Reactions of N- and C-alkenylanilines: I. Synthesis of anilides and amidines from ortho-alkenyl(cycloalkenyl)anilines and their transformations

Article abstract of DOI:10.1023/A:1012413715466

N-Acetyl- and N-formyl-ortho-alkenyl(cycloalkenyl)anilines were synthesized. Their reaction with P₂O, or PCl₅ afforded quinolines. By reaction of the ortho-alkenyl(cycloalkenyl)anilines with 1-methylimino- or 1-phenylimino-1-chloroethanes amidines were obtained that were cyclized in the polyphosphoric acid. The reaction with the polyphosphoric acid of amidines prepared from alkenylanilines and 1-methylimino-1-chloroethane gave rise to 3-methyl-3,4-dihydroquinazolines; on replacing in the substrate methylimine group for phenylimine one the yield of quinazoline decreased.

Full text of DOI:10.1023/A:1012413715466

Russian Journal of Organic Chemistry, Vol. 37, No. 6, 2001, pp. 834 840. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 6, 2001,
pp. 881 887.
,
Original Russian Text Copyright 2001 by Gataullin, Afon kin, Fatykhov, Spirikhin, Abdrakhmanov.
Reactions of N- and C-Alkenylanilines: I. Synthesis of Anilides
and Amidines from ortho-Alkenyl(cycloalkenyl)anilines
and Their Transformations
R. R. Gataullin, I. S. Afon,kin, A. A. Fatykhov, L. V. Spirikhin,
and I. B. Abdrakhmanov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciencs, Ufa, Bashkortostan, 450054 Russia
Received July 7, 2000
Abstract N-Acetyl- and N-formyl-ortho-alkenyl(cycloalkenyl)anilines were synthesized. Their reaction
with P2O5 or PCl5 afforded quinolines. By reaction of the ortho-alkenyl(cycloalkenyl)anilines with
1-methylimino- or 1-phenylimino-1-chloroethanes amidines were obtained that were cyclized in the
polyphosphoric acid. The reaction with the polyphosphoric acid of amidines prepared from alkenylanilines
and 1-methylimino-1-chloroethane gave rise to 3-methyl-3,4-dihydroquinazolines; on replacing in the
substrate methylimine group for phenylimine one the yield of quinazoline decreased.
Quinazoline series compounds possess a wide
range of biological activity and thus attract the
interest of researchers [1 12]. The principal methods
of preparation thereof is the synthesis from
anthranilic acid derivatives [1 5], from 3,1-benzoxa-
zines [6 8] and 2-aminomethylanilines [9, 10], and
also by addition of alkyl isocyanates to N-triphenyl-
phosphite of methyl aminocinnamate [13]. The
anthranilic acids or benzoxazines furnish quinazolin-
4-ones, and cyclization of N-phenyl-N -acylsubstitut-
ed ureas in the polyphosphoric acid gives rise to
quinazolin-2-ones [14]. In the synthesis of 4H-deriv-
atives are commonly used 2-aminomethylanilines [9,
10] or esters of 2-aminocinnamic acid [13]. The
available ortho-alkenylanilines whose preparative
synthesis has been known already since 40 years [15]
unfortunately are poorly studied in the synthesis of
quinazolines. In this investigation we synthesized
from the ortho-alkenyl(cycloalkenyl)anilines their
N-acetyl, N-formyl or amidine derivatives aiming to
perform their cyclization into quinazolines. To
convert the N-acetyl- and N-formyl-ortho-alkenyl-
anilines into amidines we planned to apply the known
procedures [16, 17]. The amidines prepared along the
procedure [17] from the ortho-alkenylanilines and
1-methylimino- or 1-phenylimino-1-chloroethanes
were subjected to cyclization in the polyphosphoric
acid.
furnish amidines that further relatively readily
undergo cyclization into quinazolines.
