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Benziporphyrin a Benzene-Containing Nonaromatic Porphyrin Analogue.

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[ I ] M. R. Mason. J. M . Smith. S. G . Bott. A. R. Barron. J Am. Cheni. Soc. 1993,
1i5. 4971.
[2] H. Sinn, W Kaminsky. A h Orpnoriicr. Chrii 1980, 18, 99.
[4K. Ziegler. GB-B 775384. 1957: C l i ~ ~Ahsrr.
i.
1958. 52. 12893e
[4] A. Hertog. H. W. Roeskg, Z. Zak. M. Noltemeyer. Atigeir. C/ioir. 1994. 106.
1035: A/igr,ii. C / i ( v l i . I t ? / . E d D i p / . 1994. 33. 967.
[5] D. A. Atwood. A. H. Cowley. P. R. Harris. R A . Jones. S. U . Koschmieder.
C. hl. Nunn. Orgaiiorii(,rt~//i(,.\
1993, /2. 24.
[6] S. Pasynkiewicz, Po/i./idron 1990. 9. 429.
171 Crystal data of [3(thf),] 6 T H F M = 1986.46, rhomhohedral, space group
R k . [I = h = 2353.6(3). c = 3133.0(6) pm. Y = 15.030(4) nm’. Z = 6. pL,,,Cd
=
1.317 M g m - 3 . F(000) = 6264. .; =71.073 pm, T = -120 C . p(MoK,) =
1.651 mni-’. crystal dimensions: 0.7 x0.5 xO.5 mm, 6 5 2 0 < 40 ; of the
6127 collected reflections, 2440 are independent, and these were used for the
refinement of 164 parameters with the help of 198 restraints: maximal residual
electron density: 899 enin-’. R I ( F > 4 o ( F ) )= 0.069 and wR2 = 0.199 (all
F o P\ I R Z= (Zii,F~:-Ff)*:Zii.(F3)l)il’.
data) with R1 = X l l F , l ~ k : ~ ~ , I ~and
The data here collected on a Stoe-Huher diffractometer. Intensities of 3 rapidlq
~
Semiempirical
cooled crgstiil in a n oil drop [XI Mere collected by 2 0 : method.
absorption corrections were carried out on all data. The structure was solved
hg direct methods (SHELXS-90) [9] and refined by least squares on F’ [lo].
The disorders of the T H F solvent molecules were refined with dictance restraints. The refinement of the inversion twinning paramter 11 I ] ( \ = 0.00(4)
for .r = 0 for the correct absolute structure and i= + 1 for the inverted structure) confirmed the absolute structure of3. The solution of the structure and
the refinement in the space group R5c were unsuccessful. The structure could
he solved in the space group C<,,but a refinement was also here unsuccessful.
Further details of the crystal structure investigation may he obtained from the
Director of the Cambridge Crystallographic Data Centre. 12 Union Road,
GB-Cambridge CB2 IEZ. on quoting the full journal citation.
[S] T. Kottke. D Stalke. J. Appi. (’1.1 i/a//opr. 1993. 26, 615.
[Y] G . M . Sheldrick. Acru Crj..\/u//ogr.Scct. A 1990, 46. 467.
[lo] G. M Sheldrick, SHELXL-Y3, program for crystal structure refinement.
GBttingen, 1993.
[ I l l H. D. Flack. .4(.rii C‘rwdlogr. Swr. A 1983. 39. 876.
1121 I. Waller. T. Halder. W Scharz. J. Weidlein. J. Urgcuintiier. Chetn. 1982,232.99.
1131 B. Neumiiller. F. Guhlmann. A ~ i p ’Chcrn.
.
1993. 105. 1770: A i i p ~ i iC
. / i ~ i nh .z r .
Ed. €iip/. 1993, 32. 1701.
[14] 0. T. Beachley. Jr.. M. R . Churchill. J. C. Pazik. J. W. Ziller. Orp~moii7rru//ics
1986. 5. 1814.
[15] P. Wipf. S. Lim. Ai?gaii.. Cho?i 1993. 105. 1095: A/igeiit Chcni. Inr. Ed 07g/.
1993. 32. 1068.
H
H
1
H
2a : K = Bn
2b:R=H
CH,CI,,THF
~
Benziporphyrin, a Benzene-Containing,
Nonaromatic Porphyrin Analogue
Kurt Berlin and Eberhard Breitmaier*
An interesting approach for modifying the basic porphyrin
framework for the most varied applications“] is replacing the
pyrrole ring by another five-membered ring heteroarene such as
furan and thiophene,[*l or by ~ y r i d i n e [ ~or. ~benzene.
