Synthesis of N,N-diethylhydrazine and its reactions with carboxylic acids and alkyl halides

Article abstract of DOI:10.1007/s11176-005-0499-0

N,N-Diethylhydrazine was synthesized by a modified procedure via nitrosation of diethylamine, followed by reduction of the resulting N-nitrosodiethylamine with zinc amalgam in a hydrochloric acid medium. Reactions of N, N-diethylhydrazine with carboxylic acids and alkyl halides resulted in formation of the corresponding hydrazinium salts.

Full text of DOI:10.1007/s11176-005-0499-0

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Russian Journal of General Chemistry, Vol. 75, No. 11, 2005, pp. 1720 1722. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 11, 2005,
pp. 1802 1805.
Original Russian Text Copyright
2005 by K. Akhmedov, Tadzhimukhamedov, U. Akhmedov.
Synthesis of N,N-Diethylhydrazine and Its Reactions
with Carboxylic Acids and Alkyl Halides
K. N. Akhmedov, Kh. S. Tadzhimukhamedov, and U. Ch. Akhmedov
Mirzo Ulugbek National University of Uzbekistan, Vuzgorodok, Uzbekistan, Tashkent, Uzbekistan
Received September 9, 2004
Abstract N,N-Diethylhydrazine was synthesized by a modified procedure via nitrosation of diethylamine,
followed by reduction of the resulting N-nitrosodiethylamine with zinc amalgam in a hydrochloric acid
medium. Reactions of N,N-diethylhydrazine with carboxylic acids and alkyl halides resulted in formation of
the corresponding hydrazinium salts.
Hydrazine and N,N-dialkylhydrazines possess two
highly reactive centers. Depending on the conditions,
reactions with hydrazine derivatives could involve one
or another nitrogen atom or hydrogen atoms. Some
hydrazine derivatives are widely known as pesticides
and medicines; among these, trialkylhydrazinium
halides [1, 2], N,N-dimethylsuccinohydrazide [3 5],
2,4-dihydroxyacetophenone N,N-dimethylhydrazone
[6], isonicotinic acid hydrazide, N-acetyl-p-amino-
benzaldehyde thiosemicarbazone [4], etc., may be
noted.
N,N-Diethylhydrazine was brought into reactions
with chloroacetic, oxalic, and o-, m- and p-nitro-
benzoic acids. The reactions were carried out by heat-
ing equimolar mixtures of the reactants in anhydrous
ethanol for 3 h. The corresponding salts II VI were
obtained in 10, 15, 22, 28, and 24% yield, respec-
tively (Scheme 1). The yield was increased by 6 8%
when the reaction time was prolonged to 6 h. By
heating the reactants in boiling anhydrous benzene
for 3 h we obtained hydrazinium salts II VI in 23,
49, 45, 51, and 48% yield, respectively. The reactions
with 1.2 equiv of N,N-diethylhydrazine afforded 29,
65, 60, 68, and 64% of salts II VI, respectively. The
optimal reaction time was 3 h. Further extending the
reaction time or raising the amount of N,N-diethyl-
hydrazine did not affect the yield of the target product.
The conversion of carboxylic acids was not complete,
and they were partially recovered from the reaction
mixtures.
In the present work we synthesized N,N-diethyl-
hydrazine and examined its reactions with some car-
boxylic acids and alkyl halides. We succeeded in im-
proving the procedure for the preparation of N-nitro-
sodiethylamine [7 9] which is intermediate product
in the synthesis of N,N-diethylhydrazine. The high
yield of N-nitrosodiethylamine was achieved via
addition of sulfuric or hydrochloric acid to a solution
of diethylamine and sodium nitrite. The yield rises as
the amount of the nitrosating agent increases; the
maximal yield (86%) was attained with the use of
1.6 mol of sodium nitrite per mole of diethylamine.
Further raising the amount of the nitrosating agent did
not affect the product yield. N-Nitrosodiethylamine
was isolated from the reaction mixture by extraction
with benzene or diethyl ether.
Scheme 1.
