Synthesis of derivatives of o-aminoacetophenone and o-aminobenzyl alcohol

Article abstract of DOI:10.1134/S1070428007050132

Oxidation of 2′-hydroxy-8-methylspiro[4H-benz-1,3-oxazin-2-one-6, 1′-cyclopentane] or N-mesyl-2-(cyclopent-1-en-1-yl)-6-methylaniline provided the corresponding ketones. The rearrangement of these ketones oximes under treatment with thionyl chloride gave

Full text of DOI:10.1134/S1070428007050132

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 5, pp. 723−728. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © R.R. Gataullin, I.B. Abdrakhmanov , 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 5, pp. 728−732.
Synthesis of Derivatives of o-Aminoacetophenone and
o-Aminobenzyl Alcohol
R. R. Gataullin and I. B. Abdrakhmanov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, 450054 Russia
e-mail: chemorg@anrb.ru
Received March 20, 2006. Revised version December 25, 2006
Abstract—Oxidation of 2'-hydroxy-8-methylspiro[4H-benz-1,3-oxazin-2-one-6,1'-cyclopentane] or N-mesyl-2-
(cyclopent-1-en-1-yl)-6-methylaniline provided the corresponding ketones. The rearrangement of these ketones
oximes under treatment with thionyl chloride gave rise to nitriles of 5-(2-amino-3-methylphenyl)-5-oxopentanoic
or 5-(2-methanesulfamido-3-methylphenyl)-5-hydroxypentanoic acids. By heating 5-(2-acetylamido-3-
methylphenyl)-5-oxopentanoic acid with LiH in THF 3-(2,8-dimethylquinol-4-on-3-yl)propanoic acid was obtained.
DOI: 10.1134/S1070428007050132
Derivatives of o-aminoacetophenone and o-amino-
benzyl alcohol are used in preparation of substituted
indoles [1, 2] and quinolones [3, 4]. We formerly syn-
thesized some representatives of this series by oxidation
of o-cycloalkenylanilides with hydrogen peroxide or
ozone [5]. In extension of these studies we report here
on preparation of such ketones and o-amino-benzyl
alcohol derivatives from 2'-hydroxy-8-methylspiro[4H-
benz-1-oxazin-2-on-6,1'-cyclopentane] and N-mesyl-2-
(cyclopent-1-en-1-yl)-aniline. In oxidation of benzoxazi-
none I [6] with CrO3 ketone II was obtained in 68%
yield. The reaction of ketone II with hydroxylamine gave
oxime III that treated with SOCl2 was converted into
ketonitrile IV in a fair yield, although a strong tarring of
the reaction mixture occurred.
The ketonitrile structure of the product obtained was
confirmed by spectral methods and elemental analysis.
In the 1H NMR spectrum of compound IV the methylene
groups give rise to two two-proton triplets and one two-
proton quintet. In the J-modulated spin-echo 13C NMR
Scheme 1.
O
O
O
NH2OH HCl,
NaHCO3
O
NH
O
NH
O
4
NH
CrO3, H2SO4
Aceton
Me
Me
Me
MeOH
HO
O
HON
III, 83%
I
II, 68%
SOCl2,
CH2Cl2
O
O
O
O
O
NH2
CN
+
H2O
_CO2
O
2'
O
NH
NC
Me
1'
3'
5
(CH2)3
Me
N
N+
+
IV
723

GATAULLIN, ABDRAKHMANOV
724
spectrum the carbon atoms appear as three signals at 16.6,
20.1, and 36.9 ppm that correspond to the methylene
proton signals in the CH-correlation spectrum. The
presence of the keto group was proved by the carbonyl
carbon signal at 200 ppm.
zine X and α,β-unsaturated ketone XI (Scheme 3). The
reaction mixture suffered a considerable tarring. Benz-
oxazine X is apparently a product of the subsequent
cyclization of epoxy compound B, and ketone XI may
arise by eliminating HCl from of a chloroderivative C.
