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Cyclooctadeca[cdefg]phenanthrene (У[18]Annuleno[cdefg]phenanthreneФ).

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(5),X=CIO,:
290 (14000, sh), 308 (35000, sh), 321 (75000, max), 332 (43600, min),
340 (51500, sh), 353 (90500, max), 375 (36600, min), 376 (36700, max),
387 (28800, min), 393 (30600, max), ca. 450 (ca. 750, flat min), ca. 500
(ca. IOOO, flat max) nm in CFJOOH
1.34/2.79/5.47 (3s, intensity ratio 6:2:1); also m at 1.6 ppm ( c n 10%
impurities) in CF,COOH
H3C' k H 3
X~/CF3C00~
(51
Scheme 1. Properties of compounds of types ( I ) , ( 2 ) , ( 3 ) , ( 4 ) , and ( 5 ) . Spectroscopic data in the following order:
h,,, (E in brackets); selected bands from the IR spectra; signals from the proton resonance spectrum (6 values referred
to G(TMS)=O ppm); selected signals from the mass spectra. Except for ( 2 b ) and ( 5 ) . all the compounds formulated
were obtained in homogeneous crystalline form and gave correct analytical values. Detailed description of the experiments can be found in [4].
of ca. 7.3,approximately comparable with that of a carboxylic acid'']. Treatment of ( 4 a ) with nickel acetate in boiling
acetonitrile gives the nickel complex ( 3 b ) , isolated as its
crystalline perchlorate; with cobalt(r1) chloride[9] in the
presence of sodium acetate in methanol at 50"C, the
dicyanocobalt(II1)-corphin complex ( 3 d ) can easily be
obtained following work up with cyanide in contact with
air[' '1.
The complexes ( 3 a ) and (3c), as well as the metal-free
corphinium ion (4), exist in trifluoroacetic acid as derivatives of the more highly symmetrical (trans-cis)4-1,5,9,13tetraaza[i6]annulene system ( 5 ) ; in trifluoroacetic acid
their proton resonance spectra are reduced to three singlets" '1 and the corresponding electronic spectra show
unambiguously the presence of a non-corrinoid chromophore in this solvent [cf. data for ( 5 ) in Scheme 11. The
signals of the vinyl and methylene protons of the doubly
positively charged tetraazaannulene system ( 5 ) are at distinctly higher field than the corresponding groups of signals
from the singly positively charged corphinium ion (4)I"I;
the interpretation of this shift as an effect of a paramagnetic
ring current['3] in the pericyclically conjugated 4n-x-system
( 5 ) constitutes specific support for the structural assignment.
New experimental findings" 41 concerning the biosynthesis
of vitamin B I 2 have caused us to lose confidence in a
hypothesis we have cherished for a number of years,
namely, that the corphin ligand system might play a role
in the biosynthesis of naturally occurring corrinoidsE2'.Fortunately, however, the compounds of type ( 5 ) merit interest
as the porphinoid representatives of the heteroanalogs
of carbocyclic annulenes['5].
Received: July 10, 1973 [Z 889 IE]
German version: Angew. Chem. 85,954 (1973)
181
~.
According to the UV spectrum, the
protonation pri ibly leads
to a mixture of peripherally deprotonated neutral products; these were
very sparingly soluble and were not further investigated.
[9] Cf. R . B. Woodward, Pure Appl. Chem. 25, 283 (1971).
[lo] The properties of the complexes ( 3 6 ) and (3d) are described
in detail in [4].
[ I I] For complete exchange of the methylene protons of the palladium
complex ( 3 c ) by deuterium in deuteriotrifluoroacetic acid see [2].
[I21 The same is true for the complexes ( 3 a ) [4] and ( 3 c ) [2] in
CFsCOOH. The system ( 5 ) is stable for at least some hours in pure
trifluoroacetic acid at room temperature; however, on addition of stronger
acids, such as sulfuric or perchloric acid, rearrangement occurs (presumably tautomerization), whose interpretation requires further investigation.
