Reaction of alkyl- and arylamines with 2-(hydroxyimino)-3-oxobutanal

Article abstract of DOI:10.1134/S1070428017010018

The condensation of 2-(hydroxyimino)-3-oxobutanal with primary aliphatic amines, cyclohexanamine, and amines containing an adamantane fragment afforded 4-(alkylamino)- and 4-(cyclohexylamino)-3- nitrosobut-3-en-2-ones. Analogous reaction with substituted anilines RC₆H₄NH₂ (R = H, 4-Me, 4-OMe, 4-NH₂, 4-Br, 4-I, 3-NO₂) led to the formation of 4-aryl-3-hydroxyiminobutan-2-ones.

Full text of DOI:10.1134/S1070428017010018

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 1, pp. 1–5. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.A. Yarofeeva, O.A. Tsutsura, T.A. Frolenko, E.S. Semichenko, A.A. Kondrasenko, G.A. Suboch, 2017, published in Zhurnal
Organicheskoi Khimii, 2017, Vol. 53, No. 1, pp. 9–13.
Reaction of Alkyl- and Arylamines
with 2-(Hydroxyimino)-3-oxobutanal
A. A. Yarofeevaa, O. A. Tsutsuraa, T. A. Frolenkoa, E. S. Semichenkoa,*
A. A. Kondrasenkob, and G. A. Subocha
a Siberian State Technological University, pr. Mira 82, Krasnoyarsk, 660049 Russia
*e-mail: imidazol5@yandex.ru
b Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences,
Akademgorodok 53/24, Krasnoyarsk, 660036 Russia
Received August 31, 2016
Abstract—The condensation of 2-(hydroxyimino)-3-oxobutanal with primary aliphatic amines, cyclohexan-
amine, and amines containing an adamantane fragment afforded 4-(alkylamino)- and 4-(cyclohexylamino)-3-
nitrosobut-3-en-2-ones. Analogous reaction with substituted anilines RC6H4NH2 (R = H, 4-Me, 4-OMe, 4-NH2,
4-Br, 4-I, 3-NO2) led to the formation of 4-aryl-3-hydroxyiminobutan-2-ones.
DOI: 10.1134/S1070428017010018
The direction of reactions of 1,3-dicarbonyl com-
pounds with amines is determined by enolization of
one of the carbonyl groups. For example, unsym-
metrical fluorinated 1,3-diketones react with alkyl-
amines to give Schiff bases through that carbonyl
group which is not linked to fluorinated substituent and
is not enolized [1]. Reactions of fluorinated 1,3-di-
ketones with aromatic amines lead to the formation of
mixtures of isomeric Schiff bases, in which the frac-
tion of the condensation product through the carbonyl
group at the fluorinated substituent is considerably
lower [2].
bases through the ketone carbonyl. However, 3-oxo-
butanal readily undergoes trimerization; therefore, the
corresponding Schiff bases, 4-(alkyl- and dialkyl-
amino)but-3-en-2-ones are synthesized by reaction of
amines with 3-oxobutanal dimethyl acetal [3]. If a hy-
droxyimino group is present in the 2-position of 3-oxo-
butanal, the reaction with R-benzylamines involves the
aldehyde group, and the products are 4-(R-benzyl-
amino)-3-nitrosobut-3-en-2-ones [4].
In this work we studied the reaction of 2-(hydroxy-
imino)-3-oxobutanal with aliphatic and aromatic
amines. An aqueous solution of 2-(hydroxyimino)-3-
oxobutanal (A) was obtained by nitrosation of 3-oxo-
butanal which was prepared in situ by acid hydrolysis
of 4,4-dimethoxybutan-2-one [4, 5]. Amine 1a–1c or
It may be presumed that 3-oxobutanal which is
enolized almost completely should react with amines
in a way similar to activated β-diketones to form Schiff
Scheme 1.
O
RNH2 (1a–1e)
Me
Me
NHR
–H2O
(1) H+/H2O
O
NO
(2) NaNO2, H+
O
OMe
OMe
CHO
NOH
2a–2e
Me
(1) –2MeOH
Me
O
(2) –H2O, –NaCl
ArNH2 (1f–1h)
Ar
A
N
–H2O
NOH
2f–2h
R = Bu (a), t-Bu (b), Cy (c), 1-AdCH2 (d), 1-AdCH(Me) (e); Ar = 4-BrC6H4 (f), 4-IC6H4 (g), 3-O2NC6H4 (h).
