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Novel 1 2 4-Thiadiazolidine 1-Oxides and 1 1-Dioxides from 2-Imino-1 3-thiazetidines.

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131 T Mukoiwiirr and E Yokor<r, Bull. Chem. Soc. Japan 3X. 858 (1965).
[4] 7: Mirkaivuiiru, H . Nuiiihir. and 7: K m o i n o r o , J. Org. Chem. 29. 2243
( 1 964).
[5] 7 M ~ r k o i j ~ o r t ~Ho.. Nainhrr. and I . Kirwtqiiiiu. J. Org. Chem. 28, 9 17
( I964).
[6] 7: M i ~ k u i j ~ u i i i u1.. Kuwujifiiu, and Z. Suzrrki, J. Org. Chem. ZX, 2024
(1963).
[7] I . Kuiwrjriritr and 7: Muktriyurnu. J. Org. Chem. 29. 1385 (1964).
[XI T Mukoi!,uriiir and I . Kuwujirnu, unpublished results.
[Y] 7: M r r / i o i ~ ~ t r iand
~ ~ t rM. Ueki. Tetrahedron Lett. 1967, 3429.
[IOJ
[I I]
[ 121
[ 131
[ 141
[I51
[I61
[I71
[I81
[ 191
[20]
[ Z I]
7: Erido, S. Ikrriiryu, and 7: Mukoiyurirtr. Bull. Chem. Soc. Japan 43.
2632 (1970).
M . Ueki, H. Moru!~umu,and T Mirkuiyoriio, Bull. Chem. Soc. Japan
4 4 , 1108 (1971).
7:M i ~ ! , ~ r r ~ ~Mu. ~Urki,
i i ~ . H . Murrr~~oriio,
and R. Muf.sueilrr,J. Am. Chem.
Soc. 90, 4490 (1968).
R. Morsu&. H . M t r r u ~ o r i i r i .M. Ueki, and T Mukuiytuiro. Bull. Chem.
Soc. Japan 4 4 , 1373 (1971).
T Mukuij~oriio.R. M u t s d t r , and H . M o r ~ ~ ~ ~ o Bull.
i t i u .Chem. Sac. Japan
43. 1271 (1970).
R. A. June.\ and A. R. Ktirrirzky, J. Chem. Soc. 1958. 3610.
7: Mirkaiwiiiu, R. Mirr.\iredci, and M. S r i x k i . Tetrahedron Lett. 1970,
1901.
D. 7: Cish. P . C . Kafsoyurirri.s. C . P . H r s s , and R. J . Srrdriim. J. Am.
Chem. Soc. 7X. 5954 (1956).
7: Mrrkuij,uiiiu, K . Cofo, R. Mtrf.wedu, and M . U d i , Tetrahedron Lett.
IY7ll. 5293.
7: Mriktriwiru, K . Cofo. R. Mor.suedu, A . Hu!v~.sbir/u, and M . Upki
!n 7: Kunrko: 8th Symposium on Peptide Chemistry, Osaka. 1970.
Protein Research Foundation, Osaka 1971, p. 110.
R. Murs!rn/o, H . M u r i r w m u . E . Kirtrxivrr. H . Erkohtryi. and 7: Mukuivuriiu, Bull. Chem. Soc. Japan 46, 3240 (1973).
R. M u r , w d u . E. K r f o z o i m . H . Mor~ryoriio,H . Tukuhuyi, and 7: M o k u i j ' u i i i u in H . Kortrkr' I Ith Symposium on Peptide Chemistry. Kanazawd
1973. Protcin Research Foundation. Osaka 1974. p. 40.
[22] R. Morsiredtr. H . Murrrwino. E. Kifrrzrwo, H . Erkohu~/i,and 7: M r r k criyuiiio. J. Am. Chem. Soc. 97. 2573 (1975).
[23] 7: Mukai~riiiiuand M . Hadiiriioro. J. Am. Chem. Soc. 94, 8528 (1972).
1241 7: Hotcr. I . Nokciguivu, and N. Erkdxrw.\hi, Tetrahedron Lett. 1Y72,
2931.