]
When 1,3disubstituted six-membered rings are incorporated, the macrocycle can achieve 18 n aromaticity only at the expense of the 671
aromatic system. The obvious question is which of the two rings
wins this competition. Recently we reported on the synthesis of
a modified porphyrinogen in which a pyrrole is replaced by a
pyridine
However, we could not obtain the 18 n aromatic
tautomer with maximum unsaturation which corresponds to a
porphyrin. The oxidation of the p y r i p ~ r p h y r i n o g e n ~leads
~ ] to
the ketone instead.
We report here on the first benzene-containing macrocycle
that is a porphyrin analogue. which in contrast to the pyriporp h y r i n ~ , [was
~ ] obtained simply by oxidation of the appropriate
porphyrinogen 3. Tripyrranedicarboxyhc acid 2bC5]was decar[*] Prof. Dr. E. Breitmaier. Dip].-Chem. K. Berlin
Institut fur Organische Chemie und Biochemie der Universitit
Gerhard-Domagk-Strasse 1, D-53121 Bonn ( F R G )
Telefax: Int. code (228)73-5683
+
p-chloranil
boxylated in situ and condensed with isophthalaldehyde (1) in
dichloromethane/THF with 33 YOHBr in glacial acetic acid as
the catalyst. The resulting macrocycle was then oxidized in situ
with p-chloranil to give 4. In analogy to pyriphorphin we propose the name benziporphin for the unsubstituted framework
and the numbering shown for 4a.
The spectroscopic data for the compound give no indication
of 18n aromaticity and cyclic conjugation in the tautomer. The
UV spectrum, for example, does not display the Soret band
(420 nm, Igs > 4) characteristic of porphyrins, and in the
‘H NMR spectrum the pyrrole-NH protons (6 = 8.90) and the
inner benzenoid protons (6 =7.88) d o not show the shielding
typical for the inner protons of an [18]annulene. Thus the tautomers 4a/b (4: 1 in CDC1,) have an intact benzenoid arene unit.
It is apparent that the aromatic 18n tautomer does not exist
even when only one 6n arene would have to be sacrificed. Thus
4,a prototype of macrocycles in which benzenoid rings successively replace the pyrrole rings of porphyrin, indicates that porphyrin analogues with more than one 6 n arene@]cannot be
[18]annulenes.
The successful preparation of 4 also implies that the surprising behavior of the “pyriporphyrin~gens”[~~
towards oxidants
results from the side reaction of the reactive x-alkyl group of the
pyridine rings and is not a consequence of the unattainable 18 n:
aroma ticity.
Experimental Procedure
Diester 2 a (635 mg. 1 mmol) was dissolved in 80 mL of anhydrous T H F and treated
with 200 m g o f P d / C ( l O % Pd)and0.1 mLoftriethylamine. After3 hofhydrogenation at ambient pressure the catalyst was removed by vacuum filtration and the
filtrate (2 b) added dropwise to a solution ofisophthalaldehyde ( I ) (I 34 mg, 1 mmol)
in 800 mL of dichloromethane. Argon was then bubbled through the reaction mixture for 15 min, and then 1.8 mL of a solution of HBr in glacial acetic acid (33%)
was added. The reaction mixture was stirred for 4 h with exclusion of light. 750 mg
ofp-chloranil was added, and 15 min later the reaction mixture was neutralized with
2.5 mL of triethylamine and left to stand ca. 15 h. The solvent was removed under
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vacuum and the I-esidue purified by column chromatography on neutral alumina
under argon: eluent: a) ethyl acetate,'cyc~ohexane2: 3. b) dichloromethaneipetroleum ether (b.p. 40 -60 C ) 1 :2. R, = 0.21. The dark green fraction provided 27 mg
(58.6 pmol. 5.9 "%) of black-blue crystals. Selected physical and spectroscopic data
of 4: m.p. 115-138 C (decomp): MS (70eV): ni/; (%): 463.2985 (53). calcd
?HI. 462.3 (48) [M' HI. 461.2841 (IOO), calcd 461.2831 [M']:
463.2988 [ M '
'H NMR (400 MHz. CDCI,): 6 =1.27. 1.36 (2 t. 1 2 H ; Yb-Hil3b-H), 2.34. 2.42
(2c.6H (1.4); Xa-H).2.77.2.85(2q. 8H:Ya-H. 13a-H).6.57 (s.2H; 11-H), 7.25.
