close

Вход

Забыли?

вход по аккаунту

?

Fluorosulfinyl Isocyanate.

код для вставкиСкачать
developed with chloroform. The 'H-NMR spectra of (1)-(3)
are in accord with the proposed structures (cf. [3]).
Further proof for the identity of the anilinoquinones (1)(3) was obtained by converting them into the known hydroxyquinones ( 4 ) l41, (5)[51 and (6)[,1, respectively, with refluxing
10 % H,SOJmethanol (1 : 1) for 10min (Table 1). Each reaction mixture was poured into water, the product extracted
with chloroform, the chloroform layer dried with Na2S04
before evaporation, and the resulting hydroxyquinones purified by sublimation.
Received: November 12, '1975 [Z 348 IE]
German version: Angew. Chem. 88, 87 (1976)
CAS Registry numbers:
( I ) , 57674-09-9; ( 2 ) , 57674-10-2; ( 3 ) , 21111-68-2; 14J. 615-91-8;
(S), 2446-75-5; (61, 2207-58-1
[I1
__
121
r3i
[4]
[5]
[6]
K Schafer and A . Ayuado, Angew. Chem. 83,441 (1971); Angew. Chem.
Jnt. Ed. Engl. 10, 405 (1971).
7: Zincke, Ber. Dtsch. Chem. Ges. 16, 1555 (1883).
S. Berger and A . Rieker in S. Patai: The Chemistry of Quinoid Compounds. Wiley, New York 1974, Part I, p. 163ff.
R . B. Woodward, F . Sondheimer, D.Taub, K. Heusler, and W H . McLamore,
J. Am. Chem. SOC. 74, 4223 (1952).
H . Musso, Chem. Ber. 91, 349 (1958).
K G . Hanger, W C. Howell, and A . K Johnson, J. Chem. SOC. 1958,
496.
Fluorosulfinyl Isocyanate[**]
By Hans-Joackim Krannich and Wolfgang Sundermeyer[']
All previous attempts to prepare halosulfonyl pseudohalides,
OSXY, and sulfinyl bispseudohalides, OSY (X =halogen;
Y = pseudohalogen) have failed"]. We have now succeeded
in synthesizing the first compound of type OSXY by reaction
of fluorocarbonyl bromide"] with bis(sulfony1amido)mercury(11)1~].
The fluorosulfinyl isocyanate (2) is formed in a rearrangement reaction-to our knowledge formerly unobservedfrom the expected intermediary fluorocarbonylsulfinylamine
(1 ) ; the CF bond becomes an SF bond.
the transition 109-67 is evidenced by a metastable peak
at 41 (calc. 41.18). The I9F-NMR spectrum shows a singlet
at - 55.5 ppm (CFC13ext. standard), which can be attributed
to an OSF bond in contrast to an OCF bond14](for comparison : CH,O-S(0)F
(- 55.6ppm)["I, (CF,),N-0-S(0)F
(-59.5ppm[5b1). In the IR spectrum there are no carbonyl
bands. Bands do occur, however, at 2245 (vs, v,,NCO), 2192 (m,
sh), 1348 (s, v,NCO), 1281 (vs, vSO), 753 (vs, vSF), 716 (vs,
vSN), 610 (vs, 6NCO), and 488 cm ' (m) (gas spectrum). Also
present is the combination band of the two NCO vibrations
at ca. 3580cm-'. In the Raman spectrum the intensity ratio
of the two NCO bands is typically reversed.
Our redistribution experiments on carbonyl halides and
pseudohalides[6]indicatearelatively high mobility of the fluorine atom in the neighborhood of a carbonyl group. An intermolecular exchange of the fluorine atom between the two C
atoms, observable in the case of fluorocarbonyl isocyanate
OC(F)NCO by a broad I9F-NMR signal at room temperaturel7I,leads in the case of ( I ) to an irreversible rearrangement
to (2).
~
Received: November 5, 1975 [ Z 353 IE]
German version: Angew. Chem. 88,88 (1976)
CAS Registry numbers:
OCFBr, 753-56-0; HglNSO),, 25682-06-8; fluorosulfinyl isocyanate.