[25] H . 7irkakii. E Shirnadrr, and T. Haftr, Chem. Lett., in press.
[26] 7: Hatrr, 1. N a k o ~ ~ u c and
a , Y. Nukoclo, Tetrahedron Lett. 1975. 467.
1271 M . Hrrsliinioro and 7: Mukoir.urtitr, Chem. Lett. 1973. 513.
12x1 M . Hoshiriiofo and 7: Miikoiwrriio. Chem. Lett. 1972, 595.
[29] E . J. C o r q and K . C . Nr~olrrurr,J. Am. Chem. Soc. 96, 5614 (1974).
1301 E. J . Corer, K . C . Nicoloou, and L. S . Mrlcin, J r . , J. Am. Chem.
Soc. 97, 653 11975).
[31] E . J. C o n y . K . C. Nirolcrou, and L. S. M r l r i n , J r . , J Am. Chem.
Soc. 97. 654 (1975).
1321 0. Mirsiriiohir and M. firrnudu, Bull. Chem. Soc. Japan 40. 2380 (1967).
[33] 0. Mifsrritohrr. J . Kirnuro, and E Fiijisuwu. Bull. Chem. Soc. Japan
45, 245 (1972); 0. Miraunohu. private communication.
1341 0. Mitstrnohrr and M. Eyuchi, Bull. Chem. Soc. Japan 44. 3427 (1971).
[35] 0. Mirsuriohu. K . Kuro, and J. Kirinrro, J. Am. Chem. Soc. Y1. 6510
( 1969).
1361 A. K . Boar, B. Lul, W A. Hoffinuii, and M . S. Murihu.s, Tetrahedron
Lett. 1973, 1619.
1371 0. M i r s ~ ~ t ~ oM.
h ~ Wodu.
i,
and 7: Sario, .I.Am. Chem. Soc. 94, 679 (1972).
1381 M . Wodo, T Sorio, and 0. Mirsiuiohu. Bull. Chem. Soc. Japan 46,
2833 (1973).
[39] A. Ztiriiqjski, W A . Szorek, and J. K. N . Jonrs, Carbohyd. Res. 23,
460 (1972).
[40] M. Wlrhand 0. Mif.siriiuhir, Tetrahedron Lett. 1972, 1279; 0. Mirsrniohu.
private communication.
[41] S. Birfrirr and E Assu/; Chem. Ind. (London) 1975, 281.
1421 7: M ~ r k u i y u r ~ ~Mu.. Usui. E . Shirnudrr. and K. Suiyo, Chem. Lett. 1975.
1045: 7: M u k u i ~ ~ u n i uS.. Ikedo. and S. K o h g n s b i , ihid. 1975. 1159:
E . B d d , K . Soigqo, and 7: Mukaiyuriia. ihid. 1975, 1163; 7: Mukoii~rrriio,
H . 7 i h , and S. Kohoyrrsiii. ihid. 1976, 13: 7: Mukoi~oiiiu, M . Usui.
and K . Striggo, ihrtl. 1976, 49; 7: Mukrri!~oiiiu,E Aikawo. and S. Kohrryrrshi.
ihid 1976, 51.
C 0 M M U N I CAT1 0N S
substituted thioureas, diiodomethane, and triethylamine[" *I,
leads not to the 2-imino-I ,3-thiazetidine 1 ,I-dioxides ( 3 ) , but,
surprisingly, with ring expansion to the 3-0X0-~.2.4-thiadiazolidine I-oxides ( 5 ) . The oxidation products were identified by
X-ray structure analysis of (5h;i and ( 3 ~ )since
~ ~ no
' distinction could be made between the isomers ( 3 )- ( 5 ) on the basis
of spectroscopic data (Table 1). The 1,2,4-thiadiazolidine 1 oxide system was recently mentioned for the first time in
another connection[4].
