CH3), 68.38 (CH2), 125.43 (CH), 128.21
(=CH2), 128.31 (C4), 132.43 (C5), 134.16 (C6),
134.40 (C2), 160.41 (C=O). Found, %: C 41.02;
H 4.95; Br 27.78; N 9.42; S 11.22. C10H15BrN2OS.
Calculated, %: C 41.24; H 5.15; Br 27.49; N 9.62;
S 11.00.
3
4
3
H5, 3J 5 Hz). 13C NMR spectrum (DMSO-d6),
,
ppm: 54.95 (CH3), 57.29 (CH2), 71.98 (CH2 C ),
83.61 ( CH), 128.36 (C4), 132.56 (C3), 134.04 (C2),
134.44 (C3), 163.45 (C=O). Found, %: C 41.22;
H 5.53; Br 27.79; N 9.88; S 11.32. C10H13BrN2OS.
Calculated, %: C 41.52; H 4.50; Br 27.68; N 9.69;
S 11.07.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003

1564
NAKHMANOVICH et al.
1-(2-Furoyl)-2,2-dimethyl-2-(2-propen-1-yl)-2-
N 10.02. C10H15BrN2O2. Calculated, %: C 43.64;
H 5.45; Br 29.09; N 10.18.
hydrazinium bromide (VIII) was prepared in the
same way as compound III from 1.54 g (0.01 mol)
of 1-(2-furoyl)-2,2-dimethylhydrazine (Ic) and 1.68 g
(0.01 mol) of allyl bromide. Yield of compound VIII
2.29 g (71 %). Colorless crystals, mp 127 128 C
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vol. 12, p. 801.
1
(from MeCN). IR spectrum, , cm : 3448 (NH),
3024, 2980 (CH2), 1676 (C=O), 1568 (C=C).
2. Konig, K.H. and Zeeh, B., Chem. Ber., 1970, vol. 103,
p. 2052.
1H NMR spectrum (DMSO-d6), , ppm: 3.71 s (6H,
3
2CH3), 4.74 d (2H, CH2, J 7.2 Hz), 5.64 d.d (2H,
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3
3
CH2, J 17, J 9.9 Hz), 6.02 m (1H, CH), 6.75 d.d
3
3
(1H, H4, J 3.7 Hz), 7.46 (1H, H3, J 3.7 Hz), 8.05
3
(1H, H5, J 3.7 Hz), 11.20 s (1H, NH). 13C NMR
spectrum (DMSO-d6), , ppm: 54.77 (CH3), 68.43
(CH2), 112.42 (C4), 117.94 (C3), 125.33 (=CH),
128.23 (=CH2), 143.85 (C2), 147.41 (C5), 156.15
(C=O). Found, %: C 43.48; H 5.68; Br 29.31;
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003