Synthesis and properties of 2-amino-1-chloroenones

Article abstract of DOI:10.1134/S1070428007010022

Reactions of alkyl-, allyl-, and arylamines and o-aminophenol with 1,2-dichlorovinyl alkyl ketones involve replacement of only one chlorine atom in the β-position with respect to the carbonyl group with formation of 2-alkylamino-, 2-allylamino-, and 2-ary

Full text of DOI:10.1134/S1070428007010022

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 1, pp. 35–39. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © G.V. Bozhenkov, V.A. Savosik, A.N. Mirskova, G.G. Levkovskaya, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43,
No. 1, pp. 37–40.
Synthesis and Properties of 2-Amino-1-chloroenones
G. V. Bozhenkov, V. A. Savosik, A. N. Mirskova, and G. G. Levkovskaya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: ggl@irioch.irk.ru
Received February 1, 2006
Abstract—Reactions of alkyl-, allyl-, and arylamines and o-aminophenol with 1,2-dichlorovinyl alkyl ketones
involve replacement of only one chlorine atom in the β-position with respect to the carbonyl group with
formation of 2-alkylamino-, 2-allylamino-, and 2-arylamino-1-chlorovinyl ketones. Diamines of the aromatic
and aliphatic series react with 1,2-dichlorovinyl alkyl ketone molecules to give N,N'-bis(2-acyl-2-chlorovinyl)-
substituted diamines.
DOI: 10.1134/S1070428007010022
β-Aminovinyl ketones attract attention of many
researchers due to their reactivity and sometimes un-
predictable behavior. These compounds are used in the
synthesis of various heterocyclic systems, dyes, and
light-sensitive materials. Different aspects of the
chemistry of β-aminovinyl ketones were the subjects
of numerous publications, including review articles
[1–6]. Methods of synthesis of β-aminovinyl ketones
were summarized in [1–3, 5]. In the recent years,
procedures are extensively developed for regio- and
stereoselective synthesis of aminovinyl ketones con-
taining additional functional groups which could give
rise to versatile chemical transformations.
halovinyl ketone molecules, and the products are the
corresponding N,N'-bis(2-acyl-2-chlorovinyl) deriva-
tives VI and VII formed as a result of nucleophilic
replacement of the β-chlorine atom in the initial vinyl
ketone.
Scheme 1.
O
O
R1
Cl
H
R1
NR2R3
H
+
R2R3NH
Cl
Cl
I–X
I, R1 = Me, R2 = H, R3 = Ph; II, R1 = Me, R2 = H, R3 =
4-MeOC6H4; III, R1 = Me, R2 = H, R3 = CH2=CHCH2;
IV, R1 = Pr, R2 = H, R3 = Ph; V, R1 = Pr, R2 = H, R3 = t-Bu;
VI, R1 = Pr, R2 = H, R3 = PrC(O)CCl=CHNH(CH2)2;
VII, R1 = Pr, R2 = H, R3 = 4-[PrC(O)CCl=CHNH]C6H4;
VIII, R1 = R2 = R3 = Pr; IX, R1 = Et, R2 = Me, R3 = Ph;
X, R1 = Et, R2 = H, R3 = 2-HOC6H4.
While continuing our studies on the reactivity of
alkyl 1,2-dichlorovinyl ketones synthesized previously
[7], we examined their reactions with aliphatic and
aromatic amines. It is known that reactions of alkyl-
amines with 2-chloro- and 2,2-dichlorovinyl ketones
involve replacement of the chlorine atom(s) to give
2-amino- and 2,2-diaminovinyl ketones. Aromatic
amines react with alkyl 2,2-dihalovinyl ketones at both
halogen atoms and carbonyl group, yielding N-aryl-
2,2-bis(arylamino)vinyl ketone imines [8–10].
The reactions were carried out in diethyl ether,
lower alcohols (methanol, ethanol), and DMSO, the
reactant ratio being varied from equimolar to six-fold
excess of the amine. The reactions occurred at 0 to
70°C and were accompanied by strong heat evolution.