(C2H5)2NNH2 + RCO2H
[(C2H5)2N+ HNH2] OOCR,
I
II VIII
II, R = ClCH2; III, R = CO2H; IV, R = o-O2NC6H4; V,
R = m-O2NC6H4; VI, R = p-O2NC6H4; VII, R =
p-HOC6H4; VIII, R = p-H2NC6H4.
The best results in the reduction of N-nitrosodi-
ethylamine were obtained using zinc amalgam in
hydrochloric acid [7]. Despite variation of the condi-
tions, we did not succeed in preparing N,N-diethyl-
hydrazine in more than 52% yield. Presumably, the
reduction product is formed in a relatively poor yield
owing to hydrolytic cleavage of initial N-nitrosodi-
ethylamine to diethylamine hydrochloride and nitrous
acid; the latter is then reduced to ammonia [7], nitro-
gen(IV) oxide, and probably nitrogen(II) oxide.
No salt formation was observed on heating an
equimolar mixture of N,N-diethylhydrazine with p-
hydroxy- or p-aminobenzoic acid in boiling anhydrous
ethanol for 3 h. The reaction in ethyl acetate afforded
the corresponding salts VII and VIII in 64 and 63%
yield, respectively. The unreacted acids were re-
covered from the reaction mixtures. In the reaction of
p-hydroxybenzoic acid with excess N,N-diethylhydra-
zine (1.6 mol), the yield of salt VII was 94%.
1070-3632/05/7511-1720 2005 Pleiades Publishing, Inc.

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SYNTHESIS OF N,N-DIETHYLHYDRAZINE AND ITS REACTIONS
1721
Table 1. IR spectra and elemental analyses of N,N-diethylhydrazinium salts II XI
Found, %
Calculated, %
Comp.
no.
1
IR spectrum,
or , cm
Formula
C
H
N
C
H
N
II
III
IV
3000, 3100 (NH2), 2000 (N+H), 1500 (COO )
51.63 10.16 16.50 C7H15N2O2
52.17 9.31 17.30
40.91 6.81 15.93
3145, 3270 (NH2), 2470 (N+H), 1300, 1620 (COO ) 40.28 7.60 15.43 C6H12N2O4
3240, 3350 (NH2), 2480 (N+H), 1580 (C=C, C
arom.), 1340, 1500 (NO2); : 730 (1,2-C6H4)
C
50.12 6.73 16.40 C10H17N3O4 49.32 6.76 17.24
V
3150, 3250 (NH2), 2260, 2580 (N+H), 1580 (COO ), 50.16 6.74 16.45 C10H17N3O4 49.32 6.76 17.24
1500 (C=C, C C arom.), 1330, 1550 (NO2); : 805,
880 (1,3-C6H4)
VI
3230, 3330 (NH2), 2470 (N+H), 1320, 1500 (NO2), 50.10 6.80 16.55 C10H17N3O4 49.32 6.76 17.24
1585 (C=C, C Carom); : 850 (1,4-C6H4)
VII 3000, 3140 (NH2), 2570 (N+H), 1530 (COO ), 1595 56.85 9.23 12.71 C10H18N2O3 56.07 8.41 13.07
(C=C, C Carom); : 840 (1,4-C6H4)
VIII 3260, 3320 (NH2), 2920 (N+H), 1280, 1360 (COO ), 56.98 9.76 20.35 C10H19N3O2 56.33 8.92 19.71
1590 (C=C, C Carom); : 800 (1,4-C6H4)
IX
3070, 3170 ( 1620) (NH2), 2955 (1390,
1440) 35.79 8.82 13.89 C6H17BrN2
1435) 12.53 12.52 38.96 C7H19BrN2
1430) 36.43 7.69 10.80 C8H21IN2
36.54 8.05 14.23
12.24 13.27 38.83
36.39 7.72 10.29
(C2H5), 2325, 2925 (N+ NH2)
X
3070, 3190 ( 1600) (NH2), 2545 (1385,
(C2H5), 2315, 2455 (N+ NH2)
XI
3100, 3200 ( 1600) (NH2), 2940 (1370,
(C2H5), 2040, 2410 (N+ NH2)
1
The reactions of N,N-diethylhydrazine with ethyl
bromide, propyl bromide, and butyl iodide were
carried out by mixing equimolar amounts of the re-
actants at room temperature and subsequent keeping
of the mixture for 24 h at room temperature. The
alkylation products (compounds IX XI) were isolated
in 68, 45, and 43% yield, respectively. The yields
were increased to 97, 96, and 80%, respectively, by
performing the reactions with 1.5 equiv of N,N-di-
ethylhydrazine under stirring. The optimal reaction
time was 3 h (Scheme 2.)
