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a-Sultenes and 1 3-Oxazolidinethiones by 1 3-Dipolar Cycloaddition of Thioketene S-Oxides to Azomethines.

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toluene and pentane, recrystallized from CH3N02/Et20,and
finally dried in a high vacuum; dec. pt. 118°C (in N2-filled
capillary tubes). Yield 80-90 %.
The trimethylphosphane complex [Fe(N03)PMe3]PF6(7)
is formed in an analogous way, dec. pt. 143°C.
Received: April 5, 1978 [Z 979 IE]
German version: Angew. Chem. 90, 477 (1978)
Table 1. Reaction conditions, yields, and principal IR bands of ( 4 ) , (6)
~-
(46)
(6a)
f6b)
(6c)
T
["C]
Reaction
time
Solvent
Yield
["/.I
M p
[OCl
IR (KBr)
[cm-'1
25
25
40
1d
12h
6h
1Od
Ether
Ether
None
None
70 [a]
58 [c]
72 [c]
48 [c]
97-98 [bl
103-105
9697
94-95
1575(C=C)
1485(Thioamide-B)
1480(ThioamideB)
1485(ThioamideB)
55
CAS Registry numbers:
(I), 13682-74-1; ( 4 ) , 66523-75-9; ( 5 ) , 14912-71-5; (6). 66552-49-6; (7),
66523-68-0
[a] ( 4 b ) crystallizes from a small volume of diethyl ether. [b] On melting
( 4 b ) undergoes partial conversion into ( 6 b ) . [c] Isolated by preparative
layer chromatography on silica gel (Kieselgel P F 254, eluent dichloromethane/
light petroleum or ethyl acetate/light petroleum).
[l] P. Legzdins, J. 7: Malito, Inorg. Chem. 24, 1875 (1975).
[2] W J. Geary, Coord. Chem. Rev. 7, 81 (1971).
[3] Measurements by Dr. F . J . Littersf, Physics Department, Technische
Universitat Munchen.
[4] W Beck, K . Lottes, Chem. Ber. 98,2657 (1965).
[5] I. natchenko, J. Organomet. Chem. 224, C39 (1977); D. Ballivet, C .
Billard, I . Tkatchenko, ibid. 124, C 9 (1977); D. Ballivet, I. Tkatchenko,
Inorg. Chem. 16, 945 (1977).
[6] All operations carried out under NZ.
X-Ray structure analysid5I of ( 4 b ) confirms the proposed
structure (cf. Fig. 1). The bond lengths in the C-S-CF-C
moiety largely correspond to the values already measured
for an open chain sulfenic ester, while the angles at the sulfur
The oxathiazolidine
and the nitrogen are ca. 6"
ring exists in an envelope conformation, with C-5 deviating
from the plane of the other ring atoms (k8 pm).
y -Sultenes and 1,3-0xazoIidinethiones by 1,3Dipolar
Cycloaddition of Thioketene S-Oxides to Azomethhes[**I
By Ernst Schaumann, Jorn Ehlers, and Ulrich Behrens[*]
Thioketenes undergo [I2+ 21 cycloadditions with azomethines to give P-thiolactams['I. The analogous P-thiolactam
S-oxide structure is ruled out for the 1 : 1 adduct of thioketene
S-oxide (1 b)['"] and the azomethine ( 2 a ) because, in contrast
to independently synthesized compounds (3)lzb1, the product
fails to show a S-oxide band in the IR spectrum. The spectroscopic data (Table 1) are in accord with the structure of a
1,2,4-oxathiazolidine( 4 ) , i. e. a representative of the still largely
unknown['] cyclic esters of sulfenic acid (sultenes). Thus (1)
surprisingly reacts as a 1,3 dipole[4"]. Although a dipolar
resonance structure has been considered in the description
of the ground state of other thiocarbonyl oxides[4b1,it has
not previously been detected in reactions.
R:
The oxathiazolidines ( 4 a ) and ( 4 c ) cannot be obtained
in pure form by reaction of ( I a ) with ( 2 a ) or of ( 1 b ) with
( 2 b ) because rearrangement to the 1,3-oxazolidine-4-thiones
( 6 ) competes with formation of ( 4 ) .
0
c, =c-s,
RZ
13)
Fig. 1. Principal bond lengths [pm] (standard deviation 0.7 pm) and angles
["I (standard deviation 0.4") in y-sultene ( 4 6 ) .
00
(2)
(4)
( l a ) , ( 4 a ) - ( 6 a ) : R' = CH(CH3)2, R 2 = C(CH3)3
( I b ) , ( 4 b , c ) - ( 6 b , c ) :R1 + R 2 = - C ( C H ~ ) ~ - ( C H Z ) ~ - C ( C H ~ ) ~ (Za), ( 4 a , b ) - ( 6 a , b ) ; R3 + R4 =
a
(261, ( 4 ~ ) - ( 6 ~R3
) := CH3, R4 = C &
p]
Prof. Dr. E. Schaumann, Dip].-Chem. J. Ehlers
Institut fur Organische Chemie und Biochemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (Germany)
Dr. U. Behrens
Institut fur Anorganische und Angewandte Chemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (Germany)
[**I This work was supported by the Fonds der Chemischen Industrie.
