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N-Fluorosulfamidoyl Fluoride Pentafluorosulfur N-Fluoro-N-(fluorosulfonyl)amide and N-(Dichloromethylene)fluoroformamide.

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bromine. The molecular weight in acetone is 228. (The compound is insoluble in other solvents; it attacks steel, the soluiton becoming immediately red.) All these facts can be accounted for by formula ( I ) .
CHZCO, ,C1
C
CHsCO' \Hg-HgCl
(2)
Formula (2) would require only one Hg-C stretching vibration and one Hg-Cl vibration at lower wave numbers; for
HgzC12 the latter i s at 260, for C6HsHgCl at 331, and for
HgC12 at 375 cm-1. Organomercury derivatives with a
Hg-Hg bond are not known.
Mercury(I1) bromide, cyanide, and acetate do not react with
acetylacetone under the above conditions; nor does mercury(1) chloride.
Received: June 14, 1968
[Z 803 IE]
German version: Angew. Chem. 80, 664 (1968).
[*I Prof. Lib. Doc., Dr. F. Bonati and Dr. G. Minghetti
Istituto di Chimica Generale dell'Universit a
via Venezian 21
1-20133 Milano (Italy)
[l] S . Tanafar and E. Kurowsky, J. NSS. physik.-chem. Ges. 40,
580 (1908); Chem. Zbl. I908 11, 1096. Further references:
J. P. Facklerjr., Progr. inorg. Chem. 7, 388 (1966).
N-FluorosuIfamidoyl Fluoride, Pentaffuorosulfur
N-Fluoro-N-(fluorosulfonyl)amide, and
N-(Dichloromethy1ene)fluoroformamide I * J
By H. W. Roesky[*]
Sulfamidoyl fluoride ( I ) 121 reacts with elemental fluorine at
room temperature, giving N-fluorosulfamidoyl fluoride (2).
FSOzNHz+ Fz + FS02-NHFf
(1)
(2)
HF
(2) is a colorless liquid that decomposes appreciably in Pyrex
glass vessels within one day, with formation of SiF4. It can
be considered as the first derivative of difluoroamine HNFz
in which one fluorine atom has been replaced by the FS02
group. Reaction of (2) with an excess of fluorine gives N,Ndifluorosulfamidoyl fluoride ( 3 ) 131.
(2)
+ F2
+ FSOzNFz
+ HF
(3)
Formation of sulfonyl fluoride SOzF2 was not observed
during the fluorination.
Elemental analysis proves the composition of (2). The
19F-NMR spectrum shows a doublet at SF = -39.6 ppm for
the FSOz group and a doublet at SF = 91.8 ppm for the N F
group (referred to CCI3F. external; intensity ratio 1:l;
JFF = 7.7 Hz). The 1H-NMR spectrum contains a singlet at
SH = -7.8 ppm (referred to TMS, external).
The following absorptions appear in the NaCl and KBr
regions of the IR spectrum (capillary film on AgCl plates):
3700s, 3250s, 3050m, 2780111, 1638m,1472vs, 13701x1, 1240~s.
lOOOvs, 820~s.695vs, 575vs,480s cm-1. In this determination
some (I) was probably also formed.
The mass spectrum shows, besides the molecular ion
FSOzNHF+ 117 (62.9 %). fragments at m/e 98 (13.5 %)
SOzNHF, 85 (61.8 %) FSNHF, 83 (100 %) FS02,67 (43.8 %)
FSO, 64 (67.3%) SOz, 48 (35.9%) SO, and 99 (33.7%)
FSOzNHz.
Difluorosulfur N-(fluorosulfony1)imide (41,prepared from
( 1 ) and tetrafluorosulfur [41, reacts with elemental fluorine,
giving pentafluorosulfur N-(fluoro)-N-(fluorosu1fonyl)amide
(5).