In no case we succeeded in obtaining products of
replacement of the chlorine atom in the α-position with
respect to the carbonyl group; likewise, no products of
amine addition at the carbonyl group of the initial
enones were detected.
We have found that reactions of alkyl-, allyl-, and
arylamines and o-aminophenol with alkyl 1,2-dichloro-
vinyl ketones involve replacement of only one chlorine
atom in the β-position with respect to the carbonyl
group, leading to 2-alkyl(aryl, allyl)amino-1-chloro-
vinyl ketones I–V and VIII–X (Scheme 1). Diamines
of the aromatic and aliphatic series, such as ethane-1,2-
diamine and benzene-1,2-diamine, react with two di-
Compounds I–X are stable to storage. Despite the
presence of N–H and C–Cl bonds, aminovinyl ketones
35

BOZHENKOV et al.
36
I–VII and X did not undergo cyclization to aziridine
derivatives under the examined conditions. The reac-
tions of 1,2-dihalo enones with 1,2-ethylenediamine
were not accompanied by intramolecular cyclization of
the initially formed 2-amino-1-chlorovinyl ketone to
the corresponding 1,2,3,4-tetrahydropyrazine or diaze-
pine. 1-Chloro-2-(2-hydroxyphenyl)aminovinyl ketone
X failed to undergo cyclization to 3-butyroyl-1,4-benz-
oxazine (via intramolecular ring closure with participa-
tion of the C–Cl and O–H bonds).
mination of the steric structure of compounds I–X.
Aminovinyl ketones I–VII and X containing a secon-
dary amino group can exist as two isomers stabilized
by intramolecular hydrogen bonds. 2-Aminovinyl
ketones having no substituent in the α-position with
respect to the carbonyl group are known to exist as
mixtures of E and Z isomers, while in weakly polar
solvents the corresponding Z isomers are present ex-
clusively [12–14]. The reason is strong intramolecular
hydrogen bonding (six-membered H-chelate ring).
The chemical properties of 2-amino-1-chlorovinyl
ketones I–X differed from the properties of analogous
2- and 2,2-diaminovinyl ketones having no chlorine
atom in the α-position with respect to the carbonyl
group [8, 9, 11]. Unlike 2-mono- and 2,2-bis(aryl-
amino)vinyl ketones which are known to undergo intra-
molecular cyclization to quinoline derivatives on heat-
ing in polyphosphoric acid (PPA) [8, 9, 11], heating of
compounds I, II, and V in PPA for several hours at
120–180°C did not lead to formation of the corre-
sponding quinolines (Scheme 2).
R3
H
N
O
H
O
R3
R1
R1
Cl
H
Cl
Z, s-cis
E, s-cis
On the other hand, α-bromo-β-aminovinyl trifluoro-
methyl ketones were reported to have Z (s-cis) con-
figuration [6, 15]. The vicinal coupling constant JHH
3
between the olefinic proton and proton of the amino
group in these compounds is equal to 13–14 Hz. In the
1H NMR spectra of I–VII and X, the coupling constant
3JHH changes from 12.8 to 13.3 Hz. Taking into ac-
count structural similarity between α-chloro-β-amino-
vinyl ketones I–X and α-bromo-β-aminovinyl trifluoro-
methyl ketones [6], comparison of the corresponding
1H NMR data suggests that aminovinyl ketones I–VII
and X having a secondary amino group in weakly
polar solvents (CDCl3) also exist mainly as Z/s-cis-
isomers. It should be noted that the chemical shifts of
Scheme 2.
R
O
PPA
120–180°C
Cl
R
HN
H
N
Cl
The structure of aminovinyl ketones I–X was
1
13
studied by IR and H and C NMR spectroscopy and
gas chromatography–mass spectrometry. The mass
spectra of compounds V and VIII contained the
molecular ion peaks. Compounds I–X showed in the
IR spectra strong absorption bands belonging to
stretching vibrations of the carbonyl groups (1645–
1675 cm–1) and C=C (1550–1600 cm–1) and C–H
bonds (3020–3090 cm–1); amines I–VII and X were
also characterized by N–H absorption bands at 3250
and 3250–3380 cm–1. The intensity of the C=C band
considerably exceeded that of the C=O group; presum-
ably, the reason is strong effect of the fluorine atom
and amino group on the electron density distribution in
1-chloro-2-aminoenone molecules.