The reaction of ClO2 with olefins is known to provide
both epoxides and ketone type compounds with a halogen
attached to the adjacent carbon atom [9]. The
composition and structure of compounds X and XI
obtained were con-firmed by spectral methods and
elemental analysis. The NMR spectra of benzoxazine
hydrochloride are in agree-ment with the spectra of the
free base [7]. The ketone structure is proved by the
presence in the 13C NMR spec-trum of a peak in the
region 210 ppm. The signals of atoms C1' and C2' (145
and 166 ppm) are shifted down-field.All the three signals
are close to those in the spec-trum of analogous ketone
we have described before [10].
The oxidation of N-mesylate V with hydrogen
peroxide gave ketone VI in 62% yield (Scheme 2).
Evidently keto derivative VI formed as a result of
a rearrangement of epoxide A not infrequent in similar
systems [6]. The presence of an ortho-methyl group
favored a single reaction route. We formerly [7] observed
formation of four reaction products lacking ketone in
oxidation under these conditions of both tosylate and
mesylate analogs of compound V without the ortho-
methyl group.
By reaction of ketone VI with hydroxylamine oxime
VII was obtained in 86% yield. By the treatment with
SOCl2 oxime VII was converted into hydroxynitrile VIII
in 45% yield. The structure of nitriles IV and VIII
obtained suggests that oximes III and VII apparently
have an anti-location of OH group and atoms C1' and C4
of compounds III and VII respectively.
Oxidation of anilides IXa and IXb [5] with the hydro-
gen peroxide in formic acid takes the third route giving
ketoacids (Scheme 4). Ketoacids XIIa and XIIb [5] are
apparently products of epoxides D transformations [6,
11, 12]. The heating of ketocarboxylic acid XIIb with
lithium hydride in THF gives 4-quinolone-3-carboxylic
acid XIII in 50% yield; this acid is characterized by
a considerably higher melting point (283°C) than the
initial ketoacid (145°C). The quinolone structure was
proved by spectral methods. In the 1H NMR spectrum of
compound XIII only two triplets of methylene groups
protons are observed whereas the spectrum of initial
compound XIIb contains signals of three methylene
groups. The other signals in the NMR spectra of quino-
lone XIII are consistent with the suggested structure. In
From N-acetylated derivatives of the aminobenzyl
alcohol of VIII type 2,3-disubstituted indoles may be
synthesized [1, 2]. We previously established that it was
impossible to obtain from the N-acylated analogs of
N-mesylate V cyclopentanones similar to ketone VI by
oxidation with the hydrogen peroxide in the system
Na2WO4–H3PO4 or in the presence of alkali, or with
dimethyldioxirane. In all instances the reaction led to
the formation of benzoxazines or indolines [7, 8].Aiming
at preparation of a ketone type compound with an
N-acetyl group we attempted an oxidation of anilide IXa
with ClO2. The reaction provided a mixture of benzoxa-
Scheme 2.
MsNH
NH2OH HCl,
NaHCO3
H2O2,
NaOH
MeCN
MsNH
MsNH
MsNH
1'
O
Me
Me
Me
Me
MeOH
NOH
O
VII
VI
SOCl2,
CH2Cl2
V
A
MsNH OH
MsNH
MsNH
CN
Me
HO_
+
(CH2)3
Me
+
CN
Me
N
VIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

SYNTHESIS OF DERIVATIVES OF o-AMINOACETOPHENONE
725
Scheme 3.
Me
AcNH
AcNH
O
N HCl
ClO2
MeCN, 20oC
O
OH
IXa
X
HCl
XI
_HCl
ClO2
AcNH
AcNH
AcNH
Cl
O
_ClO
O
OClO
B
C
Cl
_HClO
Scheme 4.