However when we applied this procedure to
preparation of amidines (A) or (B) from N-acetyl-
ortho-(1-cycloalken-1-yl)anilines I [18] or II [19]
we obtained only quinolines III and IV respectively
(Scheme 1). Acetyl derivatives V [18] or VI contain-
ing an allyl double bond also easily cyclize into
quinolines III or IV (Table 1). 3,1-Benzoxazine (VII)
prepared previously by method [18] under these
conditions affords quinoline III in 36% yield.
Apparently under conditions developed in [16] the
amidine formation from amides I, II, V, and VI is
impossible, and the reaction is directed to their
cyclization into quinolines [20].
Table 1. Yields of quinolines depending on the initial
compounds and reagents
Initial
compd. no.
Reagent
Quinoline
no.
Yield, %
I
II
V
VI
VII
IX
P2O5/Bu3N
P2O5/Bu3N
P2O5/Bu3N
P2O5/Bu3N
P2O5/Bu3N
PCl5
III
IV
II
IV
III
X
43
36
37
31
36
28
6
It is known [16] that at heating N-acetylanthranilic
acid with P2O5 in the presence of alkylammonium
chlorides in a trialkylamine the oxygen atom in the
acetyl group is replaced by the alkylamine moiety to
XXVI Polyphosphoric
III
acid
1070-4280/01/3706-0834$25.00 2001 MAIK Nauka/Interperiodica

REACTIONS OF N- AND C-ALKENYLANILINES: I.
835
Scheme 1.
n = 1, R = Me (I, III, V); n = 2, R = H (II, IV, VI). Reagents and conditions: a, HCl, CH2Cl2, 20 C, 9 h;
b, P2O5, Bu3N, [MeNH3]+ Cl or [NH4]+ Cl , 160 170 C, 2 h.
Scheme 2.
The attempt to obtain amidine VIII (Scheme 2) at
treating N-formyl derivative IX with PCl5 at molar
ratio 1: 1 results in cyclization of compound IX into
quinoline X in 28% yield at 34% conversion of the
initial amide IX.
Here form in high yield N-(alkenylphenyl)-N -
methylacetamidines XIV XVI (Schemes 3 and 4).
Amidines XVII and XVIII were obtained in a
similar way by reaction of amine XII and 2-[(Z)-1-
methyl-1-buten-1-yl]-4-methylaniline (XIX) [22] with
1-phenylimino-1-chloroethane in 94 95% yield. The
keeping of amidines XIV, XV in polyphosphoric acid
for 4 h at 150 160 C gives rise to cyclized product
2,3,4,6-tetramethyl-4-propyl-3,4-dihydro-1,3-quin-
azoline (XX) (Scheme 3). Under similar conditions
amidine XVI is converted into 2,3,8-trimethylspiro-
(cyclopentane-3,4-dihydroquinazoline) (XXI)
The best results in preparation of the target quin-
azolines were obtained at using amidines synthesized
by condensation of 2-[(E)-1-methyl-2-buten1-yl]-4-
methylaniline (XI) [21], 2-[(E)-1-methyl-1-buten-1-
yl]-4-methylaniline (XII) [22] or 2-(1-cyclo-penten-1-
yl)-6-methylaniline (XIII) [18] with 1-methylimino-1-
chloroethane [17] in benzene at 80 C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

836
GATAULLIN et al.
Scheme 3.
R = Me (XV, XX), Ph (XVII, XVIII, XXII). Reagents and conditions: (a) KOH, 300 C; (b) MeNC(Cl)Me or
PhNC(Cl)Me, 80 C, benzene; (c) polyphosphoric acid, 150 160 C.