630
FSOzN=SFz f 2 F2 + FS02-NF-SFS
14)
(5)
( 5 ) is a clear liquid that can be kept in glass vessels. The NaCl
and KBr regions of the IR spectrum contain absorptions at
1490vs, 1 4 4 0 ~ 1. 3 0 3 ~ 1250vs,
.
1 0 3 2 ~ 1. 0 1 0 ~ 925~s.
.
885~s.
862s, ~ ~ O V71Sw,
S , 6 2 3 ~ 572~s.
.
5 2 4 ~490w
.
cm-1.
The mass spectrum shows fragments at m/e 227 (0.2%)
FSONFSF5, 224 (0.6 %) FSOzNFSF4, 208 (0.2 %)
FSONFSF4, 205 (0.7 %) FSOzNSF4, 188 (0.13 %), 186
(1.6 %) S02NSF4, 167 (0.3 %) S02NSF3, 127 (100 %), 128
(1.1 %I. 129 (6.4 %) SFS. 108 (6.3 %), 110 (0.05 %) SF4.
Further fragments, SF3, SOzF, SF2, SOF, S02, SF, SO, and
SN, were also detected. The following chemical shifts were
obtained from the 19F-NMR spectrum: SNF = +23.2 ppm,
~ S O =
~ F
-41.0 ppm, SF = -61.7 ppm, S S F =
~ -69.0 ppm
(referred to CC13F. external).
After the preparation of N-(fluoroformy1)iminosulfur dichloride [51 we succeeded in synthesizing N-(dichloromethy1ene)fluoroformamide (7) by fluorination of N-(dichloromethy1ene)chloroformamide 161 with silver monofluoride.
0
I/
CI-C-N=CCIz
0
+ AgF ->
I
F-C-N=CClZ
(6)
+ AgCl
(7)
(7) is a liquid that has a pungent odor, b.p. 78-8OOC;
its composition is proved by elemental analysis. The
19F-NMR spectrum shows a singlet at SF = -12.65 ppm
(referred to CC13F, external).
The infrared spectrum of the liquid in the NaCl and KBr
region shows bands at 2270m, 1850~s.1730w, 1660~s.1180vs,
1061m, 955vs, 908s. 7781~1, 742w. 637~s.538s cm-1. They are
provisionally assigned to the following vibrations: v(C0)
1850, v(C=N) 1660, v(CF) 1180, v,,(CCl) 995, and vs(CCl)
908 cm-1.
Experimental:
Synthesis of (2):
Fluorine and nitrogen (Fz: Nz = 1:2, ca. 60-70 bubbles/min)
are led through 50 g of ( I ) in a quartz trap for 24 h; (2).
a little (3), and some SiF4 remain in the vessel. In an attached receiver (cooled in dry ice) 48 g of (3) is collected, and
in a further trap (cooled by liquid air) SiF4 separates. SiF4
is formed by reaction of the H F with the glass. (2) is distilled
from the reaction mixture in a vacuum into a precooled receiver: b.p. 29-30 OC/32 tom; yield 5 g.
Synthesis of ( 5 ) :
10 g of fluorine is condensed onto 33 g of (4)contained in
a 100 ml nickel autoclave cooled to the temperature of
liquid nitrogen. The mixture is then warmed to room temperature, kept there for 3 days, and then warmed at 70 "C for a
further 3 days. The volatile products are removed; they can
be identified by infrared spectroscopy as SOzFz, FSOzNF2,
SOF2, SF4, and SF6. The residue in the autoclave is distilled
in a vacuum. 3 g of (51, b.p. 30-31 "C is obtained alongside unchanged (4).
Synthesis of (7):
20 g of (6) is fluorinated by 60 g of AgF at 120-140°C in a
glass vessel. The volatile products are collected in a cooled
receiver (acetone/dry ice). Then the trap is warmed to room
temperature and the contents fractionated under atmospheric
pressure. Unchanged ( 6 ) is then accompanied by l o g of
(7). b.p. 78-80 "C.
