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Dicyclopropylacetylene by Fritsch-Buttenberg-Wiechell Rearrangement.

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T h e phenacyl bromide behaves in a n analogous fashion, b u t
the iodide yields (2) in low concentration a n d leads t o acetophenone phenylhydrazone as t h e main product.
Received: February 3, 1970
IZ 148 IEI
German version: Angew. Chem. 82. 2 5 4 (1970)
[*I Prof. W. C. Stickler and W. C. Hoffman
Department of Chemistry, University of Denver
Denver, Colorado 80210 (USA)
[ I ] See, e . g . , E . VotoEek, Coll. czechoslov. chem. Comm. 2,
681 (1930); Chem. Abstr. 25, 1488 (1931).
[2] 0. Hess, Liebigs Ann. Chem. 232, 234 (1886).
[3] For the structure of ( 2 ) see: D . Y . Curtin and E. W. Tristrain, J . Amer. chem. Soc. 72, 5238 (1950). (Their review of
previous work contains, however, some historical and factual
errors.)
[4] H . D . Hart, M . S . Thesis, University of Denver, 1952;
W. C . Stickler, H. D . Hart, and P. Yin, J. Co10.-Wyo. Acad.
Sci. 1952, 34; W. C . Stickler, W . Epstein, and L . Gachic, ibid.
I953, 24.
[5] Cf. 0.L. Chapman e f al., J. Amer.chem. SOC.86,4968 (1964).
[6] We a re indebted to Prof. J . J . Schmidt-CollPrus and his
staff, University of Denver Research Institute, and Mr. R . H .
Williams, Univ. of Illinois, for obtaining th e spectra and aiding
us in their interpretation.
[7] A . Burawoy, J . chem. SOC. (London) 1937, 1865; e x . ,
C H-N =N-C6H 5 absorbs at 403 nm.
[8] T he dienophilic structure involving C=C can be arrived at
by considering either limiting resonance structures o r tautomeric forms.
phere of argon. T h e homogeneous solution is then transferred
t o a n autoclave a n d cooled t o --20 "C. Ethylene is introduced
i n t o t h e autoclave a t 1 2 a t m an d both pressure an d temperature ar e kept constant during the t i me o f reaction
(1 hour). After withdrawal of the ethylene at t h e reaction temperature the conversion can b e determined by weighing (increase in weight minus t h e solubility o f t h e ethylene in t he
reaction solution): 34.6 g, corresponding t o a conversion of
13.0 moles o f ethylene per liter o f reaction solution per hour.
T h e reaction solution was washed with water t o remove
catalyst; so me solid polymer (0.9%) was precipitated. T h e
organic phase was fractionated by vacuum distillation (see
Tab l e 1).
Received: February 4, 1970
IZ 149 IE]
German version: Angew. Chem. 82, 255 (1970)
~
~~~~
[*IDr. G . Henrici-Olive and Dr. S. Olive
Monsanto Research S.A.,
CH-8050 Zurich, Eggbuhlstrasse 36 (Switzerland)
[l] Homogeneous Catalysis at Ti(rv) Centers, Part 3. - Part 2:
G. Henrici-OlivP and S . Olive, J. Polymer Sci., Part B, in press.
121 G. Henrici-Olivd and S . OiivP, Angew. Chem. 79, 764
(1967); Angew. Chem. internat. Edit. 6, 790 (1967).
[3] C . Henrici-OlivP and S . OlivP, Advances Polymer Sci. 6, 421
(1969), and literature cited therein.
141 H . Bestian and E. Prinz, US-Pat. 2907805 (1959), Farbwerke Hoechst.
[5] H . Bestian and K . Clauss, Angew. Chem. 75, 1068 (1963);
Angew. Chem. internat. Edit. 2, 704 (1963).
Dicyclopropylacetylene by Fritsch-ButtenbergWiechell Rearrangement
a-Olefins from Ethylene111
By Gisela Henrici-Olivk a n d Salvador Olive'[*]
By Gert Kobrich a n d Dieter Merkel [*I [**I
Ethylene is rapidly converted in to solid polyethylene by t h e
two-component catalyst Cp2TiRC1,'RAICIz (Cp = cyclopentadienyl, R = alkyl) in toluene at O°Crz,31. Besriaii et a/.,
however, have shown that t h e major products a r e liquid
oligoethylenes - mainly 2-ethyl-1-olefins ( I ) having vinylidene terminal groups - when C12TiRCI/RAIC12 is used as
catalyst in CHzC12 as solvent a t -70 "C [4,51.
By systematically changing th e reaction conditions an d t h e
ligands on titanium we have n o w been able t o prepare
C6-c40 olefins (2) having predominantly vinylic end groups.
T h e best results were obtained by using t h e following procedure:
(CzH50)3TiCI (2 mmoles) is dissolved i n toluene (100 ml)
a n d treated with CzHsAIClz (10 mmoles) under a n atmos-
Table 1.
Fractionation of oligoethylene.
