close

Вход

Забыли?

вход по аккаунту

?

New Method for Synthesis of Many-membered Hydrocarbon Rings.

код для вставкиСкачать
the azido sugar ( 8 ) .The 3-0-benzyl ether obtained by benzylation of ( 8 ) can be cleaved selectively to ( 9 ) . which reacts
with the P-chloride ( 4 ) to give a 55 2,yield of a disaccharide
mixture that contains 80 'i: of the a-form (13).
270-MHz 'H-NMR spectra of all oligosaccharide derivatives prepared could be largely analyzed and provided definite
proof of the a-linkage in each case. The azidoglycosides can
readily be converted into aminoglycosides by hydrogenation
using known techniques. The 0-benzyl groups are also
removed by hydrogenation under the usual conditions. The
demonstration of three very important types of linkage shows
the capability of the method which can clearly be extended
in many ways.
Received: May 5, 1975 [Z 242 IE]
German version: Angew. Chem. 87. 547 (1975)
CAS Registry numbers:
( l u i . 55682-47-8; i l h ] . 55682-48-9; 121. 55682-49-0;
( 3 ) . 55682-50-3: (41. 55682-51-4; ( 5 ) . 55682-52-5;
( ( i r i ) . 55682-53-6: 16h). 55682-54-7; (71. 55682-55-8:
( H I . 55682-56-9: IYI. 55682-57-0: i 1 0 1 . 55682-58-1 :
1111. 55682-59-2, ( 1 2 ) . 55723-08-5; f 131. 55723-09-6
obtained from 4,4"-bis(bromomethyI)-o-terphenyl
( I u ) and
disodium 1,2-ethanedithiolate ( 2 a ) or alternatively from 4,4"bis(mercaptomethy1)-o-terphenyl ( 1 b ) and 1,2-dibromoethane
( 2 b ) by the dilution method (DM) previously described by
us in detail on several occasionsi4! This product (3) is oxidized
to the disulfone ( 4 ) by Hz02in glacial acetic acid/benzene
in almost quantitative yield (for properties of the compounds
see Table 1 )j5].
Table I . Compounds synthesized
Cpd.
M.p.
I1
116- 117
98-99
150--153
3x0 Idec.1
143-146
132.- 134
145-147
I39 - ~ l 4 0
135-1 36
295-297
325 327
2 6 2 ~ 264
272-275
2 0 5 ~ 207
177-179
84-87
72-75
-
2
2
7
3
4
5
-
[I] R. U . L r m k u . ~ ,K . Junirs, and 7: L . Nugahirshuii, Can. J . Chem. 51.
48 (1973).
[2] Cf.. however, K . M i p i and R. W Jrunloz. Carbohyd. Res. 21, 45 (1972).
[3] If. Puulsen, H. Koehrriiirk. W Steni-el, and P. K d l . Tetrahedron Lett.
18, 1493 (1975).
[4] R. U. Lrmirux and J . Hucumi, Can. J . Chem. 43, 2162 (1965).
[S] B. Heifrri<.h, M . Mullur. and S. Kurhuch, Liebigs Ann. Chem. 1974.
1514.
[6] K . Iqarushi. J . I r i s u w . and T Honmu, Carbohvd. Res. 3Y, 341 (1975).
New Method for Synthesis of Many-membered Hydrocarbon Rings[**]
By Fritz Vogtle and Joachim Griitze[*]
We report here a new and simple method of synthesis,
on a preparative scale, of medium- and many-membered cyclic
hydrocarbons. The method originates from the ring contraction by thermolysis of cycles analogous to dibenzyl sulfone
described by us earlier"] and since found of proven value.
Whereas previously only ethano bridges could be constructed
between aromatic nuclei[2], the new method permits their
connection by -(CH2).bridges of various lengths. New
carbocyclic ring systems of theoretical and practical interest
thus become accessible rapidly and without great labor or
expense.
The method was developed for the bridged o-terphenyl
system: 2,5-Dithia[6](4,4")orthoterphenylophane (3)13] was
' H - N M R [a]
["CI
6
3
4
5
6
3
4
5
6
~
[a] Benzyl-H, 6-calues [ppm].
111
4.45 is)
3.83 id), J = 6 HZ
2.16 -2.63 ( m )
3.33 (s)
3.65 (s)
3.73 (s)
3 73 (s)
3.73 ( S )
3.70 (s)
4.36 (s)
4.23 (sl
4.21 (s)
4.25 is)
2.28-2.93 ( m )
2.44 -3.02 ( m )
2.40-2.77 (m)
2.16- 2.73 (m)
CDCI,
Surprisingly, pyrolysis of the disulfone ( 4 ) (in a quartz tube
at 500T/O.l torr['l, length of the tube furnace 4 cm) does not
lead to the [2.2]paracyclophane-analogous system (6)['1 with
