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Nonacyclo[10.8.0.02 11.04 9.04 19.06 17.07 16 (2).09 14

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isolated and identified spectroscopically as the doubly aromatized derivative of 10, namely, 12. The more slowly
eluting component could not be obtained in pure form.
The tetraasterapropellane structure of 11 can be derived
from its 'H-NMR spectrum.
.04,9.0 19.o6,17 .o7 5.0
icosane, a Double Tetraasterane**
'
.o
1
14.19
1-
By Volker T. Hoffmann and Hans Musso*
Dedicated to Professor Ukich Schollkopf
on the occasion of his 60th birthday
Replacement of the cyclohexane chair-form rings in the
vertical planes of the diamond lattice by boat-form rings
results in the wurzite lattice. If this is also carried out on
the horizontal planes, one obtains an unknown carbon
modification,l]' whose smallest characteristic structural
unit, the tetrasterane 1 , is known.lzl Earlier, we succeeded
in enlarging 1 by the addition of two cyclohexane rings to
give 2.13]We now report the synthesis of the double tetraasterane 9141(Scheme 1).
RJcjEJt:
R
r6,
R
64'.
R = Co2H
CI
r8,
'
L9,R
10,
= C0,CH3
=
R
= C0,CH3
H
12
11
R = CO,CH,
1
2
Photoexcitation of 1,4,5,8-tetrahydronaphthalene-2,3-dicarboxylic anhydride 3[5i
in dioxane with a high-pressure
mercury lamp equipped with a Solidex filter in the presence of benzophenone as photosensitizer results in the formation, in approximately 8% yield, of a sparingly soluble
mixture consisting of at least four dimers. Fractional sublimation of this mixture at
torr gave a forerun at about
250°C followed by the desired dimer 4 starting at 310°C
(relative amount in the mixture, 46%; m.p. >350°C). Compound 4 was treated with methanol/acetyl chloride to
convert it into the tetramethyl ester 6 (Table I). The anti
head-head dimer 5 undergoes sublimation already at 190200°C and was likewise characterized as the tetramethyl
ester (10). The structures of 6 and 10 were confirmed by
X-ray crystal structure a n a l y s i ~ . [ ~Chromatography
.~I
of the
mother liquors of 10 on SiOz revealed the presence of two
additional compounds. The faster eluting component was
[*I
[**I
Prof. Dr. H. Musso, Dr. V. T. Hoffmann
lnstitut fur Organische Chemie der Universitat
Richard-Willstatter-Allee 2, D-7500 Karlsruhe
Asteranes, Part 19. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. We
thank A . Kuiper. P. Lung. 1. M a i m I . Rossnagel, I . Suss. and U. Tanger
for numerous spectra, gas chromatograms, and elemental analyses.Part 18: A. Otterbach, H. Musso, Angew Chem. 99 (1987) 588; Angew.
Chem. Inr. Ed. Engl. 26 (1987) 554.
1006
0 VCH Verlagsgesellschafr mbH, D-6940 Weinheim, 1987
Scheme 1. a) 3 (6.8 g, 33.6 mmol), benzophenone (200 mg), dioxane (200 mL)
under N2. Philips HPK (I25 W), Solidex filter, irradiated for 4 d. 560 mg (8%)
4 + 5 (see text). b) 4 (65 mg, 0.16 mmol), methanol (IOmL), acetyl chloride
(1.0 mL), refluxed for 5 d, heterogeneous reaction, 69 mg (87%) 6,
m.p.=324"C. c) 5 (200 mg, 0.48 mmol) was added to a solution containing
sodium (50 mg) in methanol (15 mL) and the solution was acidified with dilute H,S04. The monoester was extracted with ether and then treated with
diazomethane in ether, affording 124 mg (51%) 10, m.p.=230"C. d) 6
(400 mg, 0.99 mmol) dissolved in 2 N NaOH (50 mL) over 30 min. The solution was then acidified with 2 N H$04, resulting in the formation of a fine,
colorless precipitate, 396 mg (90%) 7 . e) A suspension of 7 (690mg,
1.56 mrnol), N-chlorosuccinimide (3.22 g, 24 mmol), and Pb(OAc), (5.0 g,
6.3 mmol) in dimethylformamide/glacial acetic acid ( 5 : I ) (30 mL) was
heated under N 2 ; the reaction occurred at 45-60°C. Workup with water and
pentane and sublimation afforded 14 mg (2%) 8 , m.p. >350"C, containing a
small amount of a pentachloro derivative. 0 A refluxing suspension of 8
(50 mg, 0.13 mmol) in ethanol (40 mL) was treated over 3 h with sodium
(3.0 g, 0.13 mmol) added in the form of small pieces Workup with water and
pentane afforded 7.0 mg (21%) 9 as colorless needles, m.p.=230-23SoC (methanol). M e (calcd)=264.1878, Ma (found)=264.1885.