1

YAROFEEVA et al.
2
a solution of amine 1d–1g in ethanol was added with
stirring to an aqueous solution of A at 0‒5°C
(Scheme 1). In the reaction with 3-nitroaniline (1h),
aldehyde A was preliminarily extracted with diethyl
ether, and a solution of amine 1h in diethyl ether was
added to the extract. The precipitate of 4-(alkylamino)-
3-nitrosobut-3-en-2-one 2a or 2c–2e or 4-(arylimino)-
3-(hydroxyimino)butan-2-one 2f–2g was filtered off.
Compound 2b was isolated from the reaction mixture
by extraction with methylene chloride.
(CDCl3), the position of signals of the enamine carbon
atom and proton attached thereto depended on the
substituent on the nitrogen atom. The signals shifted
upfield in going from compound 2a (R = Bu; δC 150.2,
δ 8.03 ppm) to 2d [R = Ad-1-CH(Me); δC 148.0,
δ 7.92 ppm] and 2b (R = t-Bu; δC 144.0, δ 7.91 ppm)
possessing bulky substituents on the nitrogen.
The hydroxyimino proton of 2f–2l resonated in the
1H NMR spectra at δ 18.00–17.35 ppm, indicating
formation of intramolecular hydrogen bond with that
1
The condensation of substituted anilines 1i–1l with
2-(hydroxyimino)-3-oxobutanal (A) was carried out in
the presence of acetic acid (Scheme 2); we thus syn-
thesized 4-(arylimino)-3-(hydroxyimino)butan-2-ones
2i–2l. By reaction of 2-(hydroxyimino)-3-oxobutanal
(A) with 2-aminoethane-1-thiol we obtained 1-(hy-
droxyimino)-1-(thiazolidin-2-yl)propan-2-one (3)
(Scheme 2).
proton. The 13C and H signals of the N=CH group of
compounds 2f–2h containing an electron-withdrawing
substituent in the para position of the benzene ring
were located in a stronger field than the corresponding
signals of 2g–2l.
EXPERIMENTAL
The electronic absorption spectra were measured on
a Helios Omega spectrophotometer from solutions in
CHCl3 with concentrations of 5×10–5 (λ 200‒500 nm)
and 5×10–3 M (λ 500‒800 nm); cell path length 1 cm.
Scheme 2.
4-RC6H4NH2 (1i–1l)
AcOH
4-RC6H4
NOH
Me
N
1
The H and 13C NMR spectra were recorded on
A
–H2O
O
a Bruker Avance III 600 spectrometer at the Krasno-
yarsk Joint Regional Center (Siberian Branch, Russian
Academy of Sciences). The progress of reactions was
monitored by TLC on Sorbfil PTSKh-AF-V plates
(Krasnodar, Russia) with fluorescent indicator using
hexane–ethyl acetate (4:1) as eluent. Neutral silica gel
L 100/400 (Chemapol) was used for column chro-
matography.
2i–2l
R = H (i), 4-Me (j), 4-MeO (k), 4-H2N (l).
O
HN
H2NCH2CH2SH
–H2O
A
S
Me
NOH
3
4-(Butylamino)-3-nitrosobut-3-en-2-one (1a).
A mixture of 1.32 g (10 mmol) of 4,4-dimethoxybutan-
2-one and 10 mL (10 mmol) of 1 N aqueous HCl was
stirred for 30 min at 20°C. The mixture was cooled to
0°C, a solution of 0.76 g (11 mmol) of sodium nitrite
in 4 mL of water was added dropwise, the mixture was
freed from nitrogen oxides by keeping for 30 min
under reduced pressure (water-jet pump), 0.657 g
(9 mmol) of butylamine was added dropwise at 0°C,
and the mixture was stirred for 30 min. The light violet
crystals were filtered off. Yield 1.18 g (77%), mp 80‒
82°C. Electronic absorption spectrum, λmax, nm
(ε, L mol–1 cm–1): 259 (8620), 338 (6000), 588 (47).
