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Fulvenes and Fulvalenes of a Heterocyclic System with 12 ElectronsЧPseudophenafulvenes and Pentapseudophenafulvalenes.

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( 4 6 ) with LiAIH4 to the alcohol, which was used for oligosaccharide synthesis (see Table 1).
Fulvenes and Fulvalenes of a Heterocyclic System with
12 7c Electrons-Pseudophenafulvenes and Pentapseudophenafulvalenes[**]"1
Table 1, Glycosides and oligosaccharides synthesized [a]
Cpd.
Yield [h]
[x)]
M.p. ["C]
[21386 ["I
+81.5
-21.4
-36.2
9.2
f20.8
(40)
83
viscous oil
(4b)
87
83
71
94
79
57
93
(4c)
(4d)
(61
(7)
[a]
[b]
[c]
[d]
viscous oil
106
viscous oil
+
+64.8
(2.696 [c])
(2.183 [c])
(2.150 [c])
(1.4X9 [c])
(0.255 [c])
(1.164 [d])
By Richard Neidlein and Arnold D.Kraemerpl
We recently reported the first synthesis of deeply colored
cations[2' which we could prepare from 2-phenyl-5H-naphtho[l,8-hc]thiophen-5-one(l )I3]. Wehavenow found an entry
to deeply colored fulvenes (3) and fulvalenes [(2), ( 4 ) ] of
this system.
All compounds gave correct elemental analyses.
Isolated yield.
Concentration in CHC13.
Concentration in CH,OH.
Since the anomeric ratios depend neither upon the halogenose used, nor upon the reaction temperaturec5],nor upon
the molar excess of the alcohol component[s1, we assume
the intermediacy of a dioxanorbornene ( 3 ) which is attacked
mainly from the side facing away from the carboxylate group,
i. e. from the a-side[@.
The carboxylate function serving as assisting and protecting
group in this oligosaccharide synthesis can be reduced by
LiAIH4 to the hydroxymethyl group. In this way the protected
trisaccharide (6) was obtained quantitatively from (4 d ) . However, the isopropylidene group can only be removed without
R
It',
( 3 ) : It = R2 ,c:
&6H5
14): R =
(7)
HO
OH
decomposition of the remaining compound if an cc-glycosidic
bond is present or the compound is unsubstituted at C-I.
The unprotected cx-linked disaccharide (7) is therefore accessible in good yield from ( 4 c ) by reduction of the carboxylate
group, hydrogenolytic removal of the benzyl group, and acidcatalyzed removal of the isopropylidene group.
Received: October 21, 1976 [Z 588 I€]
German version: Angew. Chem. 89.58 (1977)
CAS Registry numbers:
( I ), 60949-62-4; (2). 60949-63-5:
( ~ I J )60949-64-6;
,
(4 b). 60949-65-7; ( 4 c),
60949-66-8: ( 4 1 1 ) , 60949-67-9; ( 5 a ) , 50767-74-3; ( S b ) , 60949-68-0: ( 5 c ) ,
60949-69-1 ; ( 5 d ) . 60949-704: (61, 60949-71-5; ( 7 ) . 60949-72-6
[I]
[Z]
[3]
141
[S]
[6]
a) G. Wulffand G. Rdhle, Angew. Chem. 86, 163 (1974): Angew. Chem.
Int. Ed. Engl. 13, 157 (1974); b) C. Schuerch, Acc. Chem. Res. 6, 184
(1973). and references cited therein.
H. P U N ~ S ~Adv.
I I , Carbohydr. Chem. 26, 127 (1971): H. Puu/.su!i, H .
Behrr. and C. P . Herold, Fortschr. Chem. Forsch. 14, 472 (1970).
R . R . Schmidt, D.Heermann, and K . H . Jung. Justus Liebigs Ann. Chem.
1974,1856; K . H. Jung. Dissertation, Universitiit Stuttgart, in preparation.
The isomer ratio was determined by NMR spectroscopy.
Temperature range 0 to 60°C; 0 to 100 molar excess of the alcohol
component.
Other mechanistic interpretations cannot be ruled out, particularly since
the mechanism of the Koenigs-Knorr reaction is not known in detail
[la].
A n g w . . Clion. Inr. E d . EngI. 16 ( 1 9 7 7 ) N o . 1
8
Heating of ( I ) with 1,2,3,4-tetrachlorocyclopentadiene in
acetic anhydride affords the deep blue crystalline fulvalene
(2). The compounds listed in Table 1 react analogously with
(1 ) to form the fulvenes ( 3 a ) to (3f).