Fraction
Parts by weigl
Vjnylidene ( I )
No.
( %)
(%) [bl
1
2.3
2
3
4
5
6
7
8
9
10
13.7
11
16.0
2.0
12.0
6.7
8.0
9.5
13.4
15.5
0.9
56 [cl
8 4 [cl
112 [cl
150
175
195
215
225
292
465
solid
Reaction of 1-chloro-2,2-dicyclopropylethylene(Z),prepared
from dicyclopropyl ketone ( I ) by chloroolefination 111, with
n-butyllithium i n T H F between -110 an d +2OoC afforded
t h e hitherto unknown dicyclopropylacetylene ( 5 ) as a stable,
colorless liquid, beside 1,I-dicyclopropyl-1-hexene ( 4 ) .
Hydrogenation of t h e acetylene ( 5 ) over a Lindlar catalyst
proceeded almost quantitatively an d stereospecifically t o
give cis-l,2-dicyclopropylethylene( 6 ) 121.
T h e supposedcarbenoid intermediate (3) has n o t been detected
so far probably because t h e electron-repelling a n d bulky
cyclopropyl groups slow down metalation o f ( 2 ) , on t h e o n e
hand, an d accelerate decomposition of (3) [31 o n t h e other.
I
(C~H,),P=CHCI
100
>95
395
>90
2 9 0
390
290
>SO
%
>70
270
-
[a] Number average molecular weight, Mn, determined by vaporpressure osmometry.
lbl Percentage of molecules with vinyl- and
vinylidene end groups calculated from the absorption at 9 1 0 and 890
cm-1 resp.
[cl The first three fractions distilled together with the
toluene and were identified gas-chromatographically as I-butene,
I-hexene, and 1-octene.
Angew. Chem. internut. Edit. J Vol. 9 (1970)
No. 3
243
95/13
10 [cl
83 [cl
I
97 [d]
IR (cm-1)
[a I
NMR
[bl
1 SO28
3080 and 3005
(C-H);
1620 (C C )
1.4725
3075, 3000,
and 2955
to 2855
4.24 (1
C--H/
s); 7.7-8.3
(1 cwallylHim);
8.8-9.7
(9 H/m)
4.95 (1 +C-H/
t); 7.7-9.8
(19 H/m)
151/760
1.4900
1401760
1.4803
(C-H);
1650 ( C = C )
3080 and 3000
(C-H);
2200 (CEC),
Raman band
3070 and 3000
(C-H);
1690 and
1660 (C=C);
1043, 1015,
949. and 886
8.6-9.3 ( 2 H /
m); 9.3-9.6
(8 H / m )
5 . 3 8 ( 2 = C - H)
and 8.41
(2 allyl-H)
as AzB2
system; 9.05
to 9.9
(8 Him)
[a] Measured on capillary film.
[b] T scale; measured in CC14 with
TM S as internal standard.
[c] Based on (21.
[dl Based on ( 5 ) .
Interestingly, (3) does not undergo a dimerizing a-elimination t o give butatriene (71, as has been observed for analogous P,@-dialkylderivatives under similar conditions [3al, but
owing to the "olefinic behabior" of the three-membered
rings [41 enters into a Fritsch-Buttenberg-Wiechell rearrangement that is characteristic of unsaturated @ substituents
(aryl[51, alkenyl, and alkynyl groups [3b1).
Experimental:
A solution of (2) (100 mmoles), prepared according to the
general procedure given in ref. [61 and purified by distillation
(spinning band column), in T H F (200ml) or THF,'ether/
light petroleum (50-70 "C) (4 : 1 : 1) (Trapp mixture 13al)
(200 ml) is treated with a solution of butyllithium (120
mmoles) in light petroleum at 20 O C under an inert gas and
the reaction mixture stirred overnight. The crude product obtained after hydrolysis and the usual working up procedure
contained ( 5 ) and (4) in 8 3 and 10% yield, respectively,
(based on (21, determined by gas chromatography) which
were obtained about 97% pure on fractional distillation over
a spinning band column, and free from impurities by preparative gas chromatography ( 6 m column, SE 30). Hydrogenation of ( 5 ) (10 mmoles) with Lindlar catalyst (0.5 g) and
quinoline 171 (0.2 g) in a shaking apparatus (70 min at 20 "C)
gave a 97% yield of (6) along with 3 % of lower boiling
products which were removed by preparative gas chromatography.
Received: January 31, 1970
[Z 150 IE]
German version: Angew. Chem. 82, 251 (1970)
__-.
[*I Prof. Dr. G. Kobrich and Dipl.-Chem. D. Merkel
Institut fiir Organische Chemie der Univerntat
69 Heidelberg, Tiergartenstrasse (Germany)
[**I This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, and Badische
Anilin- & Soda-Fabrik AG, Ludwigshafen.
[l] The structures of the new compounds were confirmed by
combustion analysis and spectroscopic methods.
[2] The compound was mentioned but not described by W. Y.