O
H2O2
HCOOH
O
NH
NH
NH
Me
R
R
R
Me
O
Me
O
O
D
IXa, IXb
O
O
CO2H
CO2H
[O]
LiH
THF, boiling
18 h
NH
N
H
Me
R
Me
Me
XIIa, XIIb
O
XIII, 50%
R = H (a), Me (b).
the J-modulated spin-echo 13C NMR spectrum appear
three signals from atoms C5, C6, and C7, and also
7 singlets corresponding to the quaternary carbons of
the aromatic ring, carbonyl, and carboxy groups. In the
mass spectrum molecular ion peak was observed with
m/z 245.
pentanoic acid with LiH in THF gave 3-(2,8-dimethyl-
quinol-4-on-3-yl)propanoic acid.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer UR-
1
20. H and 13C NMR spectra were registered on
Thus the oxidation of N-acyl-2-(1-cyclopenten-1-yl)-
anilines led to the formation of 5-(2-amino-3-methyl-
phenyl)-5-oxopentanoic or 5-(2-methanesulfamido-3-
methylphenyl)-5-hydroxypentanoic acids, and the heat-
ing of 5-(2-acetylamido-3-methylphenyl)-5-oxo-
a spectrometer Bruker AM-300 at operating frequencies
300.13 and 75.45 MHz respectively, internal reference
TMS. Elemental analysis was carried out on a CHN
Analyzer M-185B. For column chromatography was used
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

GATAULLIN, ABDRAKHMANOV
726
5-(2-Amino-3-methylphenyl)-5-oxopentanoic acid
nitrile (IV). In 5 ml of dichloromethane was dispersed
0.44 g (1.77 mmol) of oxime III, and maintaining the
temperature of the mixture at 0°C was added dropwise
while stirring 0.6 g (5.04 mmol) of SOCl2 in 4 ml of
CH2Cl2. The stirring at this temperature was continued
for 2 h, the a saturated solution of NaHCO3 was added
till neutral reaction, the mixture was diluted with 80 ml
of CH2Cl2, washed with water (30 ml), and dried with
MgSO4. On evaporating the solvent in a vacuum we
obtained a brown substance subjected to chromatography
on silica gel (eluent hexane–EtOAc). We isolated
compound IV in 0.13 g (35%) yield, Rf 0.4 (hexane–
EtOAc, 4:1). 1H NMR spectrum (CDCl3), δ, ppm:
2.05 q (CH2, J 6.9 Hz), 2.14 s (CH3), 2.46 t (CH2,
J 7.2 Hz), 3.10 t (CH2, J 7.1 Hz), 6.42 br.s (NH2), 6.58 t
(H5, J 7.5 Hz), 7.19 d (H4, J 7.2 Hz), 7.61 d (H6,
J 8.2 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 17.1
(CH3), 16.6, 20.2, 36.9 (3CH2), 115.1, 128.8, 135.1 (C4',
C5', C6'), 116.7, 119.6, 123.5 (Ca”N, C2, C3'), 148.9 (C1'),
200.3 (C=O). Found, %: C 71.20; H 6.92; N 13.87.
C12H14N2O. Calculated, %: C 71.26; H 6.98; N 13.85.
silica gel 40/70 μm (Lancaster). Qualitative TLC analysis
was performed of Silufol plates Sorbfil PTSKh-AF-V-
UV (Join-Stock Co Sorbpolymer, Stavropol), spots were
visualized by UV irradiation (λ 254 nm) or by iodine
vapor. Mass spectra were taken on a spectrometer MKh
..
1320 (70 eV). Melting points were measured on a Boetius
heating block.
2'-Oxo-8-methylspiro[4H-benz-1-oxazin-2-one-
6,1'-cyclopentane] (II). To a solution of 2 g (8.58 mmol)
of compound I in 60 ml of acetone was added 20 ml of
Jones’ reagent prepared by dissolving 14 g of CrO3 in
100 ml of water with subsequent addition of 12 ml of
concn. H2SO4. The mixture was left standing for 15 h.