monium moiety. In the H NMR spectra of N,N,N-
triethylhydrazinium bromide (IX) and N,N-diethy-
lhydrazinium p-nitrobenzoate (VI), the CH3 and CH2
signals were displaced upfield relative to the corres-
ponding signals of N,N-diethylhydrazine due to salt
formation.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Specord
1
1
IR75 spectrometer (400 4000 cm ). The H NMR
spectra were obtained on a Varian XL-100/15 spec-
trometer (100 MHz) from solutions in D2O (slow
scan mode) using HMDS as internal reference (the
chemical shifts were measured with an accuracy
of 1 ppm) and on a Tesla BS567A instrument
(100 MHz) from solutions in CD3CO2D and
(CD3)2SO using HMDS as internal reference.
Scheme 2.
+
I + RX
[(C2H5)2NRNH2]X ,
IX XI
IX, R = Et; X, R = Pr; XI, R = Bu; IX, X, X = Br; XI,
X = I.
N-Nitrosodiethylamine was obtained in 86% yield.
bp 172 176 C, n2D0 1.4376; published data: yield 74%
[8], bp 176.9 C, n2D0 1.4379 [10]). N,N-Diethylhydra-
zine was synthesized by reduction of N-nitrosodiethyl-
amine with zinc amalgam in hydrochloric acid. Yield
The structure of hydrazinium salts II XI was con-
firmed by their elemental compositions and IR and
1H NMR spectra (Tables 1, 2). Salts II XI showed in
the IR spectra absorption bands due to stretching vib-
rations of free N H bonds and ammonium (N+ H and
N+ R) fragments. The N H stretching vibration fre-
quency in the IR spectra of II XI was lower by 100
52%, bp 96 101 C, n2D0 1.4280; published data [10]:
yield 60%, bp 99.0 99.2 C, n2D0 1.4213.
1
300 cm than the corresponding frequency of initial
N,N-diethylhydrazine [3] due to effect of the am-
N,N-Diethylhydrazinium chloroacetate (II).
A solution of 1.3 ml of diethylhydrazine (I) and
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1722
AKHMEDOV et al.
1
Table 2. H NMR spectra of N,N-diethylhydrazinium salts
II XI, , ppm
from compound I and p-aminobenzoic acid. Yield
94%, mp 129 130 C (from ethyl acetate).
N,N,N-Triethylhydrazinium bromide (IX). N,N-
Diethylhydrazine (I), 3.29 ml, was slowly mixed with
1.49 ml of ethyl bromide. The mixture was heated to
70 C, stirred for 3 h at that temperature, and kept for
12 h at 20 C. The precipitate was dried in a desiccator
over calcium chloride and recrystallized from an-
hydrous benzenea. Yield 3.8 g (97%), mp 135 136 C.
Comp. CH2CH3, t, CH2CH3,
H
arom, m
no.
6H
q, 4H
II
1.15 1.26
1.19 1.28
1.15 1.30
1.16 1.29
1.00 1.20
0.83 1.15
0.82 1.10
1.22 1.32
1.24 1.38
1.22 1.37
3.11 3.25
3.20 3.30
3.14 3.33
3.10 3.30
2.86 3.10
2.40 2.70
2.33 2.55
3.38 3.60
3.21 3.60
3.30 3.60
III
IV
V
VI
VII
VIII
IX
X
7.53 7.80
7.50 8.64
7.90 8.20
6.12 7.88
6.38 7.63
N,N-Diethyl-N-propylhydrazinium bromide (X)
was synthesized in a similar way from compound I
and propyl bromide. Yield 96%, mp 138 139 C (from
benzene).