Angew. Chem. Int. Ed. Engl. 17 (1978) No. 6
The structure of the isomerization products has been proved
~ ' . crystalline product
by X-ray analysis in the case of ( 6 ~ ) [ The
( 4 b ) is also unstable in solution, rearranging via rupture
of the SO bond with a half-life of 14h (at 52°C in CDC13)
to ( 6 b ) ; a 1,5 dipole or 1,5 diradical ( 5 ) is assumed as
intermediate. Rearrangement of the sultenes ( 4 ) is apparently
favored by the absence of neighboring groups with hetero
atoms, in contrast to other heterocycles with the SO structural
which precludes stabilization by no-bond
res~nance'~].
Received: March 23, 1978 [Z 969 IE]
German version: Angew. Chem. 90,480 (1978)
E. Schaumann, Chem. Ber. 109,906 (1976).
[2] a) E. Schaumann, K-R. Klein, Tetrahedron Lett. 1977, 3457; b) E. Schaumann, J . Ehlers, to be published.
[1]
455
PI
a) G. W Astrologes, J . C. Martin, J. Am. Chem. SOC.97, 6909 (1975):
b) P. H. W Lau, J . C . Martin, J. Chem. Soc. Chem. Commun. 1977.
521.
a) R. Huisgen, Angew. Chem. 75, 604 (1963); Angew. Chem. Int. Ed.
Engl. 2, 565 (1963); b) G. Opirz, ibid. 79, 161 (1967) and 6, 107 (1967)
respectively.
a=1200.7(3), b=822.8(3), c=1894.q15)pm, b=98.27(5)" space group
P2,/a, Z=4; 1605 independent reflections (F >3o); R=0.060. Recorded
by the Oj20 scan technique on a four-circle single crystal diffractometer
(Syntex P2') with monochromatic C U K irradiation.
~
Solved by direct
methods (Multan). We are indebted to Dr. Th. Greiser for determining
the crystal parameters.
W C. Hamilton, S . 1. LaPlaca, J. Am. Chem. SOC.86, 2289 (1964).
E. Schaumann, J . Ehlers, U . Behrens, to be published.
N . Lozac'h, Adv. Heterocycl. Chem. 13, 161 (1971).
R. Gleiter, R. Cygax, Top. Curr. Chem. 63, 49 (1976).
r41
r51
r61
r71
PI
r91
7.9 (mc, 6H), 8.3 (mc, 4H). ( 4 4 , X=C104: m.p. 183°C (dec.).
( 4 c ) , X=Br: m.p. 175--180°C (dec.). ( 4 c ) , X=SbC16: m.p.
188 "C (dec.)]. Compounds ( 4 c ) are structurally related with
pentacarbonylchr~mium-~~~*
'I, pentacarbonylm~lybdenum-[~~
and palladium dichloride
of diphenylcyclopropylidene ; the PdClz complex of bis(diisopropy1amino)cyclopropylidene can be transformed into a metallocyclopropenylium salt by treatment with antimony p e n t a ~ h l o r i d d ~ ~ ~ .
R'
R
o-Dicarbonylcyclopentadienyliron Derivatives of
Cyclopropenes and Cyclopropenylium salts^**]
By Rudolf Gompper and Ekkehard Bartmannpl
We have synthesized dicarbonyl(q-cyclopentadienyl)(l,2,3triphenylcyc1opropenyl)iron ( 3 a) as a potential masked cyclopropenyl anion from triphenylcyclopropenylium salts (I a)
and sodium dicarbonyl(cyclopentadieny1)ferrate (,)['I.
However, ( 3 a) does not react as a cyclopropenyl anion with electrophiles[']. In order to establish whether cyclopropenyl-[Fe]
R'
R'
( I a ) , R', R2= Ph, X = BF4, Br
/Ib), R'=rBu, R2=Me, X=C104
(Ic), R'=Ph, R2= H , X=C104
( i d ) , R'=tBu, R2=OCH3, X=FSO3 [2]
( l e ) , R'=Ph, R2=C1, X=BFI
( I f ) , R'=Ph, R2=OCHs, X=FSO3
( I g ) , R'=EtzN, R2=CI, X=CIO,
( I h ) , R'=iPr2N, R2=CI,X=C104
( 3 a ) , R', R2=P h
(3 b ) , R' = tBu, R2 = Me
( 3 C ) , R1=P h, P 2 = H
[Fel= [Fe(C&)(C0)2]
derivatives act as synthetic equivalents of cyclopropenyl anions
we have now prepared the derivative ( 3 b ) [yellow crystals;
'H-NMR (CSZ): 6=1.18 (s, 18H), 1.49 (s, 3H), 4.67 (s, 5H)]
from (1 b ) and ( 2 ) . Compound ( 3 b ) is highly decomposable;
it reacts similarly to ( 3 a ) with iodine in dichloromethane
at - 70°C to form di-tert-butyl(methy1)cyclopropenyliumpenobtained
taiodide (67 %) and [Fel-I (ca. 60 %). Green et
only dimers from (I b ) and ( 2 ) .
