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Cyclooctasulfur Monoxide from Cyclooctasulfur.

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C A S Registry N u m b e r s :
141. 52225-68-0 1 ( 5 ) 52225-69-1
f 6 u ) . 52225-45-3 ,
l t j h ) . 52225-46-4 i I 7 u i 1 52248-68-7
( 7 h ) : 52248-69-8
( , Y o ) . 52248-70-1
(;i'h/ : 52248-71-2 1 (911) 52248-72-3 /
( Y h i . 52248-73-4 // ( 1 0 1 ( R ' = H ) : 52225-47-5 / (10) ( R ' = M e ) 52225-70-4
'
'
Reactions of lndole Derivatives. Part 23. - - P a r t 22: J . D.Wilcock a n d
E . Wiii~cvfddi.Cheni. Ber. /07. 975 (1974).
[2] M . He>\c,. Indolalknloide i n Tabellen. Springer Vrrlap, Berlin 1964.
[ 3 ] 2.1. Fer/r\. Collect. C7ech Chein. Commun. 74, 2323 1 1964).
[4] C'. Krmj and H Rupoporr. J. Amer. C'hem. SOC. 94. 8615 (1972).
[ 5 ] D. I. L w . C . J Morroiv. a n d H. Ropoport, J. O r p Chem. 3Y, 893
(1974).
163 C. Diero.w. H. J . Moririwo, A Wcilscr. a n d L. J Drirhcini. .) Amer.
Chem. Soc. KK. 1792 (1966).
[7] All the substances were chardclerired by IR, N M R . and mass spectra
a n d correct elemental analyses.
[I]
Hexamanganato(vrr )manganic(iv)Acid :A "Pseudopermanganic Acid[**]
By Burit Krebs and Kluirs-Dirter Husse[*l
If an aqueous solution of permanganic acid (prepared by
reaction of stoichiometric amounts of Ba(Mn04)z with
H ~ S O Jis) concentrated under reduced pressure, one obtains
different products, depending upon the experimental conditions: dimanganese heptoxide, water, manganese dioxide
phases (with liberation of oxygen), and a new crystalline compound which has not yet been exactly identified(''. On the
basis of chemical analysis and its redox equivalent, the substance was assumed to be a "solid permanganic acid" having
the composition MnzO7.2HzO('I. This violet compound is
thermally very sensitive and decomposes mainly to MnZO7,
oxygen. manganese dioxides, and water above - 4 T , reacts
vigorously with oxidizable substances, but can be obtained
pure as large bipyramidal crystals under optimal reaction
conditions (distillation at -40 T / i 0 - torr, cf. ref. [ 13).
X-Ray structure analysis at - 120 'C has now shown that
the compound concerned is a complex hexamanganato(vi1)manganic(1v) acid; the redox equivalent per Mn (6.57)corresponding to the exact formula (H,O),[Mn(MnO,),] .I
1H,O
( / ) approaches that of a "true" permanganic acid.
In the [Mn(MnO&,J2- anion, a central Mn"' atom, which
is surrounded octahedrally by bridging 0 atoms, is coordinated with six Mnv"04 tetrahedra with a trigonal prismatic
arrangement of the Mn"" relative to the central Mnl"; the
complete anion approximates well to C2 symmetry. The mean
bond lengths amount to Mn'"-O(bridge)
1.90 (individual
1.74 (1.69
values between 1.85 and 1.94), Mn""-O(bridge)
to 1.73, Mnv"-O(terminal) 1.60A (1.55 to 1.66A).
The hexamanganato(vll)manganate(lv)iorl (Fig. 1 ) represents
a new type of a "heteropolyanion" in which both components
arise from the same element in different oxidation states.
The chemical properties are largely determined by the MnV"
centers present in excess.
The excess protons are clearly present as H 3 0 + ions, which
are linked to the other HzO molecules of the lattice by a
hydrogen bond system (O(H)...O distances in the bridges
anion in solid Iiexamaiigaiiato(ViIIFig. I . Srructure of the [Mn(Mn0,)6]'
manganic(l\') acid (H.,C))~[Mn(MnOl)h]-I I H K ) f I i .
originating from the H 3 0 + groups between 2.48 and 2.60A).
Crystal data of compound ( l ) (cf. ref. [l]): orthorh:mbic.
CiY-Fdd2; u = 17.77(2), h=63.97(8), C = 10.48(2)A (at
- 120°C);Z = 16 ; d,,,,, = 2 . 2 4 g ~ m -The
~ . structure was determined from 1457 film data and refined to R =0.092.
The behavior of aqueous permanganic acid solutions on concentration under various conditions will be reported at :i
later date. The question of the existence of a pure "solid
permanganic acid" still remains open. However, results
obtained so far, the behavior of Mn207121towards water,
and crystd~~ochemica!
considerations cast doubt upon the stability o f a solid phase in the Mn2O7-H2O system (as hydrate
MnzO,.x-HzO or, as formerly postulated, as H M n 0 4 or as
H30'MnOi['l).