(Scheme 4). In a similar cyclization of amidines XVII
and XVIII into a 3-phenyl-substituted quinazoline
XXII (Scheme 3) the yield of the product is smaller
(Table 2). Amidine XIV is converted into quinazoline
XX through preliminary shift of a double bond
toward the aromatic ring resulting in vinyl derivative
XV (according to GLC data). It is known that in reac-
tion between the polyphosphoric acid and amine XI at
100 140 C originally arises trans-alkenylaniline XII
[22] and then the successive isomerizations in the
alkenyl fragment result in formation of a mixture of
indoline XXIII and aminoindane XXIV [23].
in amidines XVII, XVIII, XXVI is reduced, and the
probability of the side processes grows. Therefore in
reaction with polyphosphoric acid of amidines XVII,
XVIII (Scheme 3) decreases the quinazoline yield,
and amidine XXVI affords alongside quinazoline
XXVII also indoline XXV (up to 24%) and quinoline
III (6%) (Scheme 4).
We reported formerly on formation of 3,1-benz-
oxazines from N-acetylated derivatives of arylamines
I, II, XII when treated with HCl gas at room
temperature [18, 20]. Apparently due to high thermal
stability of salts amidines XV, XVI do not afford
quinazolines even at heating their hydrochlorides to
180 C.
Unlike the reaction described in [23] with amidines
XV and XVI due to the high basicity of the nitrogen
atom on the MeNH group occurred intramolecular
cyclization into six-membered heterocycles XX or
XXI, and the expected under these relatively stringent
conditions indoline XXIII and aminoindane XXIV
from amidines XIV, XV or perhydrocyclopent[b]-
indoline (XXV) [24] from amidine XVI formed in
small amount (3 5%).
The composition and structure of the compounds
synthesized were established from elemental analyses
1
and spectral data. Thus in the H NMR spectrum of
quinolines III, IV are present characteristic triplet
signals of methylene protons H1 and H3 in the region
3.1 and 3.0 ppm respectively (Table 3). The signals
of aromatic protons are observed at 7.3 7.6 ppm, and
the signal from H4 proton of quinoline X appears as a
downfield singlet (8.8 ppm) [25]. In the 13C NMR
The replacement of the methyl group by phenyl
(Schemes 3 and 4) the basicity of the amine nitrogen
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

REACTIONS OF N- AND C-ALKENYLANILINES: I.
837
Scheme 4.
R = Me (XVI, XXI), Ph (XXVI, XXVII).
Table 2. Yields, Rf values, melting points, IR spectra, and elemental analyses of compounds III, IV, VI, IX, X,
XIV XVIII, XX XXII, XXVI, XXVII
Compd. Yield,
R
(CHCl3)
IR spectrum,
Found, %
H
Calculated, %
H
f
1
no.
%
or mp,
C
, cm
Formula
C
N
C
N
III
36 43
31 36
0.16
1354, 1450, 1509 85.02 7.43
[ (C C)]
1378, 1441, 1523 84.85 7.23
[ (C C)]
6.83 C14H15N
6.89 C14H15N
85.22 7.67
85.22 7.67
7.11
7.11
IV
82
(85 [20])
0.4
VI
IX
95
95
3280 (NH)
3280 (NH)
77.80 7.48
77.33 7.22
6.16 C14H17NO
6.54 C13H15NO
78.10 7.96
77.58 7.51
6.50
6.96
102 104
(from hexane)
82 85a
X
28
1376, 1460, 1508 84.97
[ (C C)]
6.89 7.36
C13H13N
85.20 7.16
7.64
XIV
XV
93
97
0.2
95 96
3216 (NH)
3210 (NH)
77.89 9.33
78.02 9.21
11.80
11.83
C15H22N2
C15H22N2
78.21 9.63
78.21 9.63
12.16
12.16
(from pentane)
XVI
94
95
94
70
70
51
93
40
0.2
0.2
0.2
0.4
0.4
0.4
0.2
0.4
3220 (NH)
3230 (NH)
3254 (NH)
1247 (C N)
1245 (C N)
1252 (C N)
3270 (NH)
1257 (C N)
78.60 8.53
82.00 8.07
81.65 8.16
77.93 9.29
78.53 8.69
81.70 8.14
82.40 7.31
82.33 7.55
11.94
9.34 C20H24N2
9.40 C20H24N2
11.85
11.97
9.30 C20H24N2
9.29 C20H22N2
9.46 C20H22N2
C15H20N2
78.89 8.83
82.15 8.27
82.15 8.27
78.21 9.63
78.89 8.83
82.15 8.27
82.72 7.63
82.72 7.63
12.27
9.58
9.58
12.16
12.27
9.58
XVII
XVIII
XX
C15H22N2
C15H20N2
XXI
XXII
XXVI
XXVII
9.65
9.65
a
After sublimation in a vacuum.