1131 J . A. Pople and K . G . Untch, J. Amer. Chem. SOC.88, 481 1 (1966);
cf. F. Sondheimer, Accounts Chem. Res. 5 , 81 (1972); J . F M . 0 t h and
.
J . - M . Gdles, Tetrahedron Lett. 1968. 6259.
[I41 C. E . Brown, J . J . Katz, and D. Shemin, Proc. Nat. Acad. Sci.
USA 69,2585 (1972); A. I. Scott, C. A. Townsend, K . Okada, M . Kajiwara,
P . J . Whirman, and R . J . Cushley, J . Amer. Chem. Sac. 94, 8267, 8269
( 1972).
[I51 A porphinoid hexaaza-analog of [I6]annulene has been prepared
by R . Schefold and J . Loliger [personal communication from R . Srheffold;
cf. J . Loliger, Dissertation, Fribourg (Switzerland) 19711.
Cyclooctadeca[cdefgIIphenanthrene ("[181Annuleno[cdefg] phenanthrene")[ J
By U t e Meissner, Bernd Meissner, and Heinz A . Staab[*]
In 3,3':6',3":6",6-triphenanthrylene (1 ) the annulene conjugation that can be formulated as (1 a)+I 6 ) is completely suppressed in favor of x-interaction within the
phenanthrene units: the 'H-NMR spectrum does not show
any diamagnetic ring current in the macrocyclic system
but is in accordance with the existence of three largely
unperturbed phenanthrene unitsc21.
-~
[I] A. Fischliand A. Eschenmoser, Angew. Chem. 79,865 (1967); Angew.
Chem. internat. Edit. 6, 866 (1967); A. Eschenmoser, Quart. Rev. Chem.
SOC.24, 366 (1970); H . 4 . Wild, Dissertation, ETH Zurich 1972.
121 A. P. Johnson, P . Wehrli, R . Fletcher, and A. Eschenmoser, Angew.
Chem. 80, 622 (1968); Angew. Chem. internat. Edit. 7, 623 (1968).
[3] A zinc(![) octaethylphenylhexahydroxycorphin derivative has been
described by H. H. Inhogen and N . Miiller (Tetrahedron Lett. 1969,
3209).
[4] Cf. P . M . Miifler, Dissertation ETH Zurich, 1973.
[ S ] E. Gotschi, W. Hunkeler, H.-J. Wild, P. Schnrider, W. Fuhrer, J.
Gleason, and A. Eschenmoser, Angew. Chem. 85, 950 (1973); Angew.
Chem. internat. Edit. 12, 910 (1973).
163 The yields of the palladium complexes denoted as (6) and 1 8 )
in [2] have meanwhile been considerably improved: (8) can be obtained
in about 6 0 % yield from the trans-precursor complex (61, and ( 6 )
can be prepared in 85% yield by light-induced isomerization of the
corresponding cis-complex ( ( 5 ) in [2]); for details see [4].
[7] Cf. W Simon, Helv. Chim. Acta 41, 1835 (1958).
916
(101
(Ib/
In connection with the problem of the perturbation of
annulenes by condensation with benzenoid systems we
became interested in cyclooctadeca[cdefg]phenanthrene
[*I Dr. U. Meissner, Dr. B. Meissner, and Prof. Dr. H. A. Staab
Institut fur Organische Chemie der Universitat
69 Heidelberg, Im Neuenheimer Feld 7 (Germany)
Angew. Chem. internat. Edit.
Vol. 12 (1973)
/ No. I 1
45
IL’
l,B9JO 2.7 12,21 11,22
1,89,l02,7
11,22
Z i L,5
12.21 15J8
external protons
internal protons
Fig. I Comparison of the ‘H-NMR spectra of ( 4 ) and ( 2 )
( 2 ) ,in which the annulene conjugation competes with only
one benzenoid phenanthrene unit.