Received: M a y 20, 1968
[Z 804 IE]
German version: Angew. Chem. 80, 626 (1968)
[*I Dr. H. W. Roesky
Anorganisch-Chemisches Institut der Universitat
34 Gottingen, Hospitalstr. 8-9 (Germany)
[l] Part XI11 of Sulfur-Nitrogen Compounds. - Part XII:
H . W. Roesky, Angew. Chem. 80, 236 (1968);pngew. Chem.
internat. Edit. 7, 218 (1968).
Angew. Chem. internat. Edit.
Vol. 7 (1968) I No. 8
[2] R. Appel and G. Eisenhauer, Z . anorg. allg. Chem. 310, 90
(1961).
[3] M . Lustig. C. L. Bumgardner, F. A. Johnson, and J. K . Ruff,
Inorg. Chem. 3, 1165 (1964).
[41 0. Glemser, H. W. Roesky, and P . R. Heinze, Angew. Chem.
79, 153 (1967); Angew. Chem. internat. Edit. 6, 179 (1967).
[5] H . W. Roesky and R. Mews, Angew. Chem. 80, 235 (1968);
Angew. Chern. internat. Edit. 7 , 217 (1968).
[6] E. Degener, H . Holtschmidt, and K . Swincicki, German Pat.
1167848 (1964), Farbenfabriken Bayer.
Organic Compounds in Fossil Plants
( Voltziu brongniurti, Coniferales)111
By H . Knoche, P . Albrecht, and G. Ourisson [*I
We recently reported our work on a fossil horsetail recovered
from a clay inclusion in the variagated sandstone of the
Northern Vosges (Trias, 2 x 108 years old) [31. The fossil plants
Voltria brongniarti (Coniferales) are also found in this same
sandstone[3]. Pieces of this fossil plant. about 1-5 cm long,
were collected in Hangviller (Moselle), care being taken
during collection to obtain as pure specimens as possible
and the working up being controlled by blank experiments.
Inorganic analysis gave a content of 6 0 % goethite,
FeZO3-H20 [41.
The dry fossil (2.6 kg) was ground and extracted with a 3 : l
benzene-methanol mixture (3 1) under the action of ultrasound. After centrifugation, decantation, and removal of the
solvent by distillation, there remained 42 mg (16 ppm) of
residue. The hydrocarbon fraction (3 mg, 1 . 2 ppm) was
isolated by column chromatography on silica gel; it was
crystalline and was shown by its gas chromatogram[5J to
consist almost wholly of one component. This substance was
identified as n-CZ8H58 by gas chromatography o n filled and
capillary columns [61,by inclusion in molecular sieves (Linde
5 A), and by the mass spectrum. n-Octacosane has not
previously, to our knowledge, been found as chief component
of the cuticular wax of a plant. As is well known, it is mainly
the odd-numbered hydrocarbons that occur in such waxes,
and furthermore as mixtures of homologs; in conifers nonacosane, C29H60. occurs most frequently, alongside hydroxy
esters and alcohols 17981.
We regard it as extremely unlikely that Voltzia, alone among
the conifers, contained an almost homogeneous even-numbered hydrocarbon, and we conclude that we are dealing with
a transformation product. It is not possible to study directly
what its precursor in Voltziu was, since this plant is extinct.
Of extant conifers the family Taxodiaceae is the most closely
related [91. We have therefore studied the wax of two members
of this family in the hope of identifying possible precursors
of the n-octacosane. In the wax of Cryptomeriajuponica Don.
only 10-nonacosanol was found -this is a widely distributed
constituent of many conifer waxes; it can hardly be considered as precursor of the octacosane. However, the wax of
Taxodium distichurn Rich. contains I-octacosanol as well'as
10-nonacosanol. The former alcohol was previously found
only in the wax of one other conifer, Gingko biloba L. [lo].