1
spectra the signal of C4 carbon linked directly to
nitrogen in quinolines III, X (150 154 ppm), and C6
in 6-methyl-7,8,9,10-tetrahydrophenanthridine (IV)
(158.3 ppm) are shifted downfield [25] (Table 4).
tions is present at 3200 3270 cm (Table 2). In the
1H NMR spectra of amidines XV, XVII, XVIII the
protons H2 of alkenyl fragments appear as triplet in
the 5.3 5.6 ppm region (J 6.6 7.1 Hz), and in the
spectrum of amidine XVI this signal is a singlet at
5.9 ppm (Table 3). The proton signals from H2 and
In the IR spectra of amidines XIV XVIII, XXVI
the absorption band of NH group stretching vibra-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

838
GATAULLIN et al.
1
Table 3. H NMR spectra (CDCl3) of compounds III, IV, VI, IX, X, XIV XVIII, XX XXII, XXVI, XXVII
Compd.
no.
, ppm (J, Hz)
III
IV
2.2 m (C2H2), 2.7 s, 2.8 s (2 CH3), 3.0 t (C1H2, 6.8), 3.2 t (C3H2, 7.2), 7.3 m (H8), 7.5 d (H9, 6.4),
7.6 d (H7, 7.8)
1.5 2.6 m (C8H2, C9H2), 2.5 s (CH3), 2.6 m (C10H2), 2.9 m (C7H2), 7.4 t (H2, 7.0), 7.5 t (H3), 7.7 d
(H4, 8.3), 7.9 d (H1, 8.3)
VI
IX
X
1.1 2.2 m (3 CH2), 2.0 s (CH3), 3.4 m (C1 H), 5.6 6.0 m (HC=CH), 6.9 7.7 m (Ar H), 7.4 s (NH)
2.0 s (C_ _H3), 2.0 2.6 m (3 CH2), 5.9 t, 6.0 t (HC=C, 2.1), 7.1 m (Ar H), 7.6 s, 8.1 s (NH, CHO)
2.2 m (C2H2), 2.5 s (CH3), 3.0 t (C1H2, 7.5), 3.2 t (C3H2, 7.4), 7.3 m (H8), 7.4 d (H7, 8.3), 7.6 d
(H9, 6.3), 8.8 s (H4)
XIV
XV
1.2 d (7.0), 1.6 d (6.1), 1.7 s, 2.3 s, 2.9 s (5 CH3), 3.8 m (C1 H), 4.4 s (NH), 5.4 d.q (H2 , 6.1,
15.4), 5.5 d.d (H3 , 7.4), 6.5 d (H6, 7.1), 6.9 d (H5, 7.1), 7.9 s(H3)
1.0 t (7.6), 1.6 s, 1.9 s, 2.2 s, 2.8 s (5 CH3), 2.1 q (C3 H2, 7.1), 4.4 s (NH), 5.4 t (H2 , 7.1), 6.6 d
(H6, 7.8), 6.8 s (H3), 6.9 d (H5, 7.8)
XVI
XVII
XVIII
1.4 s, 2.1 s, 2.8 s (3 CH3), 1.9 m (C4 H2), 2.3 m (C3 H2), 2.7 m (C5 H2), 4.9 s (NH), 5.9 s (H2 ), 6.8 t
(H4, 7.5), 7.0 d (H3, 7.5), 7.1 d (H5)
1.0 t (7.5), 1.9 m (C3 H2), 2.0 s, 2.1 s, 2.4 s (4 CH3), 5.6 t (H3 , 6.9), 7.0 s (H3), 7.1 7.4 m (7H,
Ar H), 7.6 s (NH)
1.1 t (7.5), 1.9 s, 2.1 s, 2.4 s (4 CH3), 2.3 q (C3 H2, 7.4), 5.5 t (H2 , 6.6), 7.0 7.4 m (8H, Ar H),
7.3 s (NH)
XX
0.8 t (7.3), 1.3 m (C2 H2), 1.5 s, 1.9 s, 2.2 s, 2.8 s (5 CH3), 2.1 m (C1 H2), 6.7 6.9 m (3H, Ar H)
1.5 2.7 m (4 CH2), 2.1 s, 2.3 s, 2.9 s (3 CH3), 6.8 7.9 m (3H, Ar H)
XXI
XXII
XXVI
0.8 t (7.3), 1.3 m (C2 H2), 1.5 s, 1.9 s, 2.2 s, 2.8 s (5 CH3), 2.1 m (C1 H2), 6.9 7.4 m (8H, Ar H)