1
the NH proton and olefinic proton in the H NMR
spectra of compounds I–X strongly depend on the
solvent nature; presumably, this is the result of inter-
molecular interactions.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Specord
75IR spectrometer. The 1H and C NMR spectra were
13
measured on a Bruker DPX-400 spectrometer at
400.13 and 100.61 MHz, respectively, using HMDS as
internal reference. The mass spectra were obtained on
a Shimadzu GCMS-QP5050A instrument.
1
In the H NMR spectra of aminovinyl ketones I–X
3-Chloro-4-phenylaminobut-3-en-2-one (I). Ani-
line, 0.93 g (0.01 mol), was added dropwise under
stirring to a solution of 1.39 g (0.01 mol) of 3,4-di-
chlorobut-3-en-2-one in 15 ml of anhydrous diethyl
ether. The mixture was stirred for 2 h, and the precip-
itate was filtered off, washed with a solution of sodium
carbonate and water, and dried. Yield 1.80 g (87%),
signals from protons in the RC(O) and NR groups and
a singlet (VIII, IX) or doublet (I–VII, X) from the
olefinic protons were present. Analysis of the 1H NMR
spectra indicated that compounds I–X in solution exist
as a single stereoisomer. However, the presence of
only one olefinic proton strongly complicated deter-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

SYNTHESIS AND PROPERTIES OF 2-AMINO-1-CHLOROENONES
37
mp 135–136°C. IR spectrum, ν, cm–1: 3284 (NH);
3050 (=CH), 3000 (CH3), 1675 (C=O), 1600 (C=C).
1H NMR spectrum (CDCl3), δ, ppm: 8.08 d (1H, =CH,
(0.02 mol) of aniline in 10 ml of 50% ethanol. The
mixture was stirred for 1 h at 60°C, cooled, poured
into water, and adjusted to pH 8 by adding a solution
of sodium carbonate. The precipitate was filtered off
and dried. Yield 3.70 g (85%), mp 74–76°C. IR spec-
trum, ν, cm–1: 3330 (NH); 3050 (=CH); 2960, 2925,
2865 (C3H7); 1635 (C=O); 1610 (C=C). 1H NMR spec-
trum (CDCl3), δ, ppm: 8.18 d (1H, =CH, J = 13.2 Hz);
7.39 d, 7.13 t, and 7.09 d (5H, Harom, J = 7.7 Hz);
7.02 br.d (1H, NH, J = 13.2 Hz); 2.72 t (2H, CH2, J =
7.45 Hz); 1.76 m (2H, CH2, J = 7.45 Hz); 1.03 t (3H,
CH3, J = 7.45 Hz). 13C NMR spectrum, δC, ppm:
192.89 (C=O), 141.65, 139.65, 135.27, 129.95, 123.77,
116.22, 107.25, 40.05 (CH2), 18.45 (CH2), 13.96
(CH3). Found, %: C 64.13; H 6.32; Cl 15.91; N 6.28.
C12H14ClNO. Calculated, %: C 64.43; H 6.31;
Cl 15.85; N 6.26.
J = 13.3 Hz); 7.33 t, 7.08 t, and 7.03 d (5H, Harom
,
J = 7.7 Hz); 6.95 br.d (1H, NH, J = 13.3 Hz); 3.36 s
1
(3H, CH3). H NMR spectrum (DMSO-d6), δ, ppm:
9.16 br.d (1H, NH, J = 12.8); 8.25 d (1H, =CH–, J =
12.8); 7.42 d, 7.32 t, and 7.03 t (5H, Harom, J = 7.7 Hz);
2.34 s (3H, CH3). 13C NMR spectrum, δC, ppm: 192.87
(C=O), 139.52, 135.92, 129.99, 123.94, 116.29, 26.00
(CH3). Found, %: C 61.33; H 5.30; Cl 18.45; N 7.21.