Received: April 30. 1974 [Z6 5 I[.]
Cierniaii versioii. Anpcw. C'liem. NO. 647 (1974)
[ I ] B. K w h \ a n d X:D. I f i i . \ w . %. N,iturforsch 2Hh. Z I X (19711. t i 1 xliicli
publication 0.5rnM should read 0.5 M (begiiiiiing o f third paragr,iphl. ,tnd
- 18 C should read - 1HO (~(end of third p;tr;igraphl.
L?]
0. C ; I i w i \ u and I I S i h r i 2 r r . L. Anorg. Allg. ('hem. 271. 193 (19531
131 N A . Frigrrio, J . Ainer Chcni. Soc. 91. 0700 (196")).
Cyclooctasulfur Monoxide from Cyclooctasulfur[' I
By Ralf'Steiidrl and Jiiry L a u d * ]
Cyclooctasulfur monoxide was first obtained as a product
of the reaction of thionyl chloride with "crude sulkme" HrS,,12i.
We have now found that cyclooctasulfur can be oxidized
directly with trifluoroperacetic acid (molar ratio 1 : I ) in a
simple manner :
Sx
+ CF.tC'C).!H
-+
SxO
+ C'F<SO?lI
[*] Prof. Dr. B. Krebs a n d DiplLChem. K.-D. Hassr
Institut fur Anorganische Chcmie der Universitit
23 Kiel, Olshausenstrasse 40---60 (Germany)
Present address.
Fakultitt ftir Chernie der Universitjt
48 Bielefeld. Postfach 8640 ( G e r m a n y )
["'I
This work was supported by the Deutschc Forschungsgemeinschaft
and the F o n d s der Chemischen Industrie.
Angew. Chem. inlrrnat. Edit. / Vol. 13 ( 1 9 7 4 ) 1 No. 9
The S 8 0 obtained in cu. 45 o/o yield by this method is identical
in color, crystal form, decomposition temperature, solubility,
[*] Prof. Dr. R . Stcudel a n d DiplLChem. J. Latte
Instittit fur Anorgantsche und Analyttsche Cliemic der Technischeii
Uniwrsiliit
1 Berlin 12, Strasse d<s 17. Juni 135 (Germany)
603
composition, and IR spectrumi3] with the product prepared
from SOClz and HzS,. This new, more productive synthetic
route requires much less time and experimental effort than
the former preparation.
Procedtwe:
Sg (3.76g, 14.7mmol)isdissolved in CHzC12 (800ml)by refluxing. The homogeneous solution is slowly cooled to 0°C and
protected from light by a black cloth. A freshly prepared
solution of trifluoroperacetic acid [obtained by suspension
of 50% H r 0 2 ( l g , 14.7mmol) in CH2C12 (50ml) at 0°C
and rapid addition of trifluoroacetic anhydride ( 5 ml,
36mniol)l is added dropwise over 1 h to the stirred reaction
mixture, which assumes an intense yellow hue. Concentration
in a vacuum at 20°C bath temperature to 1/3 of the original
volume leads to precipitation. Further crystallization is
induced by cooling to -20°C. The precipitate is collected
on a glass frit, washed with CHzC12, and dried in a vacuum.
The procedure yields 1.8g of almost pure S 8 0 which can
be isolated analytically pure by recrystallization from CS2.
Received: May 3, 1974 [Z 67 IE]
German version: Angew. Chem. 86. 648 (1974)
Sulfur-Oxygen Compounds. Part 23.-~-Part22 is considered to he: H .
B a k , 8. Soloirki, P. Rosmus, and R. Sreiidel, Angew. Chem. 85, 987 (1973);
Angew. Chem. internat. Edit. 12, 933 (i973).-.- Part 21: 131.
[2] R. Srrtrilrl and M . Rrhsch, Angew. Chem. 84, 344 (1972): Angew. Chem.
internat. Edit. 11, 302 (1972): R Srriirlri, P. L i y r r , H . Briiilacxk. and M .
Rchwh. ibid. 85. 452 (1973) and 12, 423 (1973). resp.
[ 3 ] R. Slrirdcd and M . RrhsOi, 1. Mol. Spectrosc. 5 1 . 314 (1974).
[I]
Synthesis of Pyrazolo Heteroaromatic Compounds by
Means of 5-Amino-3-methyl-l-phenylpyrazole-4-carbaldehyde
By Jochen Ha@ and Eberhard Breitmaierl']
5-Amino-3-methyl-1 -phenylpyrazole-4-carbaldehyde ( 3 ) is
formed in a modified Vilsmeyer synthesis['.21: reaction of
5-amino-3-methyl-1-phenylpyrazole( I )i31 with an excess of
N,N-dimethylformamide (DMF) and phosphorus oxide
chloride affords crystalline 5-[(N,N-dimethylamino)n~ethyleneamino]-3-methyl-l-phenylpyrazole-4-carba~dehyde (2).
which is converted in good yield into ( 3 ) by acid hydrolysis.
