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Bis(dimethylamido)bis(N-fluorosulfonylimido)-sulfur a Covalent Compound Containing the SN4 Group.

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vmax(KBr) 3240, 3070, 1658, 1555, 1465, 1323, 1270, 1206,
872, 859, and 800cm-1; U V Amax(EtOH)232nm (log e =
4.23), 285 (3.62), 301 (3.69). 338 (3.99,and 414 (3.90). The
intermediates of this reaction should be 1.4-dihydroxy-8cyanoheptafulvenes, (3u) and ( 3 b ) , which probably isomerize
to each other through the tropone structures, (3c) or ( 3 d ) .
particularly under basic conditions. The compound ( 4 ) can
be formed by intramolecular cyclization of ( 3 ~ ) .
Received: June 9, 1969
[Z 41 IE]
German version: Angew. Chem. 81, 702 (1969)
[*] Dipl.-Chem. M. Oda and Prof. Dr. Y . Kitahara
Department of Chemistry, Faculty of Science
Tohoku University, Sendai 980 (Japan)
[l] M . Udu and Y. Kifuharu, Chem. Commun., in press.
[2] Cf. G. Dufruisse, G . Rio, and W. A . Burris. C.R. hebd. Seances
Acad. Sci. 244, 2674 (1957).
131 Structure evidence: The IR and UV spectra are comparable
[4].
with those of 3-cyano-1-oxaazulane-2-imine
[4] T . Nozoe, T . Mukai, and T. Suzuki, Bull. chem. Soc. Japan
36, 38 (1963).
Dimeric 1,3,4,2-Oxadiaza-Pv-phospholes,
Ten-Membered Tricyclic Compounds Containing
Pentacoordinated Phosphorus as a Bridgehead
Atom[ll
By J. Ebeling and A . Schmidpeter [*I
Acetohydrazide reacts with trichlorophosphoranes to eliminate 3 mol. equiv. of HCl. The reaction products (see Table),
having the composition C ~ H ~ N Z O P X
are
Z ,colorless crystals,
readily soluble even in nonpolar solvents, and sublimable in
vacuum. They are thermally stable and resistant to oxidation,
such behavior ruling out their formulation as acetylphosphinodiimines but being in accord with cyclic phosphazenes isomeric to them; moreover, their molecular weights
are found by osmometry and mass spectrometry to correspond to twice that of the empirical formula. Of the various
structural isomers consistent with the above data, the nuclear
magnetic resonance spectra provide unequivocal evidence in
favor of formula (I) [21: The large positive 3*P shift can be
attributed only to pentacoordinated phosphorus, and the
multiplet structure of the IH-NMR signal when X = CH3
and N(CH3)z can only be due to a H,PP'H, spin system
with proximate phosphorus atoms.
Compounds ( I ) should be regarded as products of phosphazene dimerization. Although dimerization of a phosphazene to the 1,3,2,4-diazadiphosphetidine ring is known in
principle, the reaction has hitherto been limited to iminotrihalogenophosphoranes with strongly basic imino nitrogen
carrying a not too bulky substituent 131; phosphazines are
known only as monomers. The dimerization of an oxadiazaPv-phosphole is therefore unexpected, at least when
X = CH3 and N(CHJ)p, and would appear to beconnected
with the phosphorus becoming member of a small ring. For
an oxadiazaphosphole an OPN angle of about 90 is required,
which can be readily realized only with pentacoordinated
phosphorus(v). Cyclophosphazenes having six or more
members in the ring show no tendency to associate.
To satisfy the angle requirements, a phosphorus atom in (1)
must participate in both the four-membered and the fivemembered ring, with one axial and one equatorial bond of
the trigonal bipyramid; the five-membered rings can be fused
onto the longer (axial) or the shorter (equatorial) sides of the
diazadiphosphetidine rectangle. If the two external rings are
assumed to be in trans position, then two structures are
possible for ( I ) , that with the electronegative oxygen in the
axial position being the most likely[41; it is confirmed for
( l b ) and (Ic) by the equivalence of the methyl protons in the
IH-NMR spectrum.
2,2,7,7-Tetruchloro-4,9-dimethyl3.8-dioxa- I.S,6,10- tetraaza2,7-diphospha-P~-tricyclo~5.3.0.0~~~/deca-4,9-diene
(dimeric 2dichloro-5-methyl-I,3,4,2-oxadiaza-P~-phospole)
(la)
An intimate equimolar mixture of PQ5 and acetohydrazide
reacts exothermally with liberation of HCI and formation of
a melt. Compound ( l a ) sublimes from the crude, glassy reaction product at 120°C/0.1 torr in the form of needleshaped crystals (yield 52%).