1H NMR spectrum (CDCl3), δ, ppm: 0.95 t (3H, CH3,
J = 7.34 Hz), 1.39 m (2H, CH2, J = 7.34 Hz), 1.67 q
(CH2, J = 7.52 Hz), 2.61 s (3H, CH3C=O), 3.52 m (2H,
NCH2, J = 5.87 Hz), 8.03 br.s (1H, =CHN), 16.65 br.s
(NH). 13C NMR spectrum (CDCl3), δC, ppm: 13.6
(CH3), 19.9 (CH2), 25.1 (CH3C=O), 31.7 (CH2), 55.3
(NCH2), 150.2 (NCH), 151.1 (CNO), 197.1 (C=O).
The structure of compounds 2a–2l and 3 was con-
firmed by elemental analyses and UV (2a–2e, 2i–2k)
1
and H and 13C NMR spectra. Signals in the NMR
spectra of 2a–2l and 3 were assigned using two-di-
mensional homo- (COSY) and heteronuclear (HSQC,
HMBC) shift correlation techniques.
Compounds 2a–2e in chloroform exist as nitroso
isomers, as follows from the presence in their elec-
tronic spectra of NO absorption band at λ 578‒592 nm
(n–π* transition). This conclusion is consistent with
the spectral parameters of the Schiff base synthesized
from 2-(hydroxyimino)-3-oxobutanal and benzylamine
according to the procedure described in [4].
1
The H NMR spectra of 2a–2e in CDCl3 charac-
teristically displayed a signal at δ 16.6‒16.8 ppm,
which was assigned to NH proton of the secondary
amino group involved in intramolecular hydrogen
1
bond. In the 13C and H NMR spectra of 2a–2e
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 1 2017

REACTION OF ALKYL- AND ARYLAMINES WITH 2-(HYDROXYIMINO)-3-OXOBUTANAL
3
Found, %: C 56.36; H 8.22; N 16.53. C8H14N2O2. Cal-
culated, %: C 56.45; H 8.29; N 16.46.
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min, and a solution of 1.485 g (9 mmol)
of (adamantan-1-yl)methanamine in 8 mL of ethanol
was added dropwise at 0°C. The mixture was stirred
for 30 min, and the precipitate was filtered off. Yield
0.56 g (24%), blue powder, mp 96°C. Electronic
absorption spectrum, λmax, nm (ε, L mol–1 cm–1): 259
4-(tert-Butylamino)-3-nitrosobut-3-en-2-one (2b).
A mixture of 1.32 g (10 mmol) of 4,4-dimethoxybutan-
2-one and 10 mL (10 mmol) of 1 N aqueous HCl was
stirred for 30 min at 20°C. The mixture was cooled to
0°C, a solution of 0.76 g (11 mmol) of sodium nitrite
in 4 mL of water was added dropwise, the mixture was
freed from nitrogen oxides by keeping under reduced
pressure (water-jet pump) for 30 min, 0.657 g
(9 mmol) of tert-butylamine was added dropwise at
0°C, and the mixture was stirred for 30 min and ex-
tracted with 20 mL of methylene chloride. The extract
was dried over sodium sulfate and evaporated under
reduced pressure with addition of 1 mL of hexane. The
oily residue was treated with 2 mL of pentane and kept
for 3 days at ‒18°C, and the dark violet crystals were
filtered off. Yield 0.17 g (11%), mp 51°C. Electronic
absorption spectrum, λmax, nm (ε, L mol–1 cm–1): 258
1
(9200), 339 (6360), 587 (46). H NMR spectrum
(CDCl3), δ, ppm: 1.51 m (6H, CH2-, Ad), 1.63–1.74 m
(6H, CH2, Ad), 2.03 m (3H, CH, Ad), 2.66 s (3H,
CH3C=O), 3.16 s (2H, NCH2), 7.90 d (1H, NCH, J =
7.04 Hz), 16.59 br.s (1H, NH). 13C NMR spectrum
(CDCl3), δC, ppm: 25.2 (CH3C=O), 28.0 (CH, Ad),
33.9 (Ad), 36.6 (CH2, Ad), 40.2 (CH2, Ad), 67.7
(NCH2), 149.9 (NCH), 151.6 (CNO), 197.1 (C=O).