loss of SO2 and ethylene, but instead the hydrocarbon
[4](4,4")orthoterphenylophane ( 5 ) is formed in 80-90 % yield.
161
ecHzx
<
+
'
Y-CH,
Y-YH,
+
'
c',CHZ
H, I
/
\
S
\
/
C HzX
(laj, X = B r
( l b ) , X = SH
(Za), Y
(Zb), Y
= SNa
= Br
(3)
(4)
[*] Prof. Dr. F. Vogtle and Dipl.-Chem. J. Grutze
lnstitut fur Organische Chemie der Universitat
87 Wiirzburg, Am Hubland (Germany)
[**I
This work was supported by the Fonds der Chemischen Industrie.
Angeiv. Chrm. i n t w i i u f . Edit.
II Vol. 14 ( 1 9 7 5 ) I N o . 8
For planning of syntheses it is of value that the cyclic
compounds ( 9 b ) - ( 9 e ) with longer bridges (Table 1) can
also be obtained in good yield by this new method which
involves two-fold extrusion of SO2 without loss of the aliphatic
-(CH2)n- bridge after starting from the sulfone (8). The
mechanism is assumed to involve stepwise extrusion of SO2"]
and radical recombination of the fragmentsL6].Although,
because of its rigidly bent molecular structure, the o-terphenyl
system appears to favor this type of ring contraction, the
method may well succeed in other cases under suitable conditions of temperature, pressure and residence time, leading
to new oligocyclic medium- and many-membered hydrocarbons and heterocycles[*!
Received: May 5. 1975 [Z 243 I€]
German version: Angew. Chem. K7. 543 (1975)
CAS Registry numbers:
f l u ) . 55759-13-2; l l h ) . 55759-14-3; / 2 u ) , 23851-16-3;
( 2 h i . 106-93-4: (31. 55759-15-4; (41. 55759-16-5:
559
observed-the chemiluminescence matching the fluorescence
spectrum of (2) and ( 4 ) , respectively.
The ratio chemiluminescence quantum yield/photooxidation depends upon the nature of the fluorophore present in
the reaction with PPO: in contrast to (2) and ( 4 ) , diphenylanthracene, rubrene, and 9,10-bis(phenylethynyl)anthracene
predominantly afford chemiluminescence; photooxidation
products, in particular "endoperoxides" such as ( 6 ) , have
not yet been detected.
( 5 ) . 55759-17-6;( 7 6 ) . 55759-18-7;( 7 c ) . 55759-19-8;
i 7 d ) , 55759-20-1; ( 7 e ) . 55759-21-2;(86). 55759-22-3;
/ 8 c ) , 55759-23-4;( 8 d ) , 55759-24-5;( 8 e ) . 55759-25-6;
(961, 55759-26-7; ( 9 c ) , 55759-27-8;( 9 d ) . 55759-28-9;
( 9 e ) . 55759-29-0
[ l ] F. Vogrle, Angew. Chem. 81,258 (1969);Angew. Chem. internat. Edit.
8, 274 ( 1 969);Chem. Ber. 102, 3077 ( 1 969).
[2] F . Vogrle and P. Neumann, Synthesis 1973, 85.
[3] For nomenclature cf. F. Viigtle and P . Neumann, Angew. Chem. 84,
75 (1972);Angew. Chem. internat. Edit. 11, 73 (1972).
[4] F. Vogtle, J. Grutze. R . Niirscher, W Wieder, E. Weber, and R. Grun,
Chem. Ber. 108, 1694 (1979,and references there cited.
[S] Correct elemental analyses and mass spectra were obtained from all
the compounds.
[6] H . A . Sraab and M . Haenel, Chem. Ber. 106, 2190 (1973).
[7] This compound is presently being synthesized.
[8] Here we have in mind, not only ortho-, meta- and para-cyclophanes,
pyridinophanes, thiophenophanes ere. but also arenes that are bridged
more than twice; e. g . the hexathia compound previously described
by us [9] could be the starting point for synthesis of [4.4.4](1,3,5)cyclophane [lo].
191 R. G. Lichrenthaler and F. Viigtle, Chem. Ber. 106, 1319 (1973).
[lo] N o t e added in proof: In the meantime the method has been successfully
employed by us for the synthesis of ring compounds containing even
longer bridges and bridges with oligoethylene glycol units, as in crown
ether compounds.
C6H5
C6H5
The high yield of ( 3 ) , the photooxidation product of (2),
shows PPO to be a very efficient chemical generator of singlet
oxygen[5]. The general applicability of this type of reaction
is presently being studied.