For the synthesis of (2), 3,6-dimethylphenanthrene was
prepared from 4,4-dimethyl-trans-stilbene (Hg high-pressure lamp, 0.01 M solution in 5 : I cyclohexane/benzene;
iodine; 61 % yield) or from 2-(4‘-methylphenethy1)magnesium bromide and 4-methylcyclohexanone ~lia4-methyl- 1(4‘-methylphenethyl)cyclohexanol~41
and 1,2,3,4,4a,9,10,10aoctahydr0-3,6-dimethylphenanthrene(overall yield 25 %).
Successive conversion into 3,6-bis(brornornethyl)phenanthrene14’ (NBS/CCl,, 57 % yield) and 3,6-bis(triphenylphosphoniomethy1)phenanthrenedibromidek4](triphenylphosphane/acetonitrile, 80% yield), and a double Wittig
reaction with 4-pentynal[’] afforded 3,6-bis(l-hexen-5ynyllphenanthrene (3) (45 % yield)[41,which was cyclized
in 50% yield to the 18-membered ring system (4)[“] by
copper(i1) acetate in dimethylformamide. Isomerization
with potassium tert-butoxide in tert-butyl alcohol/benzene
finally yielded (2)‘“l as red crystals (from cyclohexane;
dec. above 200°C; 48% yield).
(I)[’], it is precisely these protons that normally absorb
at lowest field strength.
Because of the importance of this finding the assignment
of the two 2H singlets at t=1.94 and 3.21 to 9-H, 10-H
and 4-H, 5-H, respectively, was checked by synthesis of
a molecule (2) deuteriated at the 9,lO-positions: 4,4dimethyltolane was catalytically (Pd/BaS04 pyridine,
ethyl acetate) deuteriated to a,P-dideuteriostilbene; photochemical cyclodehydrogenation afforded 9,lO-dldeuterio3,6-dimethylphenanthrene, which was converted by the
reaction series given above into a species (2) selectively
deuteriated at positions 9 and 10. With this compound
the signal at T = 1.94 did not occur; the signal at t= 3.21
can therefore be assigned unequivocally to 4-H, 5-H.
Dibenzo[ab,de]cyclooctadecene ( 5 ) differs from (2) in that
the rn-linkage of the benzene rings prevents complete cyclic
conjugation around the macrocyclic system. The synthesis
of ( 5 ) from 3,3’-dimethylbiphenyl cia 3,3’-bis(l-hexen-5yny1)biphenyl waseffectedanalogously to that of (2). ( 5 )I4]
formed dark red crystals (m. p. 160°C, dec.) that are extremely sensitive to air. Its ‘H-NMR spectrum (CS,, 100
+
H
(5)
H
H
The ‘H-NMR spectrum of (2) contains the following
absorptions (220 MHz, CS2)161:T = 1.87 and 2.15 (AB system, J A ~ = 8 H z 1-H,
,
8-H and 2-H, 7-H), 1.94 (s, 9-H,
10-H), 2.57 (d, 5=16Hz, 11-H, 22-H), 2.87-3.09 (m, 6
external H), 3.21 (br. s, 4-H, 5-H), 4.50 (-dd, 31=16Hz,
J z =10 Hz, 12-H, 21-H), 4.78 (m, 15-H, 18-H).
This spectrum is remarkable for the following reasons:
The signals cannot be divided between “aromatic” and
“olefinic” protons; instead, the signals of all the inner
protons are shifted to higher field strength and those of
the external protons are shifted to lower field strength.
This observation, which indicates a diamagnetic ring current in the macrocyclic system, is particularly clearly shown
when a comparison is made with the corresponding ‘HNMR absorptions of the precursor (4) that is not cyclically
conjugated (see Fig. l)17].
The opposite shifts of the signals of the neighboring proton
pairs 11-H, 22-H and 12-H, 21-H in, respectively, the xand the P-positions t o the phenanthrene unit are striking;
even more so is the large shift of the signals of 4-H,
5-H to higher field strength beyond those of all the external
protons, including those of the “olefinic” part of the molecule, whereas in phenanthrenes, including the macrocyclic
Anyew. Chem. internat.