Found, %: C 68.59; H 8.34; N 10.57. C15H22N2O2. Cal-
culated, %: C 68.67; H 8.45; N 10.68.
1
(8120), 336 (5600), 578 (52). H NMR spectrum
(CDCl3), δ, ppm: 1.39 s (9H, t-Bu), 2.64 s (3H,
CH3C=O), 7.91 br.s (1H, =CHN), 16.77 br.s (NH).
13C NMR spectrum (CDCl3), δC, ppm: 25.2
(CH3C=O), 29.0 (CH3), 144.0 (=CHN), 152.1 (CNO),
197.5 (C=O). Found, %: C 56.37; H 8.12; N 16.52.
C8H14N2O2. Calculated, %: C 56.45; H 8.29; N 16.46.
4-[1-(Adamantan-1-yl)ethylamino]-3-nitrosobut-
3-en-2-one (2e). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min, and a solution of 1.611 g (9 mmol)
of 1-(adamantan-1-yl)ethanamine in 8 mL of ethanol
was added dropwise at 0°C. The mixture was stirred
for 30 min, and the light violet powder was filtered off.
Yield 1.15 g (46%), mp 114°C. Electronic absorption
spectrum, λmax, nm (ε, L mol–1 cm–1): 259 (9120), 338
4-(Cyclohexylamino)-3-nitrosobut-3-en-2-one
(2c). A mixture of 1.32 g (10 mmol) of 4,4-dimethoxy-
butan-2-one and 10 mL (10 mmol) of 1 N aqueous HCl
was stirred for 30 min at 20°C. The mixture was
cooled to 0°C, a solution of 0.76 g (11 mmol) of
sodium nitrite in 4 mL of water was added dropwise,
the mixture was freed from nitrogen oxides by keeping
under reduced pressure (water-jet pump) for 30 min,
0.891 g (9 mmol) of cyclohexylamine was added drop-
wise at 0°C, and the mixture was stirred for 30 min.
The precipitate was filtered off. Yield 1.01 g (57%),
blue crystals, mp 90°C. Electronic absorption spec-
trum, λmax, nm (ε, L mol–1 cm–1): 259 (9060), 338
1
(6380), 586 (51). H NMR spectrum (CDCl3), δ, ppm:
1.22 d [3H, CH3CH(Ad), J = 6.79 Hz], 1.48 m (6H,
CH2), 1.61‒1.72 m (6H, CH2), 2.02 m (3H), 2.64 s
(3H, CH3C=O), 2.94 m (1H, CH), 7.92 d (1H, =CHN,
J = 7.20 Hz), 16.62 br.s (1H, NH). 13C NMR spectrum
(CDCl3), δC, ppm: 14.8 (CH3CH), 25.1 (CH3C=O),
28.0 (CHγ, Ad), 35.4 (Cα, Ad), 36.6 (CH2, Ad), 38.4
(CH2, Ad), 71.1 (NCH), 148.0 (=CHN), 151.3 (=CHO),
197.1 (C=O). Found, %: C 69.58; H 8.60; N 10.12.
C16H24N2O2. Calculated, %: C 69.53; H 8.75; N 10.14.
1
(5700), 592 (42). H NMR spectrum (CDCl3), δ, ppm:
1.20–2.00 m (CH2, C6H11), 2.64 s (3H, CH3C=O),
3.31 m (1H, CH, C6H11), 8.02 d (1H, =CHN, J =
4.80 Hz), 16.61 br.s (1H, NH). 13C NMR spectrum
(CDCl3), δC, ppm: 23.9 (CH2), 24.8 (CH2), 25.5
(CH3C=O), 33.2 (CH2), 63.1 (NCH), 147.2 (=CHN),
151.4 (CNO), 197.1 (C=O). Found, %: C 61.20;
H 8.22; N 14.27. C10H16N2O2. Calculated, %: C 61.29;
H 7.97; N 14.23.
4-(4-Bromophenylimino)-3-(hydroxyimino)-
butan-2-one (2f). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
4-[(Adamantan-1-yl)methylamino]-3-nitrosobut-
3-en-2-one (2d). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 1 2017

YAROFEEVA et al.