C10H10ClNO. Calculated, %: C 61.39; H 5.15;
Cl 18.12; N 7.16.
3-Chloro-4-(4-methoxyphenylamino)but-3-en-2-
one (II). 3,4-Dichlorobut-3-en-2-one, 1.39 g (0.01 mol),
was added dropwise under stirring to a solution of
1.23 g (0.01 mol) of p-methoxyaniline in 20 ml of di-
ethyl ether. The mixture was stirred for 1 h on heating
under reflux, and the precipitate was filtered off,
washed with a solution of sodium carbonate and water,
and dried. Yield 1.50 g (77%), mp 113°C. IR spectrum,
ν, cm–1: 3250 (NH), 3075 (=CH), 3000 (CH3), 1675
1-(tert-Butylamino)-2-chlorohex-1-en-3-one (V).
1,2-Dichlorohex-1-en-3-one, 3.34 g (0.02 mol), was
added dropwise under stirring to a solution of 4.39 g
(0.06 mol) of tert-butylamine in 10 ml of 50% ethanol.
The mixture was stirred for 2 h at 60°C, cooled,
poured into water, adjusted to pH 8 by adding a solu-
tion of sodium carbonate, and extracted with diethyl
ether. The extract was dried over CaCl2 and evaporated
under reduced pressure. Yield 2.44 g (60%). IR spec-
trum, ν, cm–1: 3370–3275 (NH); 3045 (=CH); 2950,
2920, 2890 (Alk); 1645 (C=O); 1600 (C=C). 1H NMR
spectrum (CDCl3), δ, ppm: 7.73 d (1H, =CH, J =
12.8 Hz), 5.27 br.d (1H, NH, J = 12.8 Hz), 2.53 t (2H,
CH2, J = 7.2 Hz), 1.65 m (2H, CH2, J = 7.2 Hz), 1.33 s
(9H, CH3), 0.93 t (3H, CH3, J = 7.2 Hz). 13C NMR
spectrum, δC, ppm: 196.62 (C=O), 146.93, 139.62,
52.48 (CMe3), 30.18 (CMe3), 41.22 (CH2), 18.69
(CH2), 13.82 (CH3). Mass spectrum, m/z (Irel, %): 203
(30) [M]+, 188 (20), 160 (8), 146 (10), 132 (10), 121
(20), 119 (75), 104 (80), 71 (12), 57 (100), 43 (32),
42 (40), 41 (95). Found, %: C 59.05; H 8.98; Cl 17.37;
N 6.85. C10H18ClNO. Calculated, %: C 58.96; H 8.91;
Cl 17.40; N 6.88. M 203.71.
1
(C=O), 1600 (C=C). H NMR spectrum (CDCl3), δ,
ppm: 7.98 d (1H, =CH, J = 13.3 Hz), 6.99 br.d (1H,
NH, J = 13.3 Hz), 6.98 d and 6.87 d (2H each, C6H4,
J = 8.9 Hz), 3.78 s (3H, OCH3); 2.34 s (3H, CH3).
Found, %: C 58.51; H 5.46; Cl 15.72; N 6.24.
C11H12ClNO. Calculated, %: C 58.54; H 5.36;
Cl 15.71; N 6.21.
4-Allylamino-3-chlorobut-3-en-2-one (III).
3,4-Dichlorobut-3-en-2-one, 1.39 g (0.01 mol), was
added dropwise under stirring to a solution of 1.71 g
(0.03 mol) of allylamine in 15 ml of anhydrous diethyl
ether. The mixture was stirred for 3 h, the precipitate
was filtered off, and the filtrate was washed with a so-
lution of Na2CO3 and water, dried over MgSO4, and
distilled. Yield 1.25 g (78%), bp 95–100°C (4–5 mm).