E . Doering and W. R . Roth, Angew. Chem. 75, 27 (1963);
Angew. Chem. internat. Edit.2,115 (1963); Tetrahedron 19,715
(1963); the trans isomer was prepared by W. LMttke [personal
communication, cf. W. Liittke and A . de Meyere, Angew. Chem.
78, 544 (1966); Angew. Chem. internat. Edit. 5, 512 (1966)l.
[3] a) G. Kobrich and W. Drischel, Tetrahedron 22,2621 (1966);
G. Kobrich, H . Heinemann, and W. Ziindorf, ibid. 23,565(1967);
G. Kobrich and H . Trapp, Chem. Ber. 99, 670, 680 (1966);
b) W. Werner, unpublished experiments.
[4] For a review, see W. A . Bernett, J. chem. Educat. 44, 17
(19 67).
244
151 For a review, see G. Kobrich, Angew. Chem. 77, 75 (1965);
Angew. Chem. internat. Edit. 4,49 (1965).
161 G. Kobrich, H . Trnpp, K . Flory, and W . Drischel, Chem.
Ber. 99, 689 (1966).
[7J H. Lindlar, Helv. chim. Acta 35, 446 (1952).
N,N'-Sulf onylbis(su1fur difluoride diimide)I1 I
By Herbert W. Roesky and Horst H . Giere[*l
Sulfamide reacts with sulfur tetrafluoride at room temperature in the presence of sodium fluoride as H F acceptor t o
give N,N'-su!fonylbis(sulfur difluoride diimide) (Z) in 22 "/,
yield.
+
H~NSO~NH
+ Z2 SF4 + F ~ S = N S O ~ N = S F Z4 H F
(1)
At higher temperatures, however, this reaction leads exclusively to formation of N-fluorosulfonylsulfur difluoride
imide FSOzN=SFz 121.
Compound ( I ) is a yellow evil-smelling liquid which loses
H F o n reaction with water. Its composition follow sfrom the
results of elemental analysis and from the mass spectrum,
which shows, in addition t o the molecular ion m!e 232 (8.7 %),
the following characteristic fragments: m / e = 167 (FSO2NSFz; 12.3%), 148 (SOzNSFz; 61.8%), 84 (NSF2; 19.7%),
83 (S02F; 18.5%), 70 (SF2; 39.473, 67 (SOF; 17.0%), 65
(NSF; 16.5%), 64 (SOz; 13.4%), 51 (SF; 10.7%), 48 (SO;
25.7 %), 46 (NS; 100.0 %), 32 (S; 6.8 "/,).
The bands in the IR spectrum (capillary) have not, as yet,
been completely identified because of the difficulties due to
coupling and superpositions. In the region of the (S=O) and
(N=S) stretching vibrations, bands occur at 1430 w, 1385 s,
1270 m, 1215 vs, and 1180 vs (cm-1). The absorptions at
820 s, 790 s, and 660 s (cm-I) have been tentatively assigned
to the (SN) and/or (SF) vibrations. The symmetry of the
molecule is confirmed by the 19F-NMR spectrum: a singlet is
observed with 8~ = -41.5 ppm (CCI3F, external) which
compares with 8~ = --40.0 ppm for FSOzNSF2.
Experimental:
Sulfur tetrafluoride (108 g, 1 mole) is condensed into a 300ml
monel cylinder cooled with liquid nitrogen and containing a
mixture of sulfamide (48 g, 0.5 mole) and sodium fluoride
(84 g, 2 moles). The cylinder is then allowed t o warm t o
room temperature and shaken for 20 hours. After removal
of gaseous components - a little SF4 and SOF2 - the reaction products are washed portionwise from the cylinder with
300ml CC14 and separated from N a F . H F by filtration
under dry nitrogen. Concentration of the filtrate followed by
distillation under vacuum affords compound ( I ) 1b.p. 49 t o
51 "Cj0.01 torr; yield 26 g (22.4x)J.
Received: December 10, 1969
[Z 152 IEI
German version: Angew. Chem. 82, 255 (1970)
[*I Univ.-Doz. Dr. H. W. Roesky and Dip1.-Chem. H. H . Giere
Anorganisch-Chemisches Institut der Universitat
34 Gottingen, Hospitalstrasse 8-9 (Germany)
[l] Sulfur-Nitrogen Compounds, Part 28. - Part 27: H . W.
Roesky, H . H . Ciere, and D . P . Babb, Inorg. Chem., in press.
[2] U . Biermnnn and 0.Gkmser, Chem. Ber. 100, 3795 (1967).
Method for Preparation of Compounds of the Type
R-(N=PX2),-N-PCl,
By Herbert W. Roesky and Ludwig F. Grimm [*I
N-Trimethylsilylaminodifluorophosphoranylidenedihalothiophosphorylamines ( I ) , prepared from the corresponding
N-trifluorophosphoranylidenedihalothiophosphorylamine
and hexamethyldisilazane [21, react with phosphorus pentaAngew. Chem. internat. Edit.
1 Vol. 9
(1970) NO. 3
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