( I b ) and ( I c )
Trichlorophosphorane (0.1 mole) is added with stirring at
0 "C to a solution of acetohydrazide (0.1 mole) and triethylamine (0.3 mole) in benzene (120 ml). After the reaction mixture has been kept at 0 OC for 3 h and at 20 "C for 15 h, the
triethylammonium chloride is filtered off and the filtrate is
evaporated to dryness. ( I b ) can be sublimed at 13OoC/0.1
torr, and ( I c ) can be recrystallized from pentane (yield 80%).
Received: June 26, 1969
[Z 44 IEI
German version: Angew. Chem. 81, 707 (1969)
I*] Dr. 3. Ebeling and Priv.-Doz. Dr. A. Schmidpeter
Institut fur Anorganische Chemie der Universitat
8 Munchen 2, Meiserstrasse 1 (Germany)
[l] Part 34 of Phosphazenes.
Compound
(la)
(lb)
(14
CI
150
CH3
180
N(CH&
153
380.4
380
264.2
264
-1.85
-2.12 [c] -1.77
0.9
-1.68 [dl -2.55 [d]
14.4
13.5
+52.7
ji42.5
t40.5
[a] Molecular ion in the mass spectrum; recorded by
Dr. H . Seidl.
- Part 33: A . Schmidpeter and C.
Weingand, Angew. Chem. 81,573(1969); Angew. Chem. internat.
Edit. 8, 615 (1969).
[2] A similar tricyclic system has recently been reported by
M . Becke-Goehring and M . R . WOE Naturwissenschaften S5,
543 (1968).
[3] V . Gutmunn, K . Utvury, and M . Bermann, Mh. Chem. 6 ,
1745 (1966).
141 R. J. Gillespie, Angew. Chem. 79, 885 (1967); Angew. Chem.
internat. Edit. 6, 819 (1967).
Bis(dimethylamido)bis(N-fluorosulfonylimido)sulfur, a Covalent Compound Containing the
SN4 Grouprll
[bl Solution in CC14 with TMS as internal standard.
I
[cl Pseudotriplet; JPOCCH
is given as coupling constant.
I
+ JPNNCCH I
1
+
[dl Multiplet; JPCH
JPNPCH
is given as coupling constant for ( l b ) , and
J~NCH J ~ N ~ N C
is H
given for (Id.
I
+
I
[el Solution in CC14 with 85 % H3P04 as external standard.
674
By H. W. Roesky and D . P. Babb[*]
During investigations on fluorosulfonyl compounds we succeeded in preparing for the first time a covalent sulfur-nitrogen compound whose sulfur atom is surrounded by four
nitrogen atoms.
Angew. Chem. internat. Edit. 1 Vol. 8 (1969)1 No. 9
Bis(N4luorosulfonylimido)sulfur difluoride [21 ( I ) reacts
with dimethylamine in diethyl ether to give dimethylamidobis(N-fluorosulfony1imido)sulfur fluoride (2).
Compound ( 5 ) is a colorless solid, m.p. 35 "C, b.p. 116 to
124°C/0.01 torr. 1H-NMR spectrum: one singlet, 8~ =
-2.99 ppm (TMS as external standard). 19F-NMR: one
singlet at 8~ = -58.5 ppm (CFC13 as external standard).
Elemental analysis confirmed the composition of the compound. I R spectrum: w 2950 s, 1470 s, 1380 vs, 1270 vs,
1190 vs, 1090 vs, 1040 s, 96&940 vs, 825 vs. 765 VS, 734 VS,
678 vs, 602 s, 547 vs cm-1.
Received: July 9, 1969
[Z 49 1E1
German version: Angew. Chem. 81. 705 (1969)
[*] Priv.-Doz. Dr. H. W. Roesky and Dr. D. P. Babb
Dimethylamine (6.8 g, 0.15 mole) is passed into a stirred
solution of ( I ) (18.5 g, 0.07 mole) in diethyl ether (300 ml) at
-78 "C during 1 h. The reaction mixture is then warmed to
room temperature and the ethereal phase separated off.
Removal of the ether under reduced pressure and subsequent
distillation of the residue at oil-pump vacuum affords 6 g
(20%) of ( 2 ) .