1.6 s, 2.1 s (2 CH3), 1.7 2.7 m (3 CH2), 5.9 s (H2 ), 6.7 7.4 m (8H, Ar H), 9.4 s (NH)
XXVII 1.5 2.3 m (4 CH2), 1.5 s, 2.5 s (2 CH3), 6.6 7.4 m (8H, Ar H)
H3 at the double bond in amidine XIV are observed
in the region of 5.4 (d.q, J1 6.0 and J2 15.4 Hz) and
5.5 ppm (d.d, J 7.4 Hz). The quintet of the methylene
protons C3 H2 of amidine XV is located in the region
of 2.1 ppm (J 7.1 Hz), and in the spectrum of quin-
azoline XX the proton signals of the two methylene
groups in the propyl moiety are shifted upfield (1.3
1.9 ppm). The carbon resonance from the N=C N
moiety in the 12C NMR spectra of amidines XIV
XVIII, XVI appears at 156 160 ppm and it does not
significantly alter in the quinazoline spectra. In the
13C NMR spectra of compounds XX, XXI, XXII,
XXVII the signals of nodal carbon atoms C4 are
observed in 61 68 ppm region respectively (Table
4). In the aromatic part of the 13C NMR spectra of
quinazolines XX, XXI appear 6 signals assigned to
respective carbon atoms basing on calculations
according to additive parameters [25].
internal reference TMS). IR spectra were recorded
on UR-20 instrument. The purity of products was
controlled by GLC on a chromatograph Chrom-5
(stationary phase SE-30 on Chromaton N-AW-DMCS,
l 1.2 m, flame-ionization detector, temperature
1
programmed at a rate 12 deg min , carrier gas
helium) and by TLC on Silufol UV-254 plates (eluent
CHCl3).
The initial anilides I, II, V were prepared by
procedure described in [18, 19].
N-Acetyl-2-(2-cyclohexen-1-yl)aniline (VI). To a
solution of 1.73 g of 2-(2-cyclohexen-1-yl)aniline in
10 ml of dichloromethane was added 2.04 g of acetic
anhydride, and the mixture was left standing for
18 h. Then the reaction mixture was diluted with
water, extracted with 100 ml of CH2Cl2, the extract
was washed with 5% water solution of NaHCO3 till
the end of CO2 liberation, then again with water
(20 ml), dried on MgSO4, and evaporated. We ob-
tained 2.04 g (95%) of oily amide VI.
EXPERIMENTAL
1H and 13C NMR spectra were registered on
spectrometer Bruker AM-300 at operating frequencies
300 and 75 MHz respectively (solvent CDCl3,
N-Formyl-2-(1-cyclopenten-1-yl)-6-methylaniline
(IX). A solution of 1 g of amine XIII in 10 ml of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

REACTIONS OF N- AND C-ALKENYLANILINES: I.