Reaction of ( 2 c ) and (2) gives a 45 % yield of dicarbonyl(qcyclopentadienyl)(2,3-diphenylcyclopropenyl)iron ( 3 c ) [IR
(CS2): 3063, 3055,2840 (CH), 1995, 1937 ( G O ) , 1782cm-'
(cyclopropene); 'H-NMR (CS2):6=2.63 (s, 1 H), 4.59 (s, 5H),
7.15-7.5 (m, 6H), 7.55-7.8 (m, 4H)]. It is much more stable
than ( 3 b ) but less so than ( 3 a ) . The reactions of ( 3 c ) differ
considerably from those of (3a). All the electrophiles E tested
so far (trityl tetrafluoroborate, HOEtZBF;, HCl, Br2, 12,
SbCl5, (MeO),C+BF;) give almost exclusively dicarbonyl(qcyclopentadienyl)(cr-2,3-diphenylcyclopro~nylidene)ironsalts
(4c) as pale yellow crystals [(4c), X=BF4: m.p. 185°C (dec.);
IR (KBr): 2045, 2005 ( e O ) , 1368, 1330, 1310, 1288cm-'
(three-membered ring); 'H-NMR (CD3CN): 6 = 5.55 (s, 5H),
[*] Prof. Dr. R. Gompper, Dip].-Chem. E. Bartmann
456
Donor/acceptor-substituted Aromatic Systems, Part 2.-Part
iPrzN
(1 e )
Li
j
Pr 2N
c104'
(51
( 4 c ) , R' =Ph; ( 4 d ) , R' = tBu, X= BF4
( 4 g ) , R1=Et2N,X=CIO,; ( 4 h ) , R'=iPr2N, X=C104
The complex salt ( 4 c ) , X=BF4, is also obtained in ca. 50%
yield on heating (1 e ) with dicarbonyl(cyclopentadienyl)(trimethylsilyl)ferratd61in dichloromethane or chloroform.
Other complex salts ( 4 ) arise from (2) and ( I d ) , (If),
(1 9). or (I h). In the case of (1 g ) and ( I h), some [Fel-CI
is added on completion of reaction to remove excess (2),
followed by NaC104; in the case of (1 d) and (Zf) workup
is performed with HOEtiBF; [ ( 4 d ) : 51 %, yellow crystals;
m.p. 189--192°C (dec.), IR (KBr): 2042, 2000 ( G O ) , 1484,
1464, 1370, 1330cm-' (three-membered ring); 'H-NMR
(CDC13): 6=1.49 (s, 18H), 5.41 (s, 5H), ( 4 9 ) : 60%, pale
yellow crystals; m.p. 108-109°C (dec.); IR (KBr): 2035, 1973
( e O ) ,1880, 1520, 1380, 1289cm-' (three-membered ring);
'H-NMR (CDC13):6=1.33 (t, 12H), 3.55 (mc, 8H), 5.25 (s,
5H). ( 4 h ) : 8 %, light yellow crystals; m.p. 178-179°C (dec.);
IR(KBr):2040,198O(GO), I846,1490,1375,1346,1322cm-'
(three-membered ring); 'H-NMR (CDCI3):6 = 1.41 (d, 24H),
4.15 (mc, 4H), 5.26 (s, 5H)J Better yields (ca. 60%) of ( 4 h )
than are obtained with (I h ) and (2) [product also free from
(6)] are achieved with dicarbonyl(cyclopentadieny1)iron
chloride and the carbenoid (5)r7bJdescribed by Yoshida-The
complex salts ( 4 ) are stable towards mineral acids.
Apart from the major product ( 4 h ) (42%), reaction of
(1 h ) with (2) affords the dication salt ( 6 ) [(6).'h CH2CIz:
m.p. 260°C (decrepitation); 'H-NMR (CH3CN): 6 = 1.31 (d),
1.43 (d), 4.00 (sept), 4.20 (sept), 5.47 (s, CHZCl2)].
1
(2),THF
iPr2Nt
NJPr2
Triafulvalene dication salts such as ( 6 ) were first obtained
by Yoshidd'], and independently by we is^[^'.
Procedure
Institut fur Organische Chemie der Universitat
Karlstrasse 23, D-8000 Munchen 2 (Germany)
['"I
k!Fel
1:
[I ].
Synthesis of ( 3 a ) : A solution of (2) in tetrahydrbfuran
(THF) (1 0 ml), prepared from dimeric dicarbonyl(cyc1opentaAngew. Chem. Int. Ed. Engl. I7 (I 978) No. 6
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oxide, azomethines, cycloadditions, thioketene, oxazolidinethiones, sultenes, dipolar
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