IR spectrum, ν, cm–1: 3310, 3275 (NH); 3010, 3055,
3090 (=CH); 2910, 2825 (Alk); 1650 (C=O); 1600
1
(C=C). H NMR spectrum (CCl4), δ, ppm: E/s-cis:
N,N'-Ethylenebis(1-amino-2-chlorohex-1-en-3-
one) (VI) was synthesized from 1.3 g (0.02 mol) of
ethane-1,2-diamine in 10 ml of 50% ethanol and 1.67 g
(0.01 mol) of 1,2-dichlorohex-1-en-3-one. The mixture
was stirred for 2 h at 60°C, cooled, and poured into
water, and the precipitate was filtered off and dried.
Yield 1.48 g (46%), mp 68–69°C. IR spectrum, ν,
cm–1: 3500–3315 (NH); 3045 (=CH); 2970, 2925,
9.52 br.s (1H, NH), 6.95 d (1H, =CH, J = 12.7 Hz),
6.00 m (1H, =CH), 5.37 t (2H, CH2), 3.95 t (2H, =CH2,
J = 5.5 Hz), 2.32 (3H, CH3); Z/s-cis: 7.57 d (1H, =CH,
J = 12.3 Hz), 6.00 m (1H, =CH), 5.37 t (2H, CH2),
4.05 t (2H, =CH2, J = 5.7 Hz), 2.31 (3H, CH3). Found,
%: C 52.91; H 6.69; Cl 22.40; N 8.89. C7H10ClNO.
Calculated, %: C 52.67; 6.31; Cl 22.21; N 8.78.
1
2-Chloro-1-phenylaminohex-1-en-3-one (IV).
1,2-Dichlorohex-1-en-3-one, 3.34 g (0.02 mol), was
added dropwise under stirring to a solution of 1.87 g
2870 (Alk); 1645 (C=O); 1570 (C=C). H NMR spec-
trum (acetone-d6), δ, ppm: 7.78 d (2H, =CH, J =
13.3 Hz), 6.40 br.s (2H, NH), 3.62 t (4H, CH2, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

BOZHENKOV et al.
38
3.3 Hz), 2.44 t (4H, CH2, J = 7.5 Hz), 1.54 m (4H,
CH2, J = 7.5 Hz), 0.85 t (3H, CH3, J = 7.5 Hz).
13C NMR spectrum, δC, ppm: 189.89 (C=O), 146.84,
49.54 (CH2); 39.23, 19.48, 14.16 (C3H7). Found, %:
C 50.14; H 6.96; Cl 21.88; N 8.68. C14H22Cl2N2O2.
Calculated, %: C 52.34; H 6.90; Cl 22.07; N 8.72.
carbonate, and extracted with methylene chloride. The
extract was dried over CaCl2 and evaporated, and the
residue was distilled under reduced pressure. Yield
1.56 g (70%), bp 148°C (2 mm). IR spectrum, ν, cm–1:
3050 (=CH); 2930, 2960 (Alk); 1670 (C=O); 1600,
1
1550 (C=C). H NMR spectrum (CDCl3), δ, ppm:
7.84 s (1H, =CH), 7.34 t and 7.13 m (5H, C6H5), 3.65 s
(3H, CH3), 2.68 q (2H, CH2, J = 7.3 Hz), 1.11 t (3H,
CH3, J = 7.3 Hz). 13C NMR spectrum, δC, ppm: 195.99
(C=O), 147.00, 141.56, 129.36, 125.20, 121.37, 116.24,
105.90, 39.76 (CH2), 31.68 (NCH3), 9.02 (CH3). Found,
%: C 64.50; H 6.50; Cl 15.90; N 6.25. C12H14ClNO.
Calculated, %: C 64.43; H 6.31; Cl 15.85; N 6.26.