4
1
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min, and a solution of 1.548 g (9 mmol)
of 4-bromoaniline in 8 mL of ethanol was added drop-
wise at 0°C. The mixture was stirred for 30 min, and
the precipitate was filtered off and dried in air. Yield
1.712 g (71%), dark green crystals, mp 123–125°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.55 s (3H,
CH3C=O), 7.23 m (2H, o-H, J = 8.8 Hz), 7.60 m (2H,
m-H, J = 8.62 Hz), 8.71 s (1H, =CHN), 17.33 br.s
(NH). 13C NMR spectrum (CDCl3), δC, ppm: 24.9
(CH3C=O), 123.2 (Co), 123.5 (Cp), 133.0 (Cm), 144.4
(Ci), 148.0 (C=NOH), 151.1 (CH=N), 196.3 (C=O).
Found, %: C 44.59; H 3.29; Br 29.61; N 10.23.
C10H9BrN2O2. Calculated, %: C 44.63; H 3.37;
Br 29.69; N 10.41.
mp 182‒183°C (from CHCl3). H NMR spectrum
(CDCl3), δ, ppm: 2.58 s (3H, CH3C=O), 7.67 m (1H,
6′-H, J = 7.89 Hz), 7.70 m (1H, 5′-H, J = 7.89 Hz),
8.22 s (1H, 2′-H), 8.28 m (1H, 4′-H, J = 7.52 Hz), 8.82 s
(1H, =CHN), 16.88 br.s (NH). 13C NMR spectrum
(CDCl3), δC, ppm: 24.9 (CH3C=O), 116.5 (C2′), 123.5
(C4′), 127.5 (C5′), 130.6 (C6′), 147.1 (C1′), 147.7
(C=NOH), 148.9 (C3′), 153.8 (CH=N), 196.0 (C=O).
Found, %: C 50.80, 50.64; H 3.80, 3.77; N 17.71.
C10H9N3O4. Calculated, %: C 51.07; H 3.86; N 17.87.
3-(Hydroxyimino)-4-(phenylimino)butan-2-one
(2i). A mixture of 1.32 g (10 mmol) of 4,4-dimethoxy-
butan-2-one and 10 mL (10 mmol) of 1 N aqueous HCl
was stirred for 30 min at 20°C. The mixture was
cooled to 0°C, a solution of 0.76 g (11 mmol) of
sodium nitrite in 4 mL of water was added dropwise,
the mixture was freed from nitrogen oxides by keeping
under reduced pressure (water-jet pump) for 30 min
and cooled to 0°C, and a solution of 0.837 g (9 mmol)
of aniline in 0.54 g (9 mmol) of acetic acid and 6 mL
of water was added dropwise with stirring. The precip-
itate was filtered off. Yield 0.826 g (48%), light green
crystals, mp 88‒90°C. Electronic absorption spectrum,
λmax, nm (ε, L mol–1 cm–1): 244 (9040), 305 (6620).
1H NMR spectrum (CDCl3), δ, ppm: 2.57 s (3H,
CH3C=O), 7.36 m (2H, o-H, J = 7.70 Hz), 7.41 m (1H,
p-H, J = 6.42 Hz), 7.48 m (2H, m-H, J = 8.07 Hz),
8.72 s (1H, HC=N), 17.63 br.s (NH). 13C NMR spec-
trum (CDCl3), δC, ppm: 24.7 (CH3C=O), 121.4 (Co),
129.3 (Cp), 129.6 (Cm), 145.0 (Ci), 148.3 (C=NOH),
150.1 (CH=N), 196.5 (C=O). Found, %: C 63.21;
H 5.22; N 14.67. C10H10N2O2. Calculated, %: C 63.15;
H 5.30; N 14.73.