Then NaHSO3 was added till disappearance of the brown
color of the upper layer, water-salt layer was separated,
acetone was partially evaporated, the residue was diluted
with 80 ml of CHCl3, washed with a saturated solution
of sodium carbonate till neutral reaction, then with water,
dried with MgSO4, and the solvent was evaporated under
a reduced pressure. The residue was subjected to column
chromatography on silica gel (eluent hexane–EtOAc,
1
4:1). Yield 1.34 g (68%), mp 209°C. H NMR spectrum
N-Methanesulfonyl-2-methyl-6-(2-oxocyclopent-
1-yl)aniline (VI). To a solution of 1.25 g (5 mmol) of
mesylate V in 6 ml of MeCN and 3 ml of MeOH was
added 0.51 g (7.5 mmol) of 50% H2O2, then 10% solution
of KOH till pH 8. The mixture was kept for 5 h, then
diluted with 60 ml of CHCl3, washed with 20 ml of 10%
Na2S2O3 solution, 20 ml of water, and dried with MgSO4.
On evaporating the solvent the reaction product was
subjected to chromatography on silica gel. Yield 0.83 g
(DMSO-d6), δ, ppm: 2.02–2.15 m (CH2), 2.23 s (CH3),
2.34 q (CH2, J 7.0 Hz), 2.45–2.57 m (CH2), 6.94 t (H6,
J 7.7 Hz), 7.07 d (H5, J 7.4 Hz), 7.14 d (H7, J 7.3 Hz),
9.72 s (NH). 13C NMR spectrum (DMSO-d6), δ, ppm:
16.9 (CH3), 17.4, 34.2, 34.7 (3CH2), 85.2 (C4), 121.8,
122.4, 131.1 (C5, C6, C7), 119.4, 123.2 (C4a, C8), 134.3
(C8a), 149.9 (C2), 211.4 (C=O). Found, %: C 67.45;
H 5.66; N 6.01. C13H13NO3. Calculated, %: C 67.52;
H 5.67; N 6.06.
1
(62%), Rf 0.3 (hexane–EtOAc, 3:1). H NMR spectrum
2'-Oxo-8-methylspiro[4H-benz-1-oxazin-2-one-
6,1'-cyclopentane] oxime (III). To a solution of 1.73 g
(7.49 mmol) of ketone II in 40 ml of methanol was added
0.63 g (9 mmol) of NH2OH·HCl, and then dropwise was
added at stirring a solution of 0.91 g (10.8 mmol) of
NaHCO3 in 20 ml of water. The mixture was stirred for
5 h, then diluted with 120 ml of CHCl3, washed with
water (30 ml), and dried with MgSO4. On complete
evaporation of the solvent the reaction product crystal-
(CDCl3), δ, ppm: 2.42 s (CH3), 2.00–2.52 m (3CH2),
3.01 s (CH3), 4.08–4.15 m (CH), 7.02 d.d (1H, ArH,
J1 3.2, J2 6.0 Hz), 7.12–7.20 m (2H, ArH), 7.45 c (NH).
13C NMR spectrum (CDCl3), δ, ppm: 19.3 (CH3), 20.8,
29.7, 38.4 (3CH2), 41.8 (CH3SO2), 51.7 (CH), 124.8 (C4),
127.7 (C3), 129.9 (C5), 134.1 (C2), 137.1 (C1), 137.8 (C6),
219.8 (C=O). Mass spectrum: m/z 267 [M]+. Found, %:
C 57.98; H 6.52; N 5.33; S 11.50. C13H17NO3S.
Calculated, %: C 58.41; H 6.41; N 5.24; S 11.99.