Edit. 1 Vol. 12 (IY73) 1 N O 11
I1
MHz) is in accordance with an aromatic and an olefinic
part in the molecule. In particular, with ( 5 ) the absorption
of the two inner aromatic protons, which correspond to
4-H, 5-H in (2), occurs at the lowest field strength (t= 1 S6).
Since the geometrical relations within the 18-membered
rings of (2) and ( 5 ) are similar, it must thence be concluded
[I] Conjugation in Macrocyclic Bonding Systems. Part 21.-Part 20:
H . A. Staab, F . GrgL K . Doernrr and A. Nisien. Chem. Ber. 104, 1159
(1971).
[2] H. A. Stuub, H . Briiunliny, and K . Schneider, Chem. Ber 101, 879
(1968).
[3] For ease of discussion of their ‘H-NMR spectra the C atoms of
the phenanthrene portions of ( 2 ) and ( 4 ) are numbered as is usual
in phenanthrenes.
[4] Correct elemental analyses and molecular weights were obtained
for these compounds; the spectroscopic data accord with the structures
assumed.
[S] F . Bohtmunn and R . Miethe, Chem. Ber. 100, 3861 (1967).
[6] We thank Dr. W! Briigel. BASF Ludwigshafen, for recording thls
spectrum.
[7] In this comparison it must, nevertheless, be remembered that in
( 4 ) , 12-H,21-H and, to a smaller extent, also 4-H, 5-H are under the
deshielding influence of the anisotropy of the diacetylene group, although
this shifts these signals by n o more than 0.5 ppm to lower held strength,
as shown by the comparison with the spectrum of (3).
917
that the strong shielding of 4-H, 5-H in (2) cannot be
the result of local anisotropic effects of the double bonds.
If the induction of a diamagnetic ring current is taken
as the criterion of aromaticity, it follows that the macrocyclic system in (Z), unlike those in ( I ) and ( 5 ) , exhibits
annulenoid aromaticity. Comparison with the very much
stronger shielding of the inner protons in the monocyclic
[ I8]annulene shows, however, that the annulene character
of (2) is substantially weakened by fusion with the
phenanthrene system and that there is here a borderline
case between benzenoid and non-benzenoid aromaticity.
Received: July 26. 1973 [Z 898 lE]
German version: Angew. Chem. 85,957 (1973)
Table 2. Hydrogenative cleavage of aryl methanesulfonates (palladiumcharcoal In methanol, triethylamine as base).
Aryl
Product
Yield
["/.I
I -Naphthyl
2-Naphthyl
3-Methoxyphenyl
4-Methoxyphenyl
3-Chlorophenyl
4-Chlorophenyl
4-Formyl-2-methoxyphenyl
Naphthalene
Naphthalene
Anisole
Anisole
Benzene
Benzene
3-Methoxybenzyl alcohol
12
91
65
72
Aryl
H2
[moll
Base
[moll
Yield
[%I
By Karl Clauss and Harald Jensen"]
Phenyl
4-Chlorophenyl
2,4.6-TrichlorophenyI
I
2
I
2
4
90
82
Bases such as sodium hydroxide solution, alkali-metal
alkoxides or tertiary amines accelerate the reaction appreciably, equivalent amounts of the base favoring smooth
reaction. Suitable solvents are water and, in particular,
methanol. It is advisable to choose a temperature between
20 and 40-C so as to prevent over-hydrogenation. Palladium on charcoal is a suitable catalyst; platinum and
nickel catalysts d o not have comparable activity. Contrary
to the case of the known fission of aryl sulfonates by
an excess of Raney nickel''- 51, catalytic amounts of palladium suffice in our reaction (1.0-1.5mg of Pd per mmol
of ester).
Examples of this hydrogenolysis are collected in Tables
1-3.
Chloro substituents are removed by the hydrogenation,
so that a correspondingly larger amount of base must
Table 1. Hydrogenative cleavage of phenyl esters C6H5-O-SO2R
benzene (palladium-charcoal as catalyst).
