S- and N,S-containing heterocycles based on sulfenyl chlorides of substituted 1,4-naphthoquinone

Full text of DOI:10.1007/s10593-010-0539-5

Chemistry of Heterocyclic Compounds, Vol. 46, No. 4, 2010
S- AND N,S-CONTAINING HETEROCYCLES BASED
ON SULFENYL CHLORIDES OF SUBSTITUTED
1,4-NAPHTHOQUINONE
I. R. Buchkevych1, M. V. Stasevych1, R. Ya. Musyanovych1,
V. I. Lubenets1, and V. P. Novikov1*
Keywords: 1,4-naphthoquinone, sulfenyl chlorides, thiazines, thioketones, thiopyrans.
We have carried out for the first time the synthesis of thiopyran and thiazine derivatives of 1,4-naphtho-
quinone by the reaction 3-hydroxy- (1), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)- (2), 3-amino- (3), 3-[(4-methyl-
phenyl)amino]-2-chlorosulfenyl-1,4-naphthoquinones (4) [1, 2] in the presence of equimolar amounts of
trimethylamine with dimethylbutadiene and styrene in chloroform at a temperature of -5 to -10°C for 5 h.
During the reaction unstable intermediate thioketones 5′,6′ or iminothioketones 7′,8′ were formed which reacted
in situ with dimethylbutadiene or styrene to give the adducts 5,6 and 7,8 respectively. On evaporating the
chloroform the compounds 5,6 were isolated as needle-like crystals which were purified by crystallization from
hexane, while the isomeric compounds 7a,b and 8a,b were separated by column chromatography (eluent 3:1
benzene–ethyl acetate).
1
In the H NMR spectra of the synthesized naphthoquinones 7a,b characteristic multiplet signals of the
protons of the naphthoquinone fragment and the phenyl substituent are observed at weak field in the 7.08 to 8.11
ppm range, while the multiplet of the CH proton of the thiazine ring depends on the nature of the heteroatom in
the α-position.
When the methine proton is next to the sulfur atom of the naphthothiazine fragment in compounds 7a, 8a
it is shifted to weaker field at 5.23 and 5.16 ppm respectively, in comparison with the signals of the regio-
isomers 7b, 8b where the peaks are observed at 4.00 and 4.82 ppm. In our view, such shifts of the signals of the
methine proton are determined by the electron-donor influence of the NR substituent and the -C effect of the
sulfur atom, and the presence of vacant d-orbitals (2px-3d interaction).
So stable thiopyran 5,6 and thiazine 7, 8 derivatives of 1,4-naphthoquinone have been synthesized for
the first time.
1H NMR spectra of DMSO-d6 solutions with TMS as internal standard were measured with a Bruker
MSL-400 (400 MHz) instrument at 25°C.
4',5'-Dimethyl-3',6'-dihydro-1H-spiro[naphtho-2,2'-thiopyran]-1,3,4-trione (5). Yield 47%; mp
1
185-187°C. H NMR spectrum, δ, ppm (J, Hz): 8.09 (2H, m, CH, Ar); 7.85 (2H, m, CH, Ar); 3.53 (2H, dd,
5
2
5
2J = 17.9, J = 3.0, CH2); 2.81 (2H, dd, J = 16.5, J = 3.0, CH2); 1.78 (3H, s, CH3); 1.70 (3H, s, CH3). Found,
%: C 66.86; H 4.28; S 12.05. C16H14O3S. Calculated, %: C 67.11; H 4.93; S 11.20.
_______
* To whom correspondence should be addressed, e-mail: vnovikov@polynet.lviv.ua.
1 Lviv Polytechnic National University, Lviv 79013, Ukraine.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 632-634, April, 2010. Original article
submitted March 16, 2010.
502
0009-3122/10/4604-0502©2010 Springer Science+Business Media, Inc.