1
lized. Yield 1.53 g (83%), mp 265–267°C. H NMR
N-Methanesulfonyl-2-methyl-6-(2-oxocyclopent-
1-yl)aniline oxime (VII) was obtained similarly to
compound III from 2.0 g (7.49 mmol) of ketone VI and
0.63 g (9 mmol) of hydroxylamine hydrochloride. On
evaporating the solvent the oily residue was recrystallized
from CCl4. Yield 1.81 g (86%), Rf 0.2 (hexane–EtOAc,
3:1). 1H NMR spectrum (CDCl3), δ, ppm: 1.73–1.84 m
(CH2), 2.05 s (CH3), 2.32–2.82 m (2CH2), 2.98 s
(CH3SO2), 4.07–4.13 m (CH), 7.02 d (1H,ArH, J 7.4 Hz),
7.04 d (1H, ArH, J 5.9 Hz), 7.17 d (H4, J 7.6 Hz), 8.08 s
spectrum (DMSO-d6), δ, ppm: 1.85–2.04 m (CH2),
2.24 s (CH3), 2.37–2.65 m (2CH2), 6.91 t (H6, J 7.3 Hz),
7.04 d (H5, J 7.5 Hz), 7.10 d (H7, J 7.1 Hz), 9.67 s (NH),
11.11 s (OH). 13C NMR spectrum (DMSO-d6), δ, ppm:
17.0 (CH3), 19.9, 25.4, 37.5 (3CH2), 87.5 (C4), 121.9,
122.0, 130.4 (C5, C6, C7), 121.7, 122.8 (C4a, C8), 134.5
(C8a), 150.3 (C2), 161.8 (C=NOH). Found, %: C 63.47;
H 5.76; N 11.29. C13H14N2O3. Calculated, %: C 63.40;
H 5.73; N 11.38.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

SYNTHESIS OF DERIVATIVES OF o-AMINOACETOPHENONE
727
(NH), 8.61 br.s (OH). 13C NMR spec-trum (CDCl3), δ,
ppm: 19.3, 42.3 (2CH3), 22.9, 28.2, 35.2 (3CH2), 44.7
(CH), 126.2 (C4), 127.7 (C5), 129.3 (C3), 133.0 (C2), 137.5
(C6), 141.1 (C1), 170.3 (C=NOH). Found, %: C 54.98;
H 6.51; N 9.85; S 11.39. C13H18N2O3S. Calculated, %:
C 55.30; H 6.43; N 9.92; S 11.35.
C 72.48; H 6.11; N 6.43. C13H13NO2. Calculated,
%: C 72.54; H 6.09; N 6.51.
5-(2-Methylcarboxyamidophenyl)-5-oxopentanoic
acid (XIIa). To a solution of 0.47 g (2.33 mmol) of anilide
IXa in 0.6 ml of 90% formic acid was added 0.6 g
(8.82 mmol) of 50% hydrogen peroxide maintaining the
reaction temperature below 40°C. The reaction mixture
was left standing for 24 h at room temperature, then
diluted with 60 ml of ethyl acetate, the solution was
washed with water (2×20 ml), and dried with MgSO4.
On evaporating the solvent the reaction product was
recrystallized from CH2Cl2. Yield 0.33 g (57%), mp 123–
5-(2-Methanesulfamido-3-methylphenyl)-5-
γθdpOqCθpentanoic acid nitrile (VIII) was prepared
similarly to compound IV from 1.77 mmol of oxime VII.
After chromatography on silica gel (hexane–EtOAc)
yield was 0.22 g (45%), Rf 0.3 (hexane–EtOAc, 3:1).
1H NMR spectrum (CDCl3), δ, ppm: 1.73–2.27 m (3CH2),
2.00–2.23 br.s (OH), 2.40 s (CH3), 3.05 s (CH3SO2),
5.57 d.d (1H, CHOH, J1 4.7, J2 8.9 Hz), 6.86 s (NH),
7.23 d (1H, ArH, J 6.4 Hz), 7.30 t (1H, H4, J 7.8 Hz),
7.47 d (1H,ArH, J 7.4 Hz). 13C NMR spectrum (CDCl3),
δ, ppm: 18.9, 41.0 (2CH3), 16.4, 22.9, 37.6 (3CH2), 57.5
(CHOH), 119.5 (C≡N), 125.9 (C4), 128.7 (C5), 130.6 (C2),
131.1 (C3), 136.7 (C6), 141.1 (C1). Found, %: C 55.38;
H 6.40; N 9.88; S 11.42. C13H18N2O3S. Calculated, %:
C 55.30; H 6.43; N 9.92; S 11.35.