We assume that ( 5 ) is formed tiu the two non-isolable
intermediates (2) and ( 4 ) . The initially formed S-oxide (2)
experiences an oxygen insertion resulting in ring expansion
analogous to the Baeyer-Villiger oxidation to give ( 4 ) . Subsequent Dimroth rearrangement leads to ( 5 ) .
Oxidation of ( 5 ) with H,OJglacial acetic acid furnishes
the 3-oxo-t,2,4-thiadiazolidine1,l-dioxides (6) (Table 1). The
reaction affords a novel entry to this class of compound,
whose preparation was first reported only recently[5!
Novel 1,2,4-Thiadiazolidine1-Oxides and 1,l-Dioxides
from ZImino-l,3thiazetidines
By Waiter R i d , Oskur Mdsinger, and Walter Schuckmnnn[*]
The action of hydrogen peroxide/glacial acetic acid on 2imino-I ,3-thiazetidines ( / I , which are accessible from N,N'-di[*] Prof. Dr. W. Ried and DipLChem. 0. Mosinger
lnstitut fur Organische Chemie der Universitit
Theodor-Stern-Kai 7. 6000 Frankfiirt/Main-70 (Germany)
Doz. Dr. W. Schuckmann
lnstitut fur Kristallographie der Universitit
Senckenberganlage 30, 6000 Frankfurt/Main-1 (Germany)
Aiiqerr. Cheiii. 1111. Ed. Eiig1.
f W)/,.lS
f
1976) N o . 2
I ,2,4- T h iarliazol idine I -0.y ides ( 5 ) and I , I -&ox ides ( 6 )
To a solution of ( I ) (5mmol) in glacial acetic acid (50ml)
[in thecaseofflf) 150mll isadded2.1 equivalentsofhydrogen
peroxide (35 aqueous solution). The mixture is allowed
to stand for 6 days at room temperature and the solvent
removed by distillation in a rotary evaporator. The residue,
in the case of ( 5 e ) and (Sf), is recrystallized (white needles)
from ethanol. In the case of ( 5 u ) - ( 5 d ) the residue is taken
up in chloroform, filtered, and the filtrate evaporated to
dryness. ( 5 n ) crystallizes on addition of ethanol/n-hexane;
( 5 b ) - ( 5 d ) are obtainable (as white crystals) after recrystallization from ethanol.
103
+
tions with reactive alkynes to give cyclobutene derivatives.
Valence isomerization of the latter affords the next higher
vinylogous annulene, i . e. benzene and cyclooctatetraene respectively". ']. A similar transformation should also be feasible
R2
RI-N
in the homologous series of nonalternant bicyclic hydrocarbons pentalene (I), azulene (2), and heptalene ( 3 ) , which
differ from each other by possessing one additional vinylene
group each, and thus provide new entries to these ring systems.
Studies on transformations of cyclopent[~d]azulene[~~,
1,3-bis(dimethylarnin~)pentalene[~J,
and he~aphenylpentalene[~J
with
H202
-tho
Table 1. Data for compounds ( 5 ) and (6). Correct analyses were obtained for all compounds.
R'
(ui
(h)
(c)
(d)
(e)
(f)
[a]
[b]
[c]
[d]
CH(CHd,
CH,
C,H,CHz
o-CH,C,H,CHZ
ChH,
CeHs
R2
CbHS
CdS
CbHS
CbHs
C ~ S
p-NO,C,H,
'H-NMR [b, c]
[kppmlq
Yield
Wl
(5)
IR [d]
[cm-ll
86
166
143
107.5
140
168
1690,
1694,
1692,
1700,
1700,
1725,
4.45
4.48
4.44
4.45
4.62
4.73
Yield
M.p.
[XI
72
34
53
60
46
46
1089
1080
1098
1099
1105
1092
(61
[%I
M.p.
c"C1
IR kdl
[cm-']
'H-NMR [b]
[S, ppm] s
35
31
111.5
137 (dec.)
1707, 1161
1715, 1159
4.70
4.79
13
11
10
108.5
120.5 (dec.)
254 (dec.)
1725, 1152
1725, 1159
1740, 1148
4.80
4.95
5.00
vC=O and vS=O in KBr.