3-(Hydroxyimino)-4-(4-iodophenylimino)butan-
2-one (2g). A mixture of 1.32 g (10 mmol) of 4,4-di-
methoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min, and a solution of 1.971 g (9 mmol)
of 4-iodoaniline in 8 mL of ethanol was added drop-
wise at 0°C. Yield 1.514 g (53%), light green crystals,
1
mp 134‒136°C. H NMR spectrum (CDCl3), δ, ppm:
2.55 s (3H, CH3C=O), 7.06 m (2H, o-H, J = 8.25 Hz),
7.74 m (2H, m-H, J = 8.07 Hz), 8.72 s (1H, =CHN),
17.27 br.s (NH). 13C NMR spectrum (CDCl3), δC, ppm:
24.6 (CH3C=O), 94.7 (Cp), 123.2 (Co), 138.9 (Cm),
144.9 (Ci), 147.9 (C=NOH), 151.0 (CH=N), 196.2
(C=O). Found, %: C 38.07; H 2.82; I 40.08; N 8.79.
C10H9IN2O2. Calculated, %: C 38.00; H 2.87;
I 40.15; N 8.86.
3-(Hydroxyimino)-4-(4-methylphenylimino)-
butan-2-one (2j). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min and cooled to 0°C, and a solution of
0.963 g (9 mmol) of p-toluidine in 5 mL of water and
0.81 g (13.5 mmol) of acetic acid was added with
stirring. The mixture was stirred for 30 min, a solution
of 0.477 g (4.5 mmol) of sodium carbonate in 5 mL of
water was added, and the precipitate was filtered off.
Yield 1.195 g (65%), light green crystals, mp 106°C.
Electronic absorption spectrum, λmax, nm (ε,
L mol–1 cm–1): 245 (9900), 327 (7340), 600 (9).
1H NMR spectrum (CDCl3), δ, ppm: 2.40 s (3H,
3-(Hydroxyimino)-4-(3-nitrophenylimino)butan-
2-one (2h). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, and the mixture was freed from nitro-
gen oxides by keeping under reduced pressure (water-
jet pump) for 30 min and extracted with 25 mL of
diethyl ether. A solution of 1.242 g (9 mmol) of
3-nitroaniline in 26 mL of diethyl ether was added
dropwise to the extract under vigorous stirring, and the
mixture was stirred for 1 h. The mixture was evaporat-
ed, and the solid residue was recrystallized from
chloroform. Yield 0.241 g (11%), dark green crystals,
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REACTION OF ALKYL- AND ARYLAMINES WITH 2-(HYDROXYIMINO)-3-OXOBUTANAL
5
CH3C6H4), 2.56 s (3H, CH3C=O), 7.27 m (4H, Harom),
8.65 s (1H, HC=N), 17.75 br.s (NH). 13C NMR spec-
trum (CDCl3), δC, ppm: 21.2 (CH3C6H4), 24.7
(CH3C=O), 121.3 (Co), 130.3 (Cm), 139.8 (Cp), 142.1
(Ci), 148.4 (C=NOH), 148.7 (CH=N), 196.6 (C=O).
Found, %: C 64.58; H 5.81; N 13.55. C11H12N2O2.
Calculated, %: C 64.69; H 5.92; N 13.72.
CH3C=O), 4.02 br.s (2H, NH2), 6.71 m (2H, m-H, J =
7.50 Hz), 7.26 (o-H, J = 8.07 Hz), 8.65 s (1H, =CHN),
18.00 br.s (NH). 13C NMR spectrum (CDCl3), δC, ppm:
24.9 (CH3C=O), 115.4 (Co), 123.5 (Cm), 135.2 (Ci),
145.0 (CH=N), 148.4 (C=NON), 148.7 (Cp), 197.0
(C=O). Found, %: C 58.56; H 5.36; N 20.41.
C10H11N3O2. Calculated, %: C 58.53; H 5.40; N 20.48.
1-(Hydroxyimino)-1-(thiazolidin-2-yl)propan-
2-one (3). A mixture of 1.32 g (10 mmol) of 4,4-di-
methoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min and cooled to 0°C, and a solution of
0.693 g (9 mmol) of 2-aminoethane-1-thiol was added
dropwise with stirring. The precipitate was filtered off.
Yield 0.305 g (35%), light yellow powder, mp 109°C
3-(Hydroxyimino)-4-(4-methoxyphenylimino)-
butan-2-one (2k). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C. The
mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min and cooled to 0°C, and a solution of
1.107 g (9 mmol) of p-anisidine in 0.54 g (9 mmol)
of acetic acid and 3.6 mL of water was added under
vigorous stirring. The precipitate was filtered off. Yield
1.656 g (84%), dark yellow crystals, mp 84–85°C.
