Investigation on 2,3′-biquinolyl series. 21. Reactions of 1′-alkyl-4′-aryl-1′,4′-dihydro-2,3′-biquinolyls and 1′-alkyl-2′-aryl-1′,2′-dihydro-2,3′- biquinolyls with sulfur

Article abstract of DOI:10.1007/s10593-006-0240-x

A method has been developed for the synthesis of 2′-and 4′-aryl-2,3′-biquinolyls based on the reaction of 1′-alkyl-2′-aryl-1′,2′-dihydro-2,3′-biquinolyls and 1′-alkyl-4′-aryl-1′,4′-dihydro-2,3′- biquinolyls with sulfur in DMF.

Full text of DOI:10.1007/s10593-006-0240-x

Chemistry of Heterocyclic Compounds, Vol. 42, No. 10, 2006
INVESTIGATION ON 2,3'-BIQUINOLYL SERIES.
2
2
1
1.* REACTIONS OF 1'-ALKYL-4'-ARYL-1',4'-DIHYDRO-
,3'-BIQUINOLYLS AND 1'-ALKYL-2'-ARYL-
',2'-DIHYDRO-2,3'-BIQUINOLYLS WITH SULFUR
1
2
1
D. V. Moiseev , V. I. Goncharov , and A. V. Aksenov
A method has been developed for the synthesis of 2'- and 4'-aryl-2,3'-biquinolyls based on the reaction
of 1'-alkyl-2'-aryl-1',2'-dihydro-2,3'-biquinolyls and 1'-alkyl-4'-aryl-1',4'-dihydro-2,3'-biquinolyls with
sulfur in DMF.
Keywords: 2,3'-biquinolyls, 1',2'-dihydro-2,3'-biquinolyls, 1',4'-dihydro-2,3'-biquinolyls, sulfur,
desalkylation, oxidation.
In a continuation of our study of the reactions of 2,3'-biquinolyls with sulfur [2-6] we have examine the
reactions of 1'-alkyl-4'-aryl-1',4'-dihydro-2,3'-biquinolyls 1 and 1'-alkyl-2'-aryl-1',2'-dihydro-2,3'-biquinolyls 2
with this reagent.
It is known that sulfur forms a donor-acceptor complex with amines [7], full transfer of an electron in
+
·
-·
which leads to an R N S ion radical pair [8]. Cation radicals generally undergo fission of a proton [9] and this
3
8
is observed, in particular, in the oxidation of dihydropyridines (quinolines). The reaction of the radicals formed
is governed by the electronic and steric effects of the R substituent. Hence we have shown before that in the
thiolation of 1'-alkyl-1',4'-dihydro-2,3'-biquinolyls both complex formation [5, 6] and steric factors [5] are
significant.
Ar
Ar
Ar
N
S8
N
N
N
.
N
R
N
R
5a–c
3a–d
.
1
a–d
HS8
1
2 2 7
a-c R = Me, d R = CH CHCH ; 1, 5 a Ar = Ph, b Ar = 1-C10H , c, d Ar = 3-indolyl
_
*
_
______
For Communication 20 see [1].
_________________________________________________________________________________________
1
2
Stavropol State University, Stavropol 355009, Russia; e-mail: k-biochem-org@stavsu.ru. Stavropol
State Medicinal Academy, Stavropol 355017, Russia; e-mail: sgma@statel.stavropol.ru. Translated from
Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1517-1519, October, 2006. Original article submitted
October 20, 2005.
1
308
0009-3122/06/4210-1308©2006 Springer Science+Business Media, Inc.

