close

Вход

Забыли?

вход по аккаунту

?

N-Fluorosulfonylsulfimide (N-(Fluorosulfonyl)sulfur Imide Dioxide).

код для вставкиСкачать
W Winrer, Angew. Chem. 87, 172 (1975); Angew. Chem. Int. Ed. Engl.
14. 170 (1975).
Examples of bridge-rupturing reactions of olefin-Rh complexes with
phosphanes or phosphites: R . R . Schrock, J. A. Osborn, J . Am. Chem.
Soc. 93,2397 (1971).
W Winter, t o be published.
Monoclinic,spacegroup C2/c; a=47.88, b = 10.62, c=19.44A. p = 108.6";
2 = 8 ; 2116 symmetry independent reflections [ I t 3 o ( I ) ; -8O"C].
Nonius CAD-4, MoKz, graphite monochromator; solution: heavy atom
method; refinement: R=0.10 (Rh. P anisotropic); one phosphite atom
is disordered. There is still another monoclinic modification of (31,
which is presently being investigated.
W Winter, Chem. Ber. 109. 2405 (1976); Z. Naturforsch. 8 3 1 . 1116
(1976).
P3
N-Fluorosulfonylsulfmide
(N-(Fluorosulfony1)sulfurImide Dioxide)[*'I
Fig. 1. Structure of the cationic complex (3) [phenyl- and (phosphite)OCH3
substituents omitted for clarity]. The standard deviations for the Rh-P.
Rh-C, and C-C bond lengths are 0.01, 0.02, and 0.03A.respectively.
The course of the reaction ( 1 ) -+ ( 4 ) reveals still further
interesting points:
1 ) When the reaction of (2) with trimethyl phosphite is
carried out at room temperature, ( 3 ) and ( 4 ) are formed
in a ratio of about 1 : 1, while on prolonged heating under
reflux (1 h) essentially only ( 4 ) is formed. However, since
( 3 ) is completely stable in boiling ethanol and is converted
into ( 4 ) only in the presence of excess trimethyl phosphite,
the transformation ( 3 ) --t ( 4 ) most likely proceeds via a dissociative mechanism :
\
2) If, instead of (2), the violet complex ( I ) is allowed
to react with P(OCH& at room temperature, only complexes
of type (3) [L=PPh3 and P(OCH,),] are formed, and no
complexes of type ( 4 ) . O n the other hand, like (2), (I)
affords exclusively the complex ( 4 ) on prolonged refluxing.
The above findings lead to the following conclusions: on
the one hand, the ring inversion of the dibenzo[bfl-q-cyclobuta[d]phosphepin ligands in the transition ( 3 ) - + ( 4 )requires
a surprisingly low free activation enthalpy [ACWQCca. 2526kcal.mol-' with an estimated half-life of 15min for ( 3 ) ]
in comparison to other non-complexed benzoannelated phosphepins (AG*: 30-34 kcal.mol-')[61; on the other, either
both conformers of this ligand must already be present in
the insoluble complex (2), or (2) forms a transition state in
which the activation threshold for inversion is "undermined"
by an intermediary phosphepin ring-opening.
The overall reaction sequence ( 1 ) -+ ( 4 ) has also been confirmed by X-ray structure analy~es1~1
of ( 1 ) and ( 4 ) .
Received: November 18, 1977 [Z 866b IE]
German version: Angew. Chem. 90, 142 (1978)
-~[ I ] A. Sanders, W P. Giering, J . Am. Cbem. S O ~96.
. 5247 (1974); 97. 919
(1975).
Angew. Chem. Int. Ed. Engl. 17 (1978) No. 2
By Herbert W Roesky and Minoru Ararnaki['I
N-Fluorosulfonylsulfimide could previously only be isolated
as the cyclic dimer ( I )I1'.
Organic derivatives of sulfimide