Treatment of ( I ) in anhydrous benzene under nitrogen
and at room temperature with an equivalent amount of
diphenylketene gives compound (3g) with evolution of COz.
Finally, ( 1 ) reacts with fluoreneketene to form the fulvalene
( 4 ) (spectroscopic properties given in Table 2).
Procedures
Syntheses of (2): Compound ( I ) (2 mmol) and tetrachlorocyclopentadiene (2 mmol) are heated under reflux for 6 h in
acetic anhydride (10ml). The solvent is distilled off and the
residue chromatographed with benzene on silica gel 60
(Merck). Recrystallization from benzene gives deep blue crystals; yield 21 %, m.p. 166 to 168°C.
Synthesis of ( 3 a ) to (3f): Compound ( I ) (2mmol) and
one of the compounds listed in Table 1 (2mmol) are heated
under reflux for 10min in acetic anhydride (7.7mI) and glacial
acetic acid (3.8ml). Workup as described for (2).
Synthesis of ( 4 ) : Compound ( 1 ) (2mmol) is dissolved in
anhydrous benzene (1 0 ml) under nitrogen. Fluoreneketene
(2mmol) is added and the mixture heated under reflux for
1 h. The residue obtained on removal of the solvent is chromatographed with benzene on silica gel 60 (Merck). Recrystallization from n-hexane gives blue-black needles with a metallic
luster; yield 38 %, m.p. 169°C.
[*] Prof. Dr. R. Neidlein and Dr. A. D . Kraemer
Pharmazentisch-Cliemisches lnstitut der Universitiit
Im Neuenheimer Feld 364, D-6900 Heidelberg (Germany)
[**I Heterocyclic 1271 and 14a Systems, Part 2. This work was supported
by the Fonds der Chemischen Industrie and by the Deutsche Forschungsgemeinschaf1.--Part 1 : ref. [2].
49
Table 1. Compounds of type ( 3 ) synthcaized
Reaction of ( 1 j with
Product
R'
R2
-CO-N(CH3)-CO-N(CH3)-CO-CO-NH-CS-NH-CO-N=C(C6H5)-O-C0-CO-(
1,2-phenyIene)-CO-CN
-CN
-CN
-CO>CZH5
-c6Hs
-CsH5
1,3-Dimethylbarbituric acid
2-Thiobarbituric acid
N-Benzoylglycine
1,3-Indandione
CHz(CN)*
NC-CH~CO~CIHS
(C6H5)2C=C=O
Table 2. Spectroscopic properties of compounds (21, ( 3 9 1 , and ( 4 ) .
( 2 ) : 'H-NMR (CDCI3): 6=7.51-8.05ppm (H3, H H7, phenyl protons),
8.20(d,H6,J=7.6Hz),8.04(d,H8,J=7.6Hz); UV (nseptane): im.,=334nm
(6=8347), 568 (20353); (CH3CN): 326 (8052), 568 (19663); (CH30H): 330
(6949), 580 (18795).
( 3 9 ) : UV (CH30H): ir,,,=413nm (e=22131), 307 (13319), 277 (12909);
'H-NMR (CDCI3): S=7.51-8.05 (H3, H1, HI. phenyl protons), 8.20 (d,
He, J=7.6Hz),8.04(d, Ha, J=7.6Hz).
( 4 j : UV (n-heptane): i,,=344nm
(~=13076),532 (30192); (CH3CN): 340
(15702). 532 (33471); (CHIOH): 334 (12986); 532 (29762).
Received: October 18, 1976 [Z 589 IE]
German version: Angew. Chem. 89.48 (1977)
[I]
Lectures by R . Neidlein at Tel-Aviv, Jerusalem, Haifa, Rehovot, Heidelberg, and Hamburg.
[2] R. Neidlein and H . Seel, Angew. Chem. 88, 810 (1976); Angew. Chem.
Int. Ed. Engl. 15,775 (1976).
[3] D. G. Hawthorne and Q. N. Porter, Aust. J. Chem. 19, 1909 (1966).
M.p.
["Cl
Yield
285
> 350
296
233
279
159
86
67
75
69
16
20
84
138
Color
["/.I
black-green
black
black-blue
metallic black-blue
red-violet
red-violet
yellow
tion; and polymerization. R3= alkyl favors lactone formation;
R5=C O ~ C H Jleads to almost quantitative deoxygenation
with formation of C 0 2 ;R' and R6=alkyl promotes formation
of acyclic ketones.