CHS
6:BH5
5-Amino-3-methyl-1 -phenplpyrazole-4-carbaldehyde( 3 ) :
POC13 (1.5mol) is added dropwise with cooling to D M F
(3.5moI). Then ( I ) (0.5mol) is added portionwise, the reaction
mixture is stirred for 17 h at 70°C (oil-bath temperature) and
subsequently poured cautiously into an excess of N a 2 C 0 3
solution (cooling). The crystals that separate after some time
[(Z)] are hydrolyzed by HC1 (ca.2Owt.-%). After 50 hours'
stirring at 40°C (oil-bath temperature), neutralization with
N a 2 C 0 3 solution, extraction with ether and removal of the
solvent, ( 3 ) is obtained as a viscous oil. Recrystallization
from 2-propanol affords a finely crystalline, pale yellow product : yield 64%, m. p. 97.5 "C.
Pyrazolo[3,4-b]p~~ridine
(4)and 6,7-dihydro-3-methyI-6-oxo-lphenylpprazolo/3,4-b]p~~ridine-5-carbonitrile
(5):
The CH-acidic carbonyl compound (0.02 mol) is refluxed with
0.02 mol of ( 3 ) in glacial acetic acid (30 ml) for ca. 30 h. For
working-up, the mixture is poured into an excess of Na,CO,
solution and extracted with ether. The crude products are
recrystallized from ethanol or ethanol/water [(4a), yield 68%,
m.p. 79.5"C; (4b), yield 79%, m.p. 96°C; (4cjL4',yield 46%,
m.p. 86°C; (5), yield SIX, m.p. 316"CI.
3-Methyl-1 -phenylpyrnzolo[3,4-d]p~~rimidine
(6) :
0.025mol of ( 3 ) is heated with 0.1 mol of formamide for
20 h at 140'C. The cooled reaction mixture is treated with
water (10m1)and extracted with chloroform. The oil remaining
on removal of the solvent is crystallized from 2-propanol;
yield 60%, m. p. 84°C.
Received: June I t . 1974 [Z 60 IE]
German versioh: Angew. Chem. 86, 671 (1974)
CAS Registry Numbers:
( I ) : 1131-18-6 1 1 3 ) : 52217-35-3 i ( 4 a ) . 52217-36-4 /
1 4 h ) . 52217-37-5 f ( 4 ~ ) 51431-29-9
:
i (S): 52217-38-6 i
1 6 ) : 52217-39-7 / ethyl 3-oxobutanoate: 141-97-9 1 2,4-pentanedione:
123-54-6 / cyclohexanone: 108-94-1 / ethyl cyanoacetate: 105-56-6 i
formamide' 75-1 2-7.
This new aldehyde opens a direct route for preparation of
condensed heterocycles of the pyrazole series. Thus cyclocondensation of ( 3 ) with 1,3-dicarbonyl compounds affords the
pyrazolo[3,4-b]pyridines (4a)-( 4 c ) , with ethyl cyanoacetate
affords the derivative ( 5 ) and with formamide the pyrazolo[3,4-d]pyrimidine ( 6 ) . The condensation product of ( 3 )
with cyclohexanone is identical with 5,6,7,8-tetrahydropyrazoio[3,4-b]quinoline (4c) prepared from 2-hydroxymethylenecyclohexanone and ( I ) [ " ] . The compounds prepared were
identified by means of spectroscopic data (IR, UV, MS, and
'H- and I3C-NMR).
[*] Dip].-Chem. J . Hlufel and Prof. Dr. E. Breitmaier
Chemisches lnstitut der Universitlt
74 Tiibingen. Auf der Morgenstelle (Germany)
604
[I]
pp.
[2]
[3]
Organikum. V E B Deutscher Verlag der Wissenschaften, Berlin 1970.
358ff
A . Vilsrn~~yer,
Chem.-Ztg. 75, 133 (1951).
E . Mohr, J . Prakt. Chem. 79, 14 (1909).
[4] J . HBi!lel and E. Bueitrnnier, Angew. Chem. 85,959 (1973); Angew Chem.
internat. Edit. 12, 922 (1973).
Conformation of trans-Cyclooctene
By Otto Ermer[*]
Previous X-ray structural studies have not hitherto given exact
structural parameters for trans-cyclooctene derivatives'']
[*] Dr. 0 . Ermer
Abteilung fur Chemie der Universitat
463 Bochum, Universitatsstrasse I50 (Germany)
Angew. Chem. internat. Edit. J Vnl. 13 0 9 7 4 ) J No. 9
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