57789-32-9
111 G . Jander and D. Ullmann, Z. Anorg. Allg. Chem. 230, 405 (1937);
C . S. Forbes and H. H . Anderson, J. Am. Chem. SOC. 65, 2271 (1943);
P. W Schenk and H . Bloching, Chem. Ber. 92, 2333 (1959).
[2] G. Siegemund, Angew. Chem. 85, 982 (1973); Angew. Chem. Int. Ed.
Engl. 12, 918 (1973).
[3] W Verbeek and W Sundermeyer, Angew. Chem. 81, 330 (1969); Angew.
Chem. Int. Ed. Engl. 8, 376 (1969).
[4] H . 4 . Horn, Fluorine Chem. Rev. 6, 135 (1973).
[5] a) F. See/, J . Boudier, and W Gombler, Chem. Ber. 102, 443 (1969);
b) J . A . Loft, D. P . Babb, K . E . Pullen, and J . M . Shreeoe, Inorg.
Chem. 7, 2593 (1968).
[6] Chr. Jackh and W Sundermeyer, Chem. Ber. 106, 1752 (1973).
[7] 0.Glemser. Li. Biermann, and M . Field, Chem. Ber. IOf), 1082 (1967).
,>
[Ir (2,4,6-C,H2(CH,) (CO)(PPh,),]-The First Example of cis-fvans Isomerism in Complexes of the
Vaska Type[**]
By Lutz Dahlenburg and Reinhard Nasd']
OCFBr (ca.27 g) is condensed via a high-vacuum apparatus
onto Hg(NSO), (5.1g) in a 200ml Duran glass ampoule;
the ampoule is then sealed and shaken for 48 h at 10--15°C.
After removal of the volatile reaction products in a high
vacuum the excess OCFBr serving as reaction medium is
separated from the product at normal pressure for further
use. The combined product after five such treatments afforded
4.5 g of (2) (yield.26.7%) as an almost colorless liquid (b. p.
60.5 "C) which slowly turns yellow at room temperature.
While elemental analysis merely affords evidence of the
presence of ( 1 ) or (2), the mass spectrum clearly indicates
presence of the isomer ( 2 ) : m/e= 109 molecular ion (rel. int.
57.8%), 90 0s-NCO (12.5), 67 OSF (loo), 64 SO2 (6.3),
48 SO (25), 46 NS (18.8), 42 NCO (14.0), and 32 S (7.8);
p]
Prof. Dr. W. Sundermeyer and Dipl.-Chem. H. J. Krannich
Anorganisch-chemisches Institut der Universitat
6900 Heidelberg 1, Im Neuenheimer Feld 270 (Germany)
[**] We thank Prof. Dr. H . Siebert for helpful discussion of the vibration
spectra. This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie.
I10
The cis-trans isomerism frequently found in planar platinum@) complexes of the type [Pt(L),(X)(Y)] has so far not
been observed in the numerous comparable iridium(1) complexes of the Vaska type IrA(CO)L, (A=univalent anion
ligand, L=tertiary phosphane or arsane). On the basis of
their 'H- and ,lP-NMR spectra and their dipole moments
all these compounds prove to have a trans configuration,
which, in two cases [A, L=CI, P(o-C,H,CH,),; C6F5,
P(C,H,),] has also been confirmed by X-ray structure analysis[', The postulated existence of cis-[IrA(CO)(PPh,),]
[A=H, C(CN),] is doubtful[31,if not already ruled
We are now able to show that the o-mesityl complex ( 2 ) .
which is accessible according to
'.
M e s = 2,4,6-CsH,(CH,),
[*] Prof. Dr. R. Nast and Dr. L. Dahlenburg
Institut fur Anorganische und Angewandte Chemie der Universitat
Martin-Luther-King-Platz 6, 2000 Hamburg 13 (Germany)
[**] This work was supported by the Fonds der Chemischen Industrie.
Angew. Chem. Inr. Ed. Engl. J Vol. I S ( 1 9 7 6 ) No. 2
Документ
Категория
Без категории
Просмотров
0
Размер файла
137 Кб
Теги
isocyanates, fluorosulfinyl
1/--страниц
Пожаловаться на содержимое документа