Electronic absorption spectrum, λmax, nm (ε, L×
1
(from CH2Cl2). H NMR spectrum (CDCl3), δ, ppm:
2.35 s (3H, CH3C=O), 2.97 d.d.d (1H, CH2N, J = 12.1,
9.6, 6.2 Hz), 3.05 d.d.d (1H, CH2S, J = 9.61, 5.72,
6.0 Hz), 3.14 d.d.d (1H, CH2S, J = 9.8, 6.0, 2.0 Hz),
3.71 d.d.d (1H, CH2N, J = 12.1, 6.0, 2.3 Hz), 4.28 br.s
(1H, NH), 5.75 s (1H, NCHS), 12.88 br.s (NOH).
13C NMR spectrum (CDCl3), δC, ppm: 26.3 (CH3C=O),
35.0 (CH2S), 52.4 (CH2N), 60.5 (SCHNH), 152.5
(C=NOH), 198.3 (C=O). Found, %: C 41.34;
H 5.80; N 16.01. C6H10N2O2S. Calculated, %: C 41.36;
H 5.79; N 16.08.
1
mol–1 cm–1): 243 (2940), 352 (3560). H NMR spec-
trum (CDCl3), δ, ppm: 2.55 s (3H, CH3C=O), 3.84 s
(3H, OCH3), 6.97 (2H, m-H, J = 9.0 Hz), 7.36 m (2H,
o-H, J = 9.0 Hz), 8.68 s (1H, CH=N), 17.81 br.s (NH).
13C NMR spectrum (CDCl3), δC, ppm: 24.7 (CH3C=O),
55.5 (OCH3), 115.0 (Cm), 123.3 (Co), 137.7 (Ci), 147.5
(CH=N), 148.5 (C=NOH), 160.9 (Cp), 196.7 (C=O).
Found, %: C 55.91; H 5.42; N 12.63. C11H12N2O3.
Calculated, %: C 59.99; H 5.49; N 12.72.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation in the framework of the base part
of state assignment.
4-(4-Aminophenylimino)-3-(hydroxyimino)-
butan-2-one (2l). A mixture of 1.32 g (10 mmol) of
4,4-dimethoxybutan-2-one and 10 mL (10 mmol) of
1 N aqueous HCl was stirred for 30 min at 20°C.
The mixture was cooled to 0°C, a solution of 0.76 g
(11 mmol) of sodium nitrite in 4 mL of water was
added dropwise, the mixture was freed from nitrogen
oxides by keeping under reduced pressure (water-jet
pump) for 30 min and cooled to 0°C, and a solution of
0.972 g (9 mmol) of benzene-1,4-diamine in 8 mL of
water and 0.59 g (9 mmol) of acetic acid was added
with vigorous stirring. The mixture was stirred for
30 min, and the precipitate was filtered off. Yield
1.22 g (66%). The product was additionally purified by
chromatography in a 50×2-cm column charged with
50 g of silica gel (eluent hexane–ethyl acetate, 5:2).
Light brown powder, mp 149‒151°C (decomp.).
1H NMR spectrum (CDCl3), δ, ppm: 2.55 s (3H,
REFERENCES
1. Pashkevich, K.I., Filyakova, V.I., Sheinker, Yu.N.,
Anisimova, O.S., Postovskii, I.Ya., and Kuleshova, E.F.,
Bull. Acad. Sci. USSR, Div. Chem. Sci., 1979, vol. 28,
p. 1924.
2. Pashkevich, K.I., Filyakova, V.I., and Postovskii, I.Ya.,
Bull. Acad. Sci. USSR, Div. Chem. Sci., 1981, vol. 30,
p. 1931.
3. Maretina, I.A., Russ. J. Org. Chem., 2005, vol. 41, p. 1.
4. Veronese, A.C., Scrimin, P., and Bergamini, P., J. Chem.
Soc., Perkin Trans. 1, 1982, no. 4, p. 1013.
5. Semichenko, E.S., Frolenko, T.A., Root, E.V., and
Suboch, G.A., Russ. J. Org. Chem., 2011, vol. 47, p. 622.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 1 2017