0.80 0.97 ta
0.79 0.96 ta
N-Butyl-N,N-diethylhydrazinium iodide (XI)
was synthesized in a similar way from compound I
and butyl iodide. Yield 80%, mp 79 80 C (from
benzene).
XI
a
3H, CH [CH CH CH , CH (CH ) ].
3
3
2
2
3
2 3
0.94 g of chloroacetic acid in 20 ml of anhydrous
benzene was heated for 3 h under reflux (on a water
bath). The solvent was distilled off, and the thick
residue was dried in a desiccator over calcium chlo-
ride and recrystallized from acetone. Yield 0.5 g
(29%), mp 215 C.
REFERENCES
1. Ioffe, B.V., Kuznetsov, M.A., and Potekhin, A.A.,
Khimiya organicheskikh proizvodnykh gidrazina
(Chemistry of Organic Hydrazine Derivatives),
Leningrad: Khimiya, 1979, p. 224.
2. Kuznetsova, V.P., Polyakova, L.P., Massalitino-
va, T.N., Koshakova, A.V., and Ovchinnikov, P.N.,
Zh. Prikl. Khim., 1987, vol. 60, no. 2, p. 432.
3. Grekov, A.P., Organicheskaya khimiya gidrazina
(Organic Chemistry of Hydrazine), Kiev: Tekhnika,
1966, p. 75.
4. Fedorova, N.M., Primenenie gidrazina v razlichnykh
otraslyakh narodnogo khozyaistva (Applications of
Hydrazine in Industry and Agriculture), Leningrad:
Leningr. Gos. Univ., 1957, p. 35.
5. Shchukina, M.N. and Sygaeva, T.P., Khim. Nauka
Promst., 1956, no. 1, p. 419.
6. US Patent no. 3362994, 1968; Ref. Zh., Khim., 1970,
no. 1 N 740.
7. Ioffe, B.V., Zh. Obshch. Khim., 1958, vol. 28, no. 5,
p. 1296.
8. Hickinbottom, W.J., Reactions of Organic Com-
pounds, London: Longmans, Green and Co., 1936.
Translated under the title Reaktsii organicheskikh
soedinenii, Moscow: ONTI, 1939, p. 371.
9. Organic Syntheses, Blatt, A.H., Ed., New York:
Wiley, 1943, Collect. vol. 2. Translated under the title
Sintezy organicheskikh preparatov, Moscow: Inostran-
naya Literatura, 1949, vol. 2, p. 199.
N,N-Diethylhydrazinium oxalate (III) was syn-
thesized in a similar way from compound I and oxalic
acid. Yield 65%, mp 138 C (from ethyl acetate).
N,N-Diethylhydrazinium o-nitrobenzoate (IV)
was synthesized in a similar way from compound I
and o-nitrobenzoic acid. Yield 60%, mp 64 65 C
(from benzene).
N,N-Diethylhydrazinium m-nitrobenzoate (V)
was synthesized in a similar way from compound I
and m-nitrobenzoic acid. Yield 68%, mp 71 72 C
(from benzene).
N,N-Diethylhydrazinium p-nitrobenzoate (VI)
was synthesized in a similar way from compound I
and p-nitrobenzoic acid. Yield 64%, mp 139 140 C
(from heptane).
N,N-Diethylhydrazinium p-hydroxybenzoate
(VII). N,N-Diethylhydrazine (I), 1.76 ml, was added
to a solution of 1.38 g of p-hydroxybenzoic acid in a
minimal volume of ethyl acetate, and the mixture was
kept for 12 h at 20 C. The precipitate was filtered off
and recrystallized from ethyl acetate. Yield 2.1 g
(94%), mp 142 143 C.
10. Svoistva organicheskikh soedinenii: Spravochnik
(Properties of organic Compounds. Handbook), Po-
tekhin, A.A., Ed., Leningrad: Khimiya, 1984, p. 131.
N,N-Diethylhydrazinium p-aminobenzoate
(VIII) was synthesized as described above for salt VII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005