Methylene groups in the heterocycle relative to H D M S O as internal standard, in CDCI,.
J,m=11.0H~.
vC=O and v S 0 , in KBr.
A solution of ( 5 ) (2mmol) in glacial acetic acid (50ml)
is treated with 1.2 equivalents of hydrogen peroxide (35%
aqueous solution) and allowed to stand for 4 weeks at room
temperature. The solution is evaporated under vacuum, and
compound (6) isolated from the residue by column chromatography on silica gel (eluant : benzene/ethyl acetate 4: 1).
Recrystallization from ethanol affords (6) as white crystals.
Received: December 15, 1975 [Z 364 IE]
German version: Angew. Chem. 88,120 (1976)
CAS Registry numbers:
( l a ) , 58151-15-8: ( I b ) , 58151-16-9: ( I c ) , 50500-04-4; ( I d ) , 58151-17-0:
( I e ) , 50500-03-3: ( I f ) , 58151-18-1: ( 5 a ) , 58151-04-5; ( 5 h ) . 58151-05-6;
f5c),58151-06-7: ( 5 d ) . 58151-07-8; ( S e ) , 58151-08-9; (Sf), 58151-09-0: f 6 u ) ,
58151-10-3; ( 6 h ) . 58151-11-4: (6d). 58151-12-5: ( 6 e ) , 58151-13-6: (6f),
dimethyl acetylenedicarboxylate into derivatives of aceheptyleneand azulene prompted us to investigate the ring expansion
of (1) to (2) and above all that of (2) to ( 3 ) . In the course
of this work we discovered a surprisingly simple and universal
synthesis of stable heptalene derivatives.
Conversion of pentalene into azulene: As expected, (4)[61
which is the simplest pentalene derivative hitherto isolated,
rapidly reacts with activated alkynes and especially with the
highly strained cyclooctyne at 270 "C (presumably oia intermediate formation of the cyclobutene derivative (5)) to give
a 70% yield of 2,4,12-tri-tert-butyl-5,6,7,8,9,10-hexahydrocycloocta[ flazulene ( 6 ) (blue radial needles, m. p. 7 G 7 2 'C)['J.
58151-14-7
[l]
M! R i d , M! Merkel, and 0. Mosinger, Justus Liebigs Ann. Chem. 1973,
1362.
121 M! R i d and 0. MBsinger, to be published.
[3] W Schuckmunn, 0. Mosinger, and M! Ried, t o be published.
[4] T Kinoshita, S. Sam, Y Furukunw, and C. Tomifro. Heterocycles 3, 1 ,
83 (1975).
151 5. A. Arbuzor, N . N . Zohoca, and N . R. Rubinow, Izv. Akad. Nauk
SSSR, Ser. Khim. 1975, 1438.
Cycloadditions of Pentalene and Azulene-A
Heptalene Synthesis[**]
Facile
By Klaus Hafner, Herbert Diehl, and Hans Ulrich Siisd'l
The two lowest homologs ofthe annulene series, i. e. cyclobutadiene and benzene, are known to undergo either thermally
or photochemically induced 12 +4] and [2 + 23 cycloaddi[*] Prof. Dr. K. Hafner, DipLIng. H. Diehl, a n d Dip1.-Chem. H. U. Suss
lnstitut fur Organische Chemie der Technischen Hochschule
Petersenstrase 15, 6100 Darmstadt (Germany)
This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen [ndustrie
[**I
104
Exclusive formation of (6) even at high temperatures indicates
on the one hand the lack of tendency of dimerization of
( 4 ) , in contrast to pentalene and its methyl derivatives['' and
on the other the marked effect of substituents upon product
formation. As in the dimerization of 2-methylpentalene[8J
and 1,5-dimethylpentalene[9! cycloaddition in the five-membered ring of ( 4 ) bearing an alkyl group in position 2 ( ~ 5 )
is hindered-mostly for obvious steric reasons.
Angew. Chem. I n t . Ed. Engl. 1 Vol. 15 (1976) N o . 2
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