1
125°C (CH2Cl2). H NMR spectrum (CDCl3), δ, ppm:
2.09 q (CH2, J 7.1 Hz), 2.25 s (CH3), 2.50 t (CH2, J7.1 Hz),
3.15 t (CH2, J 7.1 Hz), 7.10 d.t (H4', J1 1.0, J2 8.0 Hz),
7.55 d.t (H5', J1 1.0, J2 8.4 Hz), 7.91 d (H3', J 8.0 Hz),
8.75 d (H6', J 8.4 Hz), 11.70 (NH), 12.05 (COOH).
13C NMR spectrum (CDCl3), δ, ppm: 19.1 (C3), 25.5 (CH3),
32.9 (C2), 38.8 (C4), 120.9 (C3'), 121.4 (C1'), 122.4 (C5'),
130.6 (C6'), 135.1 (C4'), 140.8 (C2'), 169.8 (CONH), 178.5
(COOH), 203.8 (C5). Found, %: C 62.33; H 6.12; N 5.39.
C13H15NO4. Calculated, %: C 62.64; H 6.07 N 5.62.
Anilide IXa oxidation with chlorine dioxide.
To a solution of 0.1 g (0.5 mmol) of anilide IX in 10 ml
of MeCN was added 0.5 mmol of ClO2 in 20 ml of MeCN
at 20°C. The reaction progress was monitored by TLC,
then the solvent was evaporated. The dark residue was
subjected to column chromatography on silica gel.
3-(2,8-Dimethylquinol-4-on-3-yl)propanoic acid
(XIII). In 30 ml of THF was dissolved at boiling 65 mg
(0.25 mmol) of ketoacid XIIb. To the solution obtained
was added at heating 30 mg of LiH, colorless precipitate
separated. The reaction mixture was heated at reflux for
18 h, then cooled to room temperature, 1 ml of water
was added, then 10 ml of 5% solution of HCl. The
separated precipitate was filtered off. Yield 31 mg (50%),
2'-Hydroxy-2-methylspiro[(4H-benz-1,3-oxazine)-
6,1'-cyclopentane] hydrochloride (X). Yield 0.041 g
(32%), Rf 0.3 (MεOH–EtOAc, 1:3). 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.62–2.28 m (3CH2), 2.52 s (CH3),
4.21 t (H2', J 5.0 Hz), 4.31 br.s (OH), 7.36–7.47 m (4H,
ArH). 13C NMR spectrum (DMSO-d6), δ, ppm: 19.8
(CH3), 19.3, 31.3, 35.8 (3CH2), 77.1 (CHOH), 97.2
(C4), 117.1, 127.0, 128.3, 129.5 (C5, C6, C7, C8), 121.6,
128.8 (C8a, C4a), 170.1 (C2). Found, %: C 61.60; H 6.30;
Cl 14.02; N 5.49. C13H16ClNO2. Calculated, %: C 61.54;
H 6.36; Cl 13.97; N 5.52.
1
mp 283°C. H NMR spectrum (DMΤA-d7), δ, ppm:
2.50 t (CH2, J 7.5 Hz), 2.60 s (CH3), 2.90 t (CH2,
J 7.5 Hz), 7.20 d.t (H6, J 7.0 Hz), 7.50 d, 8.10 d (H5, H7,
J 7.0 Hz). 13C NMR spectrum (DMF-d7), δ, ppm: 17.8,
18.0 (2CH3), 22.2 (CH2), 34.2 (CH2), 119.1 (C3), 122.8,
123.7, 132.6 (C5, C6, C7), 124.6, 126.9, 139.1, 148.4 (C2,
C4a, C8, C8a), 176.4 (CO2H), 176.9 (C4). Mass spectrum,
m/z: 245 [M]+, 227 [M – H2O]+, 200 [M – CO2H]2+, 185
(max) [M – H2O – CH2CO]2+ and/or [M – CO2H – CH3]+.
N-Acetyl-2-(5-oxocyclopent-1-en-1-yl)-aniline
(XI). Yield 0.036 g (34%), Rf 0.3 (EtOAc). H NMR
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 5 2007

GATAULLIN, ABDRAKHMANOV
728
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