839
Table 4. 13C NMR spectra (CDCl3) of synthesized compounds III, IV, VI, IX, X, XIV XVIII, XX XXII, XXVI,
XXVII
Compd.
no.
Chemical shifts, C, ppm
III
18.2 (CH3), 23.2 (CH3) 23.3 (C2), 30.9 (C3), 32.1 (C1), 121.5 (C9a), 121.7 (C8), 124.6 (C9), 127.8 (C7),
136.4 (C6), 137.2 (C3a), 145.9 (C9b), 148.9 (C5a), 154.1 (C4)
IV
21.7 (C8), 22.2 (C9), 23.2 (CH3), 25.2 (C7), 26.5 (C10), 122.1 (C1), 125.1 (C4), 126.4 (C10b), 127.6 (C3),
128.7 (C2), 140.6 (C10a), 145.2 (C4a), 158.3 (C6),
VI
21.4 (C5 ), 24.8 (C6 ), 24.9 (CH3), 29.8 (C4 ), 39.1 (C1 ), 121.4 (C6), 125.7 (C3 ), 127.9 (C3), 128.2 (C5),
129.5 (C4), 129.8 (C2 ), 136.4 (C2), 138.5 (C1), 168.5 (C=O)
IX
18.9 (CH3), 23.8 (C4 ), 33.4 and 33.6 (C3 ), 36.0 and 36.3 (C5 ), 126.3, 127.0, 127.2, 127.4, 129.4, 129.6,
130.7, 130.8, 132.0, 134.3, 135.7, 136.0, 141.1 (C arom, C1 , C2 ), 159.7 and 165.1 (C=O)
18.8 (CH3), 24.6 (C2), 31.2 (C3), 31.4 (C1), 122.3 (C9a), 122.5 (C8), 126.6 (C9), 128.6 (C7), 136.5 (C3a),
137.5 (C6), 146.2 (C9b), 146.5 (C5a), 150.2 (C4)
X
XIV
XV
17.4, 18.0, 20.0, 21.0, 28.5 (CH3), 122.2, 122.7, 126.8, 127.7, 131.8, 136.6, 138.0, 142.3 (C arom,
C1 ,C2 ), 156.0 (N=CN)
14.2, 16.3, 17.7, 20.8, 21.8 (CH3), 28.5 (NCH3), 122.5 (C3), 127.7 (C5), 129.7 (C2 ), 131.1 (C1 ), 131.2
(C6), 136.1 (C4), 138.3 (C2), 141.0 (C1), 156.1 (N=CN)
XVI
XVII
XVIII
XX
16.9, 18.1, 23.7 (3 CH3), 27.7 (NCH3), 33.2 (C3 ), 35.5 (C5 ), 121.1 (C4), 126.1 (C2 ), 127.9 (C5), 128.2
(C3), 129.16 (C6), 142.1 (C1 ), 147.8 (C1), 155.2 (N=CN)
13.9, 17.0, 20.4, 24.3 (CH3), 22.3 (C3 ), 121.1 (C6), 127.9 (C5), 128.5 (C2 ), 130.7 (C3), 132.1 (C2),
133.2 (C4), 133.4 (C1 ), 145.2 (C1), 151.1 (N=CN), 122.4, 127.7, 128.5, 130.7 (Ph H)
13.7, 17.3, 18.0, 20.2 (CH3), 21.4 (C3 ), 121.2 (C6), 128.8 (C5), 129.3 (C2 ), 132.1 (C2), 132.9 (C1 ),
134.0 (C3), 139.2 (C4), 143.0 (C1), 154.0 (N=CN), 122.7, 127.8, 128.8, 134.1 (Ph H)
13.9, 21.0, 23.2, 28.7 (CH3), 17.5 (C2 ), 31.3 (NCH3), 43.2 (C1 ), 61.2 (C4), 122.5 (C8), 124.5 (C7),
127.3 (C4a), 132.8 (C6), 138.9 (C8a), 156.3 (C2)
XXI
XXII
XXVI
XXVII
17.8, 24.3 (CH3), 26.2 (C3 ,C4 ), 32.7 (NCH3), 40.8 (C2 ,C5 ), 66.3 (C4), 121.6 (C7), 123.2 (C5), 128.9
(C6), 130.8 (C8), 131.6 (C4a), 139.8 (C8a), 156.4 (C2)
13.4, 20.8, 22.7, 28.6 (CH3), 17.0 (C2 ), 45.0 (C1 ), 62.4 (C4), 121.4 (C8), 124.3 (C5), 126.9 (C4a),
128.3 (C7), 133.6 (C6), 138.7 (C8a), 156.0 (C2), 128.8, 129.3, 130.7, 136.3 (Ph H)
16.4, 18.2 (CH3), 23.4 (C4 ), 33.1 (C3 ), 35.4 (C5 ), 123.0, 125.4, 125.8, 126.3, 128.6, 128.8, 129.0,