5-Methyl-3,6-dihydropyran-2-one
( 2 ) , R3= CH,, R' =RZ=R4
to R6= H
Isoprene epoxide['' (7.0 g, 83 mmol) and [l,S-cyclooctadiene-RhC1]J5] (0.2 g, 0.4 mmol) in anhydrous carbon
tetrachloride (40 ml) are shaken under IS0 atm of carbon
monoxide for 50 h at 70°C in a stainless steel autoclave.
Fractional distillation of the yellow reaction mixture affords
5-methyl-3,6-dihydropyran-2-one(6.5 g, 75 %), b. p. 5354"C/O.I torr, &'= 1.4762. Reaction and workup must be performed with exclusion of air! 'H-NMR (CCI,): 6= 1.72ppm
(br s, 3H), 2.88 (m, 2H), 4.64 (m, 2H), 5.26 (m, 1H). MS
(70eV): m/e=112 (M+, 72%). IR (film): 1744, 1400, 1210,
1070, 796cm-'.
Received: October 25, 1976 [Z 590 IE]
German version: Angew. Chem. 89,47 (1977)
&Lactones by Carbonylation of Vinyloxiranes1']
By Rudolf Aumann and Horst Ringr]
No method is yet available for the direct linkage of carbon
dioxide with 1,3-dienes after the manner of a Diels-Alder
reaction to give 6-lactones[21.
However, transformation of 1,3dienes into &-lactonescan
be conveniently accomplished in two steps if the diene is
first epoxidized and the epoxide (1) subsequentlycarbonylated
in the presence of transition metals.
Fractional distillation gives the lactones in 10 to 75 % yield.
Use of Rh' catalysts affords P,y-unsaturated lactones ( 2 ) ,
while Fe and Co catalysts lead predominantly to a,p-unsaturated lactones (3). Competing reactions are: isomerizations
to open-chain $,y- and u,P-unsaturated ketonesc3];deoxygena-
I
Fe,Co
.,
p] Priv.-Doz. Dr. R. Aumann and DipLChem. H. Ring
Organisch-Chemisches Institut der Universitat
Orleansring 23, D-4400 Miinster (Germany)
50
CAS Registry numbers:
( I ), 1838-94-4; (2), 60920-98-1
[I] Organic Syntheses with Transition Metal Complexes, Part 5.-This work
was supported by the Deutsche Forschungsgemeinschaft and the Fonds
der Chemischen 1ndustrie.-Part 4: R . Aumann, Chem. Ber., in press.
[2] R. A . Ruden and R . Bonjouklian, J. Am. Chem. SOC.97, 6892 (1975),
and references cited therein.
[3] G. Adams, C . Bibby, and R . Grigg, J. Chem. SOC.Chem. Commun. 1972,
491.
[4] E. J . Reist, I . G . Junga, and B. R . Baker, J. Org. Chem. 25, 1673 (1960).
The compound is conveniently obtained by epoxidation of isoprene with
peroxyacetic acid in dich1oromethane.-M. Korach, D. R. Nielsen, and
ti! H.Rideout, J. Am. Chem. SOC.82,4328 (1960).
[S] J. Chatt and L. M . Venanzi, J. Chem. SOC.1957,4735.
Elimination of CO from Cyclic Carbonyl Compounds
by Flow Pyrolysis[']
By Gerhard Schaden"]
Some carbonyl compounds eliminate CO on heating, on
electron impact, or in a glow discharge. In view of the facile
mass-spectrometric elimination of CO from anthrone (I),
7H-benzCdeIanthracen-7-one (3), 1H-phenalen-I-one ( 5 ) ,
and chrysene-6J2-dione (7), thermal elimination of CO to
give fluorene (2), fluoranthene ( 4 ) , acenaphthylene ( 6 ) , and
indeno[2,1-a]indene (dibenzopentalene) (9), respectively,
appeared to be promising.
Curie point pyrolysis at 900°C and subsequent gas chromatography/mass spectrometry['' demonstrated formation of the
expected products. In order to produce larger amounts of
material, ( I ) , ( 3 ) , ( 5 ) , and (7) were pyrolyzed in a highvacuum now apparatus. Compounds (I), ( 3 ) , and ( 5 )
afforded ( 2 ) , ( 4 ) , and ( 6 ) in yields of 29 %, 42 %, and 41 %,
respectively. The major product obtained on pyrolysis of (7)
[*] Dr. G. Schaden
Fachbereich Pharmazie und Lebensmittelchemie der Universitat
Marbacher Weg 6, D-3550 Marburg (Germany)
Angew. Chem. l n t . Ed. Engl. I 6 (1977) N o . I
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fulvenes, system, heterocyclic, fulvalene, electronsчpseudophenafulvenes, pentapseudophenafulvalenes
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