o-Dibenzoylbenzene (3j from 1,3-diphenylisobenzofuran(2)
A solution of (2) (1.08g) in benzene (50ml) is shaken at
room temperature with PPO (0.66 g). After the rapid disappearance of the yellowish fluorescence the reaction mixture is
concentrated in vacuum and the residue induced to crystallize
by addition of ethanol. Recrystallization from ethanol affords
0.68g (59%) of (3), m. p. 145-146°C (ref. [3]: 145--146°C).
Phthaloyl Peroxide as an Efficient Source of Singlet
Oxygen
By Karl-Dietrich Gundermann and Manfred Steinfatt"]
Investigation of the products formed in the chemiluminescence reaction of phthaloyl peroxide (PPO)with 9,10-diphenylanthracene (DPA)['] revealed that, in addition to CO,, phthalic acid, and numerous other oxygen-containing minor products, an approximately 30% yield of 9,10-diphenyl-9,10dihydro-9,lO-anthracenediol( I ) is
This suggests
that molecular oxygen is released by PPO under the conditions
'
\
0
,b
+
6-
II
0
C6H5
PPO
D PA
cis- and trans-Dibenzoylstilbene ( 5 ) from tetraphenylcyclopentadienone ( 4 )
A solution of ( 4 ) (1.54g) in benzene (100ml) is heated
to 50-60°C for about 10min with PPO (1.32g) until the
reddish violet coloration of the solution has disappeared. The
filtered solution is concentrated in vacuum and the residue
rubbed with ethanol. The reaction yields 0.53 g (34 %) of ( 5 ) ,
m. p. 213-214 "C, after separation m. p. 233 "C (ref. [4] : 213 "C
(cis) and m. p. 232-233 "C (trans).
H5C6 OH
Received: May 6, 1975 [Z 245 IE]
German version: Angew. Chem. 87,546 (1975)
H O C6H5
CAS numbers:
(2),5471-63-6;( 3 ) , 1159-86-0;
tetraphenylfuran ( 4 ) , 1056-77-5;
cis-(5), 631326-4;trans-(5), 10496-80-7;PPO, 4733-52-2
(1)
of the chemiluminescence reaction. That the species produced
is excited singlet oxygen ' 0 2is shown by the reaction of
PPO with 1,3-diphenylisobenzofuran (2) which affords the
photooxidation product o-dibenzoylbenzene (3)[31 in 60 %
yield ; reaction with tetraphenylcyclopentadienone ( 4 ) correspondingly furnishes cis- and trans-1,2,3,4-tetraphenyl-2butene-lp-dione (dibenzoylstilbene) (5)[41 in 34 % yield. In
the reactions, either weak or no chemiluminescence is
a
0
C6H5
PPO
+
C6H5
-
-
C6H5
I
C6H5
(3)
PPO
+
[2]
[3]
[4]
[5]
K . - D . Gundermann, M . Steinfatt, and H . Fiege, Angew. Chem. 83, 43
(1971);Angew. Chem. internat. Edit. 10, 67 (1971).
M . Steinfatr, Dissertation, Technische Universitat Clausthal 1975.
C.Dufraisse and S. Ecary, C. R. Acad. Sci. 223,735 (1946).
H . H. Wasserman and J . R. Scheffer, J. Amer. Chem. SOC. 89, 3073
(1967).
W Adam, Chem.-Ztg. 99, 142 (1975).
~
Stable PyrazoliumBetaines by Addition of 1,l-Dialkylhydrazines to AcetylenecarboxylicEsters
By Wolfgang Sucrow, Marion Slopianka, and Vasilios Bardakos"]
While the addition of 1,l-dimethylhydrazine to cx,p-unsaturated esters to give pyrazolinium betaines had already been
[*]Prof. Dr. W.Sucrow and M. Slopianka
(4)
cis-(5)
trans -(5)
[*] Prof. Dr. K.-D. Gundermann and Dip1.-Chem. M. Steinfatt
Organisch-Chemisches Institut der Technischen Universitat Clausthal
D-3392 Clausthal-Zellerfeld, Leibnizstrasse 6 (Germany)
560
[l]
lnstitut fur Organische Chemie der Technischen Universitat
1 Berlin 12, Strasse des 17. Juni 115 (Germany)
Dr. V. Bardakos
Laboratory for Organicchemistry of the National Polytechnicum Athens
(Greece)
Exchange fellow of the Deutscher Akademischer Austauschdienst and the
Gesellschaft von Freunden der Technischen Universitat Berlin.
Angew. Chem. inrrrnar. Edit. 1 Vol. I 4 ( I 9 7 5 )
No. 8
Документ
Категория
Без категории
Просмотров
1
Размер файла
216 Кб
Теги
many, synthesis, hydrocarbonic, membered, method, ring, new
1/--страниц
Пожаловаться на содержимое документа