130.3, 132.9, 133.3, 137.8, 140.6 (Ar H, C1 , C2 ), 160.2 (N=CN)
17.7, 24.4 (CH3), 23.3 (C3 , C4 ), 38.3 (C2 , C5 ), 63.3 (C4), 123.7, 123.9, 125.4, 129.1, 129.2, 130.2,
130.8, 132.2, 134.9, 139.3 (Ar H), 159.7 (C2)
anhydrous formic acid was heated at reflux for
40 min, and excess acid was evaporated in a vacuum.
The residue was dissolved in toluene, and the solvent
was evaporated in a vacuum; this procedure was
repeated twice. Then the residue was recrystallized
from hexane. Yield 1.1 g (95%).
into benzene and dried on KOH. The solvent was
evaporated in a vacuum, and the residue was sub-
jected to chromatography on a column (0.5 30 cm)
packed with silica gel (3g), elution first with benzene,
then with a mixture benzene methanol, 9: 1.
4,6-Dimethyl-2,3-dihydro-1H-cyclopent[c]-quino-
line (III). In a mixture of NH4Cl, P2O5, and tri-
butylamine prepared as above was dissolved 0.22 g
of benzoxazine VII. The reaction and workup of
products was carried out as above.
Cyclization of anilides I, II, V, VI in the
presence of P2O5. To a mixture of 1.1 mmol of
methylamine hydrochloride or NH4Cl and 10 mmol
of P2O5 was added 100 mmol of tributylamine and
then 1 mmol of the appropriate acetanilide I, II,
V, or VI. The reaction mixture was heated to 160
170 C for 2 h and on cooling to room temperature it
was diluted with 100 ml of water. In small portions
was added 20% water solution of NaOH till alkaline
reaction. Reaction product III or IV was extracted
6-Methyl-2,3-dihydro-1H-cyclopent[c]quinoline
(X). To a solution of 0.48 g of PCl5 in 10 ml of
benzene was added slowly by small portions 0.4 g of
formanilide IX. Then to the mixture was added
2 mmol of NH4Cl. The reaction mixture was heated
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

840
GATAULLIN et al.
for 2.5 h at 80 C, cooled, treated with 10% water
solution of NaOH, and extracted with CHCl3
(2 20 ml). The extract was dried on Na2SO4, the
solvent was evaporated in a vacuum, the residue was
washed with hot pentane or hexane (3 10 ml), the
hydrocarbon solutions were combined, evaporated,
and the residue was subjected to chromatography
on silica gel (eluent CHCl3). We separated 0.27 g
(66%) of the original amide IX and 0.1 g (28%) of
quinoline X.
6. Vassin, F.A., Eissa, A.M.F., and Wasfy, A.A.F.,
Indian. J. Chem. B, 1994, vol. 33, no. 12,
pp. 1193 1196.
7. Kumar, P.R. and Reddy, M.S., Indian J. Chem. B,
1994, vol. 33, no. 9, pp. 883 884.
8. Ukrainets, I.V., Taran, S.G., Gorokhova, O.V.,
Bezuglyi, P.A., and Turov, A.I., Khim. Geterotsikl.