Alkaline hydrolysis of the tetramethyl ester 6 yields the
acid 7 (90%), which, upon heating or drying, is readily
converted back into the anhydride 4. Grob degradation"'
kith lead tetraacetate and N-chlorosuccinimide results in
the formation of a mixture consisting of three parts of the
expected tetrachloride 8 and roughly one part of a pentachloro compound (mass spectrum), which cannot be
completely separated by recrystallization. Dehalogenation
occurs only slowly with sodium in ethanol and affords the
0570-0833/87/1010-1006 $ 02.50/0
Angew. Chem. Inr. Ed. Engl. 26 (1987) No. I0
Table I. Melting points and 'H- and "C-NMR data [a] for the compounds I ,
6, and 9- 12 [S].
1
6
M.p. [ "C] 324-325 324
'H-NMR
olefin./
aromat.
COXHI
CH
CHI
"c-N M R
co
-
-
2.61
1.60
9
10
11
12
230-235
230
- [b]
227-229
-
3.67
3.12
1.89, 1.61
1.55
175.76 (s)
olefin./
aromat.
-.
2.65
1.40
5.70
5.71
7.05-7.20
3.63
3.61
3.51
-
-
2.84, 2.17 2.56, 2.45
2.49, 2.40 2.55
173.87 (s)
124.16 (d)
122.21 (s)
OCHi
51.77 (4)
51.81 (4)
other
C atoms
48.15 (s)
34.89 ( s )
31.93 (d)
30.89 (t)
26.83 (t)
51.70 (s)
3.46, 3.29
172.67 ( s )
136.45 ( s )
127.25 (d)
126.54 (d)
51.73 (q)
35.47 (t)
34.75 ( s ) 33.98 (t)
30.84 (d) 30.71 (t)
28.56 (t)
[a] 'H-NMR: 250 MHz, CDCI,; "C-NMR: 250 MHz, CDC13. [b] Not isolated.
pure, double tetraasterane 9 in only about 21% yield as
colorless needles (m.p. = 230-235 "C, methanol). Whereas 1
melts at very high temperature (Table 1) and is thermally
stable at temperatures over 300°C, heating of 9 in the injection part of a gas chromatograph at 270°C results in the
formation of two isomers; however, the structures of the
isomers have not yet been determined.
Received: February 2, 1987;
revised: March 6, 1987 [Z 2082 IE]
Publication delayed at authors' request
German version: Angew. Chem. 99 (1987) 1036
~
(I] S. Housmans, P. H. Honnef, Nachr. Chem. Tech. Lab. 32 (1984) 379.
121 H. G. Fritz, H.-M. Hutmacher, H. Musso, G. Ahlgren, B. Akermark, R.
Karlson, Chem. Ber. 109 (1976) 3781.
[3] G. Kaiser, H. Musso, Chem. Ber. 118 (1985) 2266.
[4] V. T. Hoffmann, Dissertation. Universitat Karlsruhe 1987.
77 (1955) 73; R. Askani,
151 W. J. Bailey, J. Rosenberg, J . Am. Chem. SOC.
Giessen, private communication.