N,N'-(p-Phenylene)bis(1-amino-2-chlorohex-1-
en-3-one) (VII) was synthesized from 0.22 g (2 mmol)
of benzene-1,4-diamine in 15 ml of ethanol and 0.75 g
(4 mmol) of 1,2-dichlorohex-1-en-3-one. The mixture
was stirred for 1 h at 60°C, cooled, poured into water,
and adjusted to pH 8 by adding Na2CO3, and the pre-
cipitate was filtered off and dried. Yield 0.71 g (96%),
mp 194–195°C. IR spectrum, ν, cm–1: 3225 (NH);
3020 (=CH); 2950, 2915, 2855 (C3H7); 1650 (C=O);
2-Chloro-1-(2-hydroxyphenylamino)pent-1-en-
3-one (X) was synthesized from 1.09 g (0.01 mol)
of 2-aminophenol in 15 ml of ethanol and 1.53 g
(0.01 mol) of 1,2-dichloropent-1-en-3-one. The mix-
ture was stirred for 2 h at 40°C, cooled, poured into
water, and adjusted to pH 7–8, and the precipitate was
filtered off and dried. Yield 1.75 g (68%), mp 161–
162°C. IR spectrum, ν, cm–1: 3355 (NH); 3200–3300
(OH); 2965, 2925 (C2H5); 1650 (C=O); 1600, 1550
(C=C). 1H NMR spectrum (acetone-d6), δ, ppm: 9.17 s
(1H, OH), 8.39 d (1H, =CH, J = 13.3 Hz), 7.59 br.d
(1H, NH, J = 13.3 Hz), 7.38 m and 6.88 m (4H, C6H4),
2.76 q (2H, CH2, J = 7.3 Hz), 1.08 t (3H, CH3, J =
7.3 Hz). Found, %: C 59.45; H 5.62; Cl 15.72; N 6.76.
C11H12ClNO. Calculated, %: C 58.54; H 5.36;
Cl 15.71; N 6.21.
1
1545 (C=C). H NMR spectrum (DMSO-d6), δ, ppm:
9.14 d (2H, NH, J = 12.8 Hz), 8.24 d (2H, =CH, J =
12.8 Hz), 7.40 s (4H, C6H4), 2.70 t (4H, CH2, J =
7.2 Hz), 1.56 m (4H, CH2, J = 7.2 Hz), 0.90 t (6H,
CH3, J = 7.2 Hz). 13C NMR spectrum, δC, ppm: 190.21
(C=O), 138.74, 136.22, 117.90, 107.22, 37.90 (CH2),
18.44 (CH2), 13.66 (CH3). Found, %: C 58.56; H 5.84;
Cl 19.60; N 8.07. C18H22Cl2N2O2. Calculated, %:
C 58.54; H 6.00; Cl 19.20; N 7.59.
2-Chloro-1-dipropylaminohex-1-en-3-one (VIII)
was synthesized from 3.04 g (0.03 mol) of dipropyl-
amine in 10 ml of 50% ethanol and 1.67 g (0.01 mol)
of 1,2-dichlorohex-1-en-3-one. The mixture was stirred
for 3 h at 60°C, cooled, poured into water, and ex-
tracted with diethyl ether, the extract was dried over
MgSO4, the solvent was distilled off, and the residue
was kept under reduced pressure. Yield 2.79 g (40%),
nD20 = 1.5245. IR spectrum, ν, cm–1: 2950, 2920, 2870
(Alk); 1650 (C=O); 1585, 1565 (C=C). 1H NMR spec-
trum (CDCl3), δ, ppm: 7.61 s (1H, =CH), 3.45 t (4H,
CH2, J = 7.5 Hz), 2.52 t (2H, CH2, J = 7.2 Hz), 1.65 m
and 1.55 m (6H, CH2), 0.88 t and 0.87 t (9H, CH3).
13C NMR spectrum, δC, ppm: 194.35 (C=O), 143.65
(=CH), 39.87 (CH2), 22.72 (CH2), 18.51 (CH2), 13.82
(CH3), 10.67 (CH3). Mass spectrum, m/z (Irel, %): 231
(70) [M]+, 202 (23), 188 (18), 160 (12), 72 (12), 71
(48), 70 (30), 43 (100), 41 (51). Found, %: C 62.43;
H 9.31; Cl 15.85; N 6.26. C12H22ClNO. Calculated, %:
C 62.19; H 9.57; Cl 15.30; N 6.04. M 231.77.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 05-03-97202).
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