N
S8
N
.
Ar
a,b
N
R
Ar
N
R
.
a,b HS8
2
4
N
Ar
N
6
a,b
2
a, b R = Me; 2, 6 a Ar = Ph, b Ar = 1-С Н
10 7
We have proposed that the reactions of compounds 1 and 2 with sulfur also lead to the corresponding
radicals 3 and 4. However, because of steric hindrance due to 2'-aryl, 4'-aryl, and 3-quinolyl the process is
completed by the transition of the 1'-alkyl to the S-radical [10]. Thus the final reaction products are the 2'- and
4
'-aryl-2,3'-biquinolyls 5 and 6.
In fact, the reaction of the dihydro derivatives 1a-d and 2a,b with sulfur gives the corresponding
arylbiquinolyls 5a-c and 6a,b in 21-57% yields.
These results can be explained in the following way. It is known that steric factors can affect a
competitive SET and polar mechanism. In compounds 2a,b there is steric hindrance to the approach of the
S-radical to the 1'-methyl on the 2' substituent side. This decreases the likelihood of a one electron transfer and
favors a radical process. The reactions of 2a,b with sulfur give complex mixtures of substances from which
compounds 6a,b are separated with difficulty and in low yields.
The increase in yield upon desalkylation of 4'-(3-indolyl) derivatives 1c,d when compared with the
4
'-phenyl derivative 1a can be explained by the π-donor effect of the indolyl substituent. As a result this eases
both the formation of the π -complexes and the subsequent electron transfer.
EXPERIMENTAL
1
3
H NMR spectra were recorded on a Bruker WP-200 (200 MHz) instrument using CD CN solvent and
TMS internal standard. Mass spectra were taken on an MAT-311A instrument. IR spectra were recorded on a
Hitachi 215 instrument. Monitoring of the reaction course and the purity of the synthesized compounds was
carried out on Silufol UV-254 plates using ethyl acetate–petroleum ether (1:1).
Compounds 1 and 2 were prepared by methods in [11, 12].
Dehydrogenation of the Dihydrobiquinolyls 1 and 2 by Sulfur (General Method). A mixture of
1
3
'-R-2'-aryl-1',2'-dihydro- or 1'-R-4'-aryl-1',4'-dihydro-2,3'-biquinolyl (2 mmol) and elemental sulfur (0.1 g,
mmol) was refluxed in DMF (10 ml) for 3 h. The reaction mixture was cooled and poured into water (100 ml).
The precipitate was filtered off, washed with water, and dried.
'-Phenyl-2,3'-biquinolyl (5a, C H N ) was prepared from 1'-methyl-4'-phenyl-1',4'-dihydro-2,3'-
4
2
4
16
2
1
biquinolyl. Yield 35%; mp 133-134°C (benzene) (mp 133-134°C [13]). The H NMR spectrum agreed with that
given in [13].
1
309

4
18 2
'-(1-Naphthyl)-2,3'-biquinolyl (5b, C28H N ) was prepared from 1'-methyl-4'-(1-naphthyl)-1',4'-
1
dihydro-2,3'-biquinolyl. Yield 42%; mp 158-159°C (benzene–hexane) (mp 158-159°C [13]). The H NMR
spectrum agreed with that given in [13].
4
'-(3-Indolyl)-2,3'-biquinolyl (5c) was prepared from 4'-(3-indolyl)-1'-methyl-1',4'-dihydro-2,3'-
biquinolyl (53% yield) and from 1'-allyl-4'-(3-indolyl)-1',4'-dihydro-2,3'-biquinolyl (46% yield); mp 173-175°C
-
1
1
(
benzene–hexane). IR spectrum (KBr tablet), ν, cm : 3210 (NH). H NMR spectrum, δ, ppm (J, Hz): 6.88 (1H,
dd, J4'',5'' = 7.95, J5'',6'' = 7.77, H-5'); 7.06 (1H, d, J3,4 = 8.97, H-3); 7.08 (1H, d, J4'',5'' = 7.95, H-4''); 7.13 (1H, dd,
J5'',6'' = 7.7, J6'',7'' = 7.56, H-6''); 7.24 (1H, d, J2''-NH = 2.56, 2''-H); 7.48 (1H, d, J6'',7'' = 7.56, H-7''); 7.55 (1H, dd,
J5,6 = 8.06, J6,7 = 7.11, H-6); 7.56 (1H, d, J5',6' = 8.29, H-5'); 7.80 (4H, m, H-4,6',7,7'); 7.96 (1H, d, J5,6 = 8.06,
H-5); 8.11 (1H, d, J7',8' = 8.45, H-8'); 8.20 (1H, d, J7,8 = 8.24, H-8); 9.31 (1H, s, H-4'); 9.64 (1H, br. d,
+
J2''-NH = 2.56, NH). Mass spectrum (70 eV), m/z (I , %): 371 [M] (82), 370 [M-1] (100). Found, %: C 84.14;
rel
H 4.57; N 11.29. C H N . Calculated, %: C 84.07; H 4.61; N 11.31.
2
6
17
3
2
'-Phenyl-2,3'-biquinolyl (6a, C H N ) was prepared from 1'-methyl-2'-phenyl-1',2'-dihydro-2,3'-
24 16 2
1
biquinolyl. Yield 24%; mp 76-77°C (benzene–hexane) (mp 76-77°C [14]). The H NMR spectrum agreed with
that given in [14].
2
'-(1-Naphthyl)-2,3'-biquinolyl (6b, C H N ) was prepared from 1'-methyl-2'-(1-naphthyl)-1',2'-
28 18 2
1
dihydro-2,3'-biquinolyl. Yield 21%; mp 77-78°C (benzene–hexane) (mp 77-78°C [14]). The H NMR spectrum
agreed with that given in [14].
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