Soed., 1994, no. 2, pp. 225 228.
9. Akazome, M.A., Kondo, T., and Watanabe, Y.,
J. Org. Chem., 1993, vol. 58, no. 2, pp. 310 312.
10. Savel,ev, V.A. and Loskutov, V.A., Khim. Getero-
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11. US Patent 5284852, 1994; Ref. Zh. Khim., 1995,
9 O 118P.
12. US Patent 5214114, 1993. Ref. Zh. Khim., 1994,
18 O 291P.
13. Molina, P., Aller, E., and Lorenzo, A., Synthesis
(BRD), 1998, no. 3, pp. 283 287, Ref. Zh. Khim.,
1999, 14 Zh 215.
14. Heinicke, G., Hung, T.V., Prager, R.H., Ward, A.D.,
Austral. J. Chem., 1984, vol. 37, no. 4, pp. 831 844.
15. Marcinkiewicz, S., Green, J., and Mamalis, P.,
Tetrahedron, 1961, vol. 17, no. 3 4, pp. 208 222.
16. Nielsen, K.E. and Pedersen, E.B., Acta Chem.
Ssand. B, 1980, vol. 34, no. 9, pp. 637 642.
17. Weygand Hilgetag, Organisch-Chemische Experi-
mentierkunst, 3d edn., Leipzig: Verlag, 1964.
18. Gataullin, R.R., Afon,kin, I.S., Pavlova, I.V.,
Abdrakhmanov, I.B., and Tolstikov, G.A., Izv. Akad.
Nauk, Ser. Khim., 1999, no. 2, pp. 398 401.
19. Gataullin, R.R., Afon,kin, I.S., Fatykhov, A.A., and
Abdrakhmanov, I.B., Izv. Akad. Nauk Ser. Khim.,
2000, no. 1, pp. 118 120.
20. Denton, D.A., Smalley, R.K. and Suschitzky, H.,
J. Chem. Soc., 1964, no. 7, pp. 2421 2425.
21. Abdrakhmanov, I.B., Sharafutdinov, V.M., Nigma-
tullin, N.G., Sagitdinov, I.A., and Tolstikov, G.A.,
Zh. Org. Khim., 1982, vol. 18, no. 7, pp. 1466 1471.
22. Gataullin, R.R., Afon,kin, I.S., Fatykhov, A.A.,
Spirikhin, L.V., Tal,vinskii, E.V., and Abdrakhma-
nov, I.B., Izv. Akad. Nauk, Ser. Khim., 2000, no. 12,
pp. 1 7.
Amidines XIV XVIII, XXVI. To a cooled solu-
tion of 0.023 mol of PCl5 in 20 ml of CHCl3 or
benzene was added slowly by small portions 0.02 mol
of an appropriate N-methyl- or N-phenylacetamide.
On completion of the reaction to the mixture was
added 0.02 mol of an appropriate alkenylaniline dis-
solved in 10 ml of CHCl3 or benzene. Then the reac-
tion mixture was heated for 2.5 h at 80 C, cooled,
treated with 10% water solution of NaOH, the pro-
duct was extracted into CHCl3 (2 20 ml), and dried
on Na2SO4. The solvent was evaporated in a vacuum,
the residue was washed with hot pentane or hexane
(3 10 ml), the hydrocarbon solutions were combined,
cooled, the precipitate was separated and dried in a
vacuum.
Cyclization of amidines XIV XVIII, XXVI.
Amidine XIV XVIII, XXVI (1 mmol) was mixed
with 1.5 g of polyphosphoric acid and heated to
150 160 C for 4 h. Then the reaction mixture was
cooled to room temperature, washed with small
portions of a concn. water solution of Na2CO3 till
alkaline reaction by universal indicator strips. The
reaction product was extracted into ethyl acetate
(3...10 ml), dried on Na2SO4, the solvent was
evaporated at reduced pressure.
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