Compound ( 2 ) is a colorless liquid (b.p. 115"C/0.01 torr)
which was identified by elemental analysis and NMR spectroscopy. The 19F-NMR spectrum recorded at room temperature shows a doublet due to the fluorine atoms of the
0 pprn
~
(CFC13 as external
FSO2 groups, 8 ~ =~-60.3
standard): JFF = 7.4Hz. The fluorine atom of the FSN3
group gives rise to a multiplet of intensity ratio 1:6:17:32:46:
52:46:32:17:6:1 by superposition of a triplet ( F F coupling),
which is split into three septets as a result of FH coupling.
is 2 3 ; ~ F S N ,= -58.4 ppm.
The intensity ratio FSO~:FSN,
I R spectrum: w 3300 w, w 3400 w, 1410 s, 124&1140 vs,
1100 s, 1045 m, 87@-770
vs, 660 s cm-1.
Compound (2) undergoes exothermic reaction with dimethylamine at room temperature in the absence of a solvent to
give bis(dimethylamido)bis(N-fluorosulfonylimido)sulfur ( 3 ) .
Anorganisch-Chemisches Institut der Universitat
34 Gottingen, Hospitalstrasse 8-9 (Germany)
[l] Part 25 of Sulfur-Nitrogen Compounds. - Part 24: 0.GIenzser, R. Mews, and H . W . Roesky, Chem. Commun., in press.
[2] H . W. Roesky and D . P. Babb, Angew. Chem. 81,494 (1969);
Angew. Chem. internat. Edit. 8, 510 (1969).
[3] H . W. Roeslcy and D . P. Babb, Inorg. Chem. 8, 1733 (1969).
Reactions of Ynamines with Iminium Salts[ll
By R. Fuks, G. S. D. King, and H . G. Viehet*l
Ynamines are highly reactive nucleophilic acetylenes [21,
which readily undergo cycloadditions with carbonyl compounds 131, imines 13.41, and other isolated 15-91. conjugated, or
cumulated multiple bond systems [4,9-121. In this communication we describe the condensation of ynamines with iminium
salts.
N.N-Dimethylphenylethynylamine( l a ) reacts readiIy at room
temperature in chloroform solution with aliphatic iminium
salts (2a)-(2e) apparently via the cyclic intermediate (3) to
give acrylamidinium perchlorates (4u)-(4e) ; in the case of
(2c)-(2e) this is noteworthy since it represents a C2-ring
expansion.
An excess of dimethylamine is passed very slowIy - in order
to avoid overheating - into compound ( 2 ) (4 g) in a 100-ml
two-necked flask. The reaction product is extracted portionwise with 100ml of ether and the extract purified, after
removal of the ether, by sublimation at oil-pump vacuum.
Yield: 1.5 g (34%).
Compound ( 3 ) is a white solid, m.p. 123OC, which was
characterized by elemental analysis and by its 1H- and 19FN M R spectra (solution in CD3CN). 19F-NMR spectrum:
one singlet, 8~= -58.7 ppm (CFCl3 as externaI standard).
1H-NMR spectrum: one singlet at 8~ = -2.90 ppm (TMS
as external standard). IR spectrum: w 3420 w, w 2950 w,
1460 m, 1392 vs, 1278 m, 1206 vs, 1100 vs, 1055 m, 962 vs,
860s, 800s. 765s, 74Ovs. 662m, 603 s, 548vs, 502w,
460 w cm-1.
Dimethylamido-N-fluorosulfonylimidosulfur oxide fluoride 131 ( 4 ) reacts with dimethylamine at room temperature,
in a manner similar t o (2), to give bis(dimethy1arnido)-Nfluorosulfonylimidosulfur oxide (5). We found that 18 g of
(4) gives 8.3 g (41 %) of (5).
The analytical and spectral data (UV, I R and NMR) confirm
the proposed structure (4). Hydrolysis of (4a) with 30%
aqueous NaOH affords p,@,N,N-tetramethyl-cr-phenylacrylamide in 84 % yield. Melting point and mixed melting point
(56 "C)are identical with that of the product obtained from
( l a ) and acetonet31.
Heteroaromatic iminium salts also condense easily with ynamines in chloroform at room temperature. Thus. with Nmethylquinolinium iodide for example, compound ( I ) gives
4-amino-N-methylquinoliniumiodide derivatives (7) possibly via intermediate ( 6 ) , which then loses an unidentified Cz-
Angew. Chem. internat. Edit. 1 Vol. 8 (1969) 1 No. 9
675
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containing, compounds, group, sn4, sulfur, dimethylamino, fluorosulfonylimido, covalent, bis
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