161 X-ray structure analysis (Mo,,, A = 71.073 pm, graphite monochromator):
6 (M. Schmidt, Diplomarbeit. Universitat Karlsruhe 1985): C28H3ZOX
(496.56): p= 1.43 g cm-',
PI, Z = 2 ; a=719.7(4), b = 1115.2(6),
c = 1534.0(8) pm, n=98.8(4), /l=89.95, y = 107.9(4)", V= 1.15689 x 10'
pm': R=0.088 (R,%=0.074). 10 [4]: C28H,208-2CH30H (560.65);
p=1.32, C2/r, Z = 4 (-86°C); a=2058.9, b=1109.5, c=1834.6 pm,
p= 137.9", Y=2.8118 x lo9 pm', 5705 reflections, R = R , . =0.067.-Further details of the crystal structure investigation may be obtained from
the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D75 14 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository
number CSD-52466, the names of the authors, and the journal citation.
171 K. B Beder, M. Geisel, C . A. Grob, F. Kuhnen, Synfhesis 1973, 493.
[8] The spectra and elemental analyses of all other new compounds (41are in
accord with the structures given.
Dimanganese Heptoxide for the Selective Oxidation
of Organic Substrates
By Martin Tromel* and Manuel Russ
2 KMn0,
M n z 0 7 + 2 KHSO,
+ 2 H,SO,
+ H20
The stability of the solutions is probably due to the fact
that oxidizable impurities and traces of water, which cause
decomposition of Mn207, are removed during its formation. The deep red solutions contain approximately 100 mg
of Mn20, per mL, are practically completely stable at
room temperature, and, in contrast to undiluted Mn,O,,
can be handled safely. Our investigations so far have
shown that selective oxidation reactions are possible which
can be carried out simply with efficient thermal control.
The course of the reaction can be observed owing to the
intense color of the Mn,O, solution themselves. The reagent is especially suitable for use in aprotic medium.
Aliphatic and alicyclic C-C bonds, C-F and C-CI
bonds, and primary C-H bonds are not usually attacked at
room temperature; the same holds true for trimethylsilyl
groups.
Primary and secondary alcohols, such as 1 and 2-6 (Table I), respectively, are smoothly oxidized to carboxylic
acids and ketones, respectively. The reactions proceed in
aprotic medium at temperatures as low as - 7 0 T , thereby
making it possible to react thermally unstable and acidsensitive compounds such as 2 and 5 , respectively.
'
'OH
k
+ 2 Mn20,
3H
C
, A
0
- 4 Mn02
1
H
84%
- 3 HZ0
0
OH
&CH3H
- 2 MnOt
2
3 O
- 3 H20
C
H
,
92%
Table 1 Oxidation of selected secondary alcohols with Mn2O7.
3
4
5
6
Alcohol
Product
Yield [%I [a]
cycloheptanol
I-cyclohexylethanol
I-phenylethanol
3-octanol
cycloheptanone
cyclohexyl methyl ketone
acetophenone
3-octanone
91
88
81
84
[a] Yields of isolated product.
Mn,O, has been described as a dark red, volatile, unstable oil,['1which, apart from its strong oxidative ability, can
explode unexpectedly (for example, on contact with or[*] Prof. Dr. M. Tromel, DipLChem. M Russ
lnstitut fur Anorganische Chemie der Universitat
Niederurseler Hang, D-6000Frankfurt am Main 50 (FRG)
Angew. Chem lnt. Ed. Engl. 26 (1987) No. 10
ganic compounds or with dust from the air). There are apparently no reports on controlled oxidation reactions, although the compound has been known for over 125 years.
The Mn-0 bond lengthsJ2] which have been determined
e~perimentally,~~]
indicate that Mn,O, should be a stronger
oxidizing agent than permanganate.
According to the most detailed investigation carried out
so far,[41solvents such as glacial acetic acid or CCl, undergo oxidation by Mnz07 even at low temperature. In
contrast, we have been able, by means of a special procedure, to obtain stable solutions of Mn,O, in CCl, or 1,1,2trifluoro-l,2,2-trichloroethane (Freon 113). Mn207, prepared by reaction of KMnO, with concentrated sulfuric
acid in the presence of the solvent according to the following reaction, is immediately taken up by the organic
phase:
Owing to the low temperature, the oxidation of primary
alcohols such as 1 can be carried out without accompanying acetalization. Ketones formed from secondary alcohols
can be easily separated by filtration from the Mn02 precipitate. In addition, the MnO, binds the water formed dur-
0 VCH Verlagsgeselischaft mbH. 0-6940 Weinheim. 1987
OS70-0833/87/1010-1007$ O2.50/0
1007
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