R
Solvent
Base
Yield
H2N
H2N
CH 1
CHI
CHxO-CONH
CbH,-CONH [a]
HzO
CH30H
CH30H
CH,OH
CH,OH
HIO
NaOH
CH,ONa
CH,ONa
EtxN
CH,ONa
NaOH
50
65
75
82
to
918
4
55
[a] Prepared by addition of methanol t o aryloxysulfonyl isocyanates
~71.
be added to bind the liberated hydrogen chloride. Groups
such as formyl, susceptible to hydrogenation, are hydrogenated, so that the otherwise difficultly accessible 3-methoxybenzyl alcohol can be obtained from vanillin in this
way.
Experimental:
The phenol is esterified with methanesulfonyl chloride in
the presence of the equivalent amount of pyridine at 20 to
60 C. For the hydrogenation, this aryl sulfonate (60mmol)
in methanol (100 ml) is stirred with triethylamine (60 mmol)
and 1.5 g ofcatalyst (containing 5 % palladium on charcoal)
under hydrogen at 25-40 'C until the calculated amount
of hydrogen has been consumed. The catalyst is filtered
off and the cleavage product is isolated (benzene was not
isolated but was determined by gas chromatography).
Received: July 27, 1973 [Z 900 IE]
German version' Angew. Chem. 85, 981 (1973)
[ I ] K . Clauss and H . Jeriscwi. Angew. Chem. 85, 965 (1973); Angew.
Chem. internat. Edit. 12, 869(1973).
[2] G . W Krnnrr and M . A . Murru?, J. Chem. SOC. 1949, S 178.
[3] S. Mireui and S . Imaizomi, J. Chem. SOC.Jap., Pure Chem. Sect.
79, 1436 (1958): Chem. Zbl. 1959, 17036.
[4] S. Mirsui, 7: Watunahe, and S. Zmaizrrmi, J. Chem. SOC.Jap., Pure
Chem. Sect. 79, 1442 (1958); Chem. Zbl. 1959, 17037.
[5] Kyowa Fermentation Industry Co. Ltd., French Pat. 1438616, April
20, 1965: Chem. Abstr. 66, 1 1 176m (1967).
[6] R. Graj, Angew. Chem. 80. I79 (1968): Angew. Chem. internat. Edit.
7, I72 ( I 968).
[7] G. Lohaus, Chem. Ber. 105, 2791 (1972).
["/.I
90
70
[a] The chloride of this acid was synthesized from benzoic acid and
chlorosulfonyl isocyanate according to 161.
[*] Dr. K. Clauss and Dr H. Jensen
Farbwerke Hoechst AG,
vormals Meister Lucius & Briining
623 Frankfurt,'Main (Germany)
85
70
Table 3. Hydrogenative cleavage of aryl N-(methoxycarbony1)amidosulfates [a] to benzene (palladium-charcoal in methanol, sodium methoxide
as base).
Hydrogenative Removal of Phenolic Hydroxyl
Groups
Dedicated to Professor Werner Schultheis on his 70th birthday
The hetero ring of 1.2,3-benzoxathiazin-4(3H)-one 2,2dioxide opens between oxygen and carbon on catalytic
hydrogenation with palladium-charcoal in the presence
of an equivalent amount of base[']. Application of this
finding to aryl sulfonates (1) showed that phenolic hydroxyl groups in general, in the form of their sulfonic
esters, can be removed by catalytic hydrogenation at
2 W O"C and atmospheric pressure.
90
Simple Synthesis of Carbonyl Chloride Fluoride and
Carbonyl Bromide Fluoride
By Giinter Siegemund ['I
Dedicated to Professor Werner Schultheis on the occasion
of his 70th birthday
The methods reported previously for preparation of carbony1 chloride fluoride and carbonyl bromide fluoride
[*] Dr G. Siegemund
Farbwerke Hoechst AG
623 Frankfurt 80, Postfach 800320 (Germany)
A n y r u . Chum. inrvrnar Edit.
1 Vol. 12 (1973) 1 No. I I
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