O
O
R1
S
R1
S
O
Me
O
O
R
Me
Et3N
5, 6
5', 6'
–HCl
SCl
CH
CH2
O
O
NR2
S
1–4
O
7', 8'
O
O
R2
N
O
R2
N
+
S
S
O
7a,b
8a,b
HN
Me
,
, 3 R = NH , 4 R =
OH
1 R = OH, 2 R =
2
5',5 R1 = O, 6',6 R1 =
7',7, 8',8 a R2 = H, b R2
=
Me
O ,
3-(3,5-Di(tert-butyl)-4-oxocyclohexa-2,5-dien-1-ylidene)-4',5'-dimethyl-3',6'-dihydro-1H-spiro-
1
[naphtho-2,2'-thiopyran]-1,4(3H)-dione (6). Yield 35%; mp 168-170°C. H NMR spectrum, δ, ppm (J, Hz):
8.36 (H, d, 4J = 2.5, CH Ar); 8.25 (2H, m, CH Ar); 7.81 (2H, m CH Ar); 7.70 (H, d, 4J = 2.5, CH Ar); 3.45 (2H,
2
5
2
dd, J =17.9, J = 2.0, CH2); 3.05 (2H, dd, J = 18.7, 5J = 1.5, CH2); 1.73 (3H, s, CH3); 1.69 (3H, s, CH3); 1.17
(18H, s, CH3). Found, %: C 75.97; H 6.98; S 6.85. C30H34O3S. Calculated, %: C 75.91; H 7.22; S 6.76.
2-Phenyl-3,4-dihydro-2H-naphtho[2,3-b]-1,4-thiazine-5,10-dione (7a). Yield 32%; mp 180-181°C. 1H
NMR spectrum, δ, ppm (J, Hz): 8.11 (2H, m, CH Ar); 7.68 (2H, m, CH Ar); 7.48 (1H, s, NH); 7.08 (5H, m, CH
Ar), 5.23 (1H, m, CH); 3.51 (2H, m, CH2). Found, %: C 71.14; H 4.53; N 4.43; S 9.94. C18H13NO2S. Calculated,
%: C 70.34; H 4.26; N 4.56; S 10.43.
4-(4-Methylphenyl)-2-phenyl-3,4-dihydro-2H-naphtho[2,3-b]-1,4-thiazine-5,10-dione (7b). Yield 7%;
mp 183-184°C. 1H NMR spectrum, δ, ppm (J, Hz): 8.07 (2H, dd, 3J = 7.7, 5J = 0.6, CH Ar); 7.73 (2H, m, CH Ar);
7.35 (4H, m, CH Ar); 7.09 (5H, m, CH Ar); 5.38 (1H, m, CH2); 4.96 (1H, m, CH); 4.69 (1H, m, CH2); 2.31 (3H, s,
CH3). Found, %: C 76.01; H 4.14; N 3.55; S 8.12. C25H19NO2S. Calculated, %: C 75.54; H 4.82; N 3.52; S 8.07.
3-Phenyl-3,4-dihydro-2H-naphtho[2,3-b]-1,4-thiazine-5,10-dione (8a). Yield 45%; mp 189-192°C. 1H
NMR spectrum, δ, ppm (J, Hz): 8.09 (2H, dd, 3J = 7.7, 5J = 0.6, CH Ar); 7.69 (2H, m, CH Ar); 7.28 (5H, m, CH
2
3
Ar); 6.67 (1H, s, NH); 5.16 (1H, m, CH); 3.76 (2H, dd, J = 1.7, J = 3.5, CH2). Found, %: C 70.28; H 4.45;
N 4.62; S 9.91. C18H13NO2S. Calculated, %: C 70.34; H 4.26; N 4.56; S 10.43.
503

4-(4-Methylphenyl)-3-phenyl-3,4-dihydro-2H-naphtho[2,3-b]-1,4-thiazine-5,10-dione (8b). Yield
1
5%; mp 192-193°C. H NMR spectrum, δ, ppm (J, Hz): 8.07 (2H, m, CH Ar); 7.75 (2H, m, CH Ar); 7.65 (2H,
m, CH Ar); 7.34 (7H, m, CH Ar); 5.57 (1H, m, CH); 4.195 (2H, dd, 2J = 1.7, 3J = 3.5, CH2); 2.29 (3H, s, CH3);
Found, %: C 75.94; H 4.24; N 3.65, S 8.22. C25H19NO2S. Calculated, %: C 75.54; H 4.82; N 3.52; S 8.07.
Supported by a Ukraine-Lithuania agreement M/43-2009.
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