were postulated as intermediates in the dehydrohalogenation
of the corresponding sulfamoyl chlorides['! We have now
found that 1 : 1 adducts of N-fluorosulfonylsulfimide are readily accessible by reaction of ( 1 ) with tetrasulfur tetranitride
or pyridine.
o
n
Lewis bases stabilize the monomeric N-fluorosulfonylsulfimide. The adducts (2) are interesting examples for the study
of SN bond lengths as a function of coordination number.
( 2 a ) is a brick red crystalline solid, ( 2 b ) a white crystalline
solid; they can be recrystallized from CH2Cl2 and stored
without decomposition in dry air. Surprisingly, in the reaction
of the dimeric sulfimide with benzonitrile
C.jHs-C,
N
\ o
,
,SGo
4
N
( I ) + 4 C6HsC-N
not the 1 : 1 adduct but the 1 :2 adduct ( 4 ) is isolated. Presumably, the initially formed, strained three-membered ring (3)
reacts further with benzonitrile to give ( 4 ) , a lh6,2,4.6-thiatriazine. Analogous reactions of (1) should lead to a wide variety
of interesting new compounds.
I'[
Prof. Dr. H. W. Roesky, M. Aramaki [ + ]
Anorganisch-chemisches Institut I der Universitat
Niederurseler Hang, D-6000 Frankfurt a m Main 50 (Germany)
[ '1 Permanent address: Central Glass Co. Ltd., Tokyo (Japan)
[**I This work was supported by Hoechst AG, Germany.
129
Procedure
(I)[']
(3.7g, 11.6mmol), diluted with CHzC12 (20ml), is
added dropwise to a solution of N4S4 (4.3g, 23.4mmol) in
CHzC12 (450ml). Dark-red (2a) immediately precipitates. The
adduct is recrystallized from CH3CN; yield 4.45 g (56 %),
dec. pt. 105--110°C; MS: m/e=283 (M+-NSO); "F-NMR
(in CH3CN): 6 = -55.8 (s),rel. CFC13 ext.
For (2b), prepared in an analogous way: M.p. 100°C; MS:
m/e=240 (M'); I9F-NMR (in CH3CN): 6 = -53.5 (s).
(1) (40g, 12.4mmol), diluted with CHzC12(IOml), is added
dropwise to a solution of benzonitrile (5.1g, 49.6mmol) in
CH2ClP (20ml). The white crystalline reaction product ( 4 )
can be recrystallized from CH3CN or C6H6;yield 5.5 g (60 %),
m.p. 145°C. MS: m/e=367 (M', loo%), 348 (M+-F, 2%);
19F-NMR (in C6H6): 6= -59.9 (s).
compounds, only the alcohols ( 2 ) , X=OH, were formed as
by-products.
The cyclopentenols ( 5 ) , which occur as a mixture of diastereomers, can be identified by Cr03-oxidationto the corresponding cyclopentenones. The spectroscopic data of the ketones
(6) are in accord with data given in the literature[3! The
structure of (76) was confirmed by I3C-NMR and mass
spectroscopy. The 'H-NMR spectrum of this compound shows
three olefinic protons [quartets at 6 = 5.82 and 6.30 (H6 and
H'; Js7=6, 5 5 6 = 5 1 7 = 3 H ~as) well as a doublet at 6=6.03
(HZ;J1 = 7 Hz)]; as expected on decoupling of the bridgehead
protons H' and H5 two doublets and a singlet are observed
in the vinylic region. Similar 'H-NMR spectra have been
reported for other 3-halobicyclo[3.2.1]octa-2,6-dienes~4].
Received: November 25, 1977 [Z 888 IE]
German version: Angew. Chem. 90, 127 (1978)
CAS Registry numbers:
( I ) , 60153-70-0; (Za), 65392-47-4; (26), 65392-46-3; (41, 65392-44-1; N4S4,
28950-34-7; C6H5C=N, 100-47-0; C5H5N, 110-86-1
K . D. Schmidt, R . Mews, 0. Glemser, Angew. Chem. 88, 646 (1976);