W e presume that n-C~sH58 was formed in the fossil by
reduction of the primary alcohol n-Cz7H55-CH20H; 10nonacosanol either was not present or was degraded in a n
unknown way. In this connection it is interesting that, according to Hoering, octadecanol is reduced to octadecane
simply by heating it with sedimentary rocks [111.
Received: June 4, 1968
[Z 806 IE]
German version: Angew. Chem. 80, 666 (1968)
[*] Prof. G. Ourisson, Dr. H. Knoche, and P. Albrecht
Universite de Strasbourg
Laboratoire attache au C.N.R.S.
1, rue Blaise Pascal, Strasbourg (France)
Angew. Chem. internat. Edit. J Vol. 7 (1968) / No. 8
[l] Part 11. - Part I: [2]. This work was carried out as part of the
research program D.G.R.S.T. No. 64-FR-058. - We thank
L. Grauvogel and J. C. Gall for help in collecting the fossils, and
Dr. P. Witz (Geigy, Basel) and G . Teller (Strasbourg) for measuring the mass spectra.
121 H . Knoche and G. Ourisson, Angew. Chem. 79, 1107 (1967);
Angew. Chem. internat. Edit. 6, 1085 (1967).
[3] W. P . Schimper and A. Mougeot: Monographie des plantes
fossiles du grks bigarre de la chaine des Vosges. Wilhelm Engelmann, Leipzig 1844.
[4] We thank S.N.P.A., Pau (France), for carrying out the
analysis.
[5] Conditions: Perkin-Elmer 226 gas chromatograph, 1.5 ?Ao
SE-30 on Aeropack 30, 80/100 mesh, 1.80 m long, diam, 3 mm,
program 6.25 "C/min, 100-290 "C, 30 ml He/min.
[6] Capillary column: 0.5 mm, SE-30, 240°C, 6.2 ml He/min.
Retention times: benzene 3.4 min; n-C~sH58,1 5 min.
[7] H . Ageta, J. pharmac. SOC.Japan (Yakugakuzasshi) 79, 47
(1959); Chem. Abstr. 53, 100310 (1959).
[ 8 ] K. Stransky, M . Streibl, and V. Herout, Collect. czechoslov.
chem. Commun. 32, 3213 (1967).
[9] J. C . Gall, personal communication.
[lo] H . Ageta, J. pharmac. SOC.Japan (Yakugakuzasshi) 79, 58
(1599); Chem. Abstr. 53, 10032c (1959).
1111 T. C. Hoering and R . M. M . Mitterer, Abstr. Annual. GSA
and Assoc. SOC.Joint Meeting, New Orleans 1967, p. 99.
Bis(tricarbonylcyclopentadienylchromium),
a Catalyst for Selective Hydrogenation
By A . Miyake and H . Kondo[*]
Tricarbonylcyclopentadienylhydridochromium ( I ) is converted by conjugated dienes at room temperature quantitatively into bis(tricarbonylcyclopentadieny1chromium) (2).
The conjugated dienes are hydrogenated in the process, e.g.
isoprene to 2-methyl-2-butene.
We also obtained (2). in ca. 80 % yield from bis(cyc1opentadienyl)chromium, by the following reaction, without the
need to isolate ( I ) :
I n contrast to dienes with conjugated double bonds, olefins
with isolated -C=C- bonds are totally unreactive towards
( I ) . Since (I) is regenerated from (2) by hydrogenrll, (2)
can with advantage be used as catalyst for selective hydrogenation. Some examples are given in Table 1. Characteristics for hydrogenation catalyzed by (2) are the following:
I. Isolated double bonds are not hydrogenated.
2. Double bonds d o not migrate.
3. Hydrogenation occurs smoothly above 7OoC and at Ha
pressures > 50 atm, but also slowly at room temperature or
atmospheric pressure.
4. Except for sterically hindered dienes, the hydrogen is
added preferentially at the ends of the conjugated system.
63 1
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fluoride, amid, fluoroformamide, fluoro, pentafluorosulfur, dichloromethylene, fluorosulfamidoyl, fluorosulfonic
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