Angew. Chem. Int. Ed. Engl. I S , 614 (1976).
[2] G. M . Atkins, Jr., E . M . Burgess, J . Am. Chem. SOC. 94, 6135 (1972).
[I]
[4
+ 31-Cycloadditions of Allenyl Cations[**]
By Herbert Mayr and Barbel Grubmiiller[*]
Cycloadditions of ally1 cations with dienes (Eq. A) have
been studied in detail by H . M. R . Hoffmann"].
li)
We now wish to report the first corresponding reactions
of allenyl cations (I ), which proceed via formation of vinyl
cations (Eq. B).
Treatment of a solution of propargyl bromide (2a), X = Br,
and cyclopentadiene in pentane with silver trifluoroacetate"]
and subsequent hydrolysis with aqueous ammonia affords
a mixture of 85 % 4-(2-propynyl)cyclopent-2-en-l-ol(5a)and
15 % bicyclo[3.2.l]oct-6-en-3-one ( 6 a ) in 46 % yield. In a
similar way reaction of 3-chloro-3-methyl-I-butyne(2 b),
X = C1, affords 28 % ( 5 b), 35 % (6 b) and 31 % 3-chloro-4,4dimethylbicyclo[3.2.l]octa-2,6-diene (7b) in a total yield of
50 %. Apart from insignificant amounts of high-molecular
[*] Dr. H. Mayr, B. Grubmiiller
Institut fur Organische Chemie der Universitat Erlangen-Numberg
Henkestrasse 42, D-8520 Erlangen (Germany)
[**] This work was supported by the Deutsche Forschungsgemeinschaft
and by gifts of silver salts from Degussa AG, Frankfurt am Main, Germany.
130
OH
(6)
(5)
( a ) : R = H;
(b): R
17.b)
= CH3
Formation of the products (5) to (7) can be explained
in terms of intermediate allenyl cations (I) which are
formed on reaction of Ag@ with (2). Cyclopentadiene
can attack (I) at the sp2 carbon atom and thus give
the alkynylcyclopentenyl cation (3), which is intercepted by
CF3COy. Hydrolysis of the resulting trifluoroacetate finally
affords the alcohol (5). A further possible explanation for
the formation of ( 3 ) is that cyclopentadiene already attacks
the alkynyl halide before the CX bond is completely cleaved.
The bicyclic products (6) and (7b) are derived from the
vinyl cation ( 4 ) , which can be formed by concerted or stepwise
cycloaddition of allenyl cation to cyclopentadiene. Reaction
of ( 4 ) with CF3COy affords a vinyl ester, whose hydrolysis
leads to the ketone (6). Alternatively, ( 4 ) can react with
(2b) with formation of (7b) and liberation of a 1,l-dimethylallenyl cation. The corresponding reaction with (2a) is not
observed, probably because the unsubstituted allenyl cation
is insufficiently stabilized. Consistent with the proposed
mechanism, (7b) is not formed if the concentration of (2b)
is kept small by slow dropwise addition.
(8)
( 4 a ) , A H = 5 . 2 kcal/mol
According to MIND0/3 calculations[51 the vinyl cation
( 4 n ) is less stabilized than the monocyclic vinyl cation (8)
by about 5 kcal/mol (Eq. C)-presumably because the optimized C2C3C4angle (146") in ( 4 a ) deviates further from
linear geometry than the corresponding angle (153") in (8Jr6'.
For both vinyl cations ( 4 a ) and ( 8 ) , MIND0/3 calculations
Angew. Chem. l n t . Ed. Engl. 17 (1978) No. 2
Документ
Категория
Без категории
Просмотров
0
Размер файла
198 Кб
Теги
dioxide, sulfur, imide, fluorosulfonylsulfimide, fluorosulfonic
1/--страниц
Пожаловаться на содержимое документа