7.28 ( 5 . ? H ( 1 . 4 ) . 6-HI. 7 74 (t. 'J(H. H ) = 8 2 Hz, 1 H ; 3-H). 7.88 (m br, 1 H ;
22-H). 7.98 (d. 2 H : 2-H). 8.90 (br. s. 1 H ; NH). I3C NMR(100 MHz. CDCI,, data
for 4a): d = I 0 2 (C-Xa), 15.3. 16.0 (C-9biC-13b). 18.0. 18.4 (C-9a/C-I3a), 92.9
(C-11). 122 4 (C-6). 124.8 (C-22). 128.7 (C-3). 133.9 (C-12). 137.2 (C-2). 140.4
(C-13). 141.0 (C-9). 141 2 (C-8). 147.7 (C-1). 156.9 (C-7). 168.8 (C-10); U V W S
), i
_,",, (Igi:)= 243 nm (4.19). 315 (4.39). 381 (4.49). 610 (3.49),632 (3.50).
716 (3.24): IR (KBr). 1: = 3309, 3040. 2960. 2928. 2865. 161X. 1587. 1572, 1434,
1101,XOY. 6X7cin.'
Received: February 9. 1994 [Z6681 IE]
German version: Angiw. Cheni. 1994. 106, 1356
+
+
We have now succeeded in synthesizing the first boron-bridged
naphthalene, 2, in a yield of 89 YOby the reaction of 1,8-dilithionaphthalene (1) with CI,BNiPr,. Colorless, crystalline 2 is thermally stable and can be sublimed without decomposition. On
the basis of spectroscopic data the molecule appears to have C ,
symmetry, which is confirmed by a crystal structure analysis
(Fig.
The slightly shortened B-N bond (1.37 A) lies al-
~
[ l ] J. L. Sessler. A. K Burrell. Top. Curr. Chem. 1991.161.177-273, and references
therein
[21 M. J Broadhurst. R Grigg, A. W. Johnson. J Cheni. SOC. C 1971. 21. 36813690
[3] D Jacoby. C. Floriani. A. Chiesi-Villa. C. Rizroli. 1 An!. Chcwi. Soc. 1993, 115.
7025 7026.
[4] K. Berlin. E Breitmaier, A n g w . Chrm. 1994.3.229-230: Angcu. Chrm. I n l . €d.
D i x I 1994. 33. 219-220. and references therein.
[5] J. L. Sessler. M. R. Johnson. V. Lynch. J Org. Chrm. 1987, 52. 4394- 4397.
[6] G . R Newkome. Y. J. Joo, D. W. Evans, S. Pappalardo. F. R. Fronczek, J. Org.
c'htv7,. 19XX. 53. 786-790. and references therein.
Synthesis and Reactivity of a
Naphtho[1,S-bclboret **
Achim Hergel, Hans Pritzkow, and Walter Siebert*
Dediccited to Professor Helmut Werner
on the occusioii o f h i s 60th birthdaj,
1 ,&Bridged naphthalene derivatives are interesting not only
structurally because of the distortion of their arene framework,
but also because of their synthetic potential owing to the
strained four-membered ring. U p to now compounds of this
type have been synthesized with sulfur, carbon, and silicon in
the bridging position;" -31 all attempts to prepare the corresponding nitrogen and oxygen analogues have
Fig. 1 . Molecular structure of 2.
Selected distances [A] and angles
[ 1: BI-NI 1.375, 1.369(5), B1-CI
1.599. 1.601(5). BI-CX 1.602.
1.601(5), Cl-C91.404, 1.403(4).
C8-CY 1.397, 1.406(4); Cl-B1-CX
86.2, 86.7(3). Bl-CI-C9 85.6.
X5.2(3), Bl-CX-C9 85.7, 85.1(3).
C1 -C9-CX 102.6. 103.0(3).
u -.c5
most in the plane of the naphthalene framework. and the angles
within the boret ring indicate that the ring is very strained.
Compound 2 reacts under mild conditions with BX, (X = CI,
Br) to give naphtho[l,8-cdl[l.2,6]azadiborinin4a, b by a novel
ring expansion. The first step is assumed to be the cleavage of a
B-C bond in 2 by BX, leading to the nonisolable intermediate 3.
which gives rise to the naphthoannelated heterocycle 4 by elimination of iPrX (or propene HX). Reaction of 2 with diborane
and diethylborane (X = H, Et) provides the p-diisopropylaminodiboranes Sa, b. In this case a B-H-B
bridge forms which
prevents further reaction. Compound 5 a is thus a stabilized
isomer of 3 (X = H). The proof for this is provided by the
replacement of the three hydrogen atoms bound to boron in Sa
by ethoxy groups. 3 (X = OEt) reacts with elimination of ethyl
isopropyl ether (or propene EtOH) and formation of 4c.
The crystal structure analysisl'] of S b (Fig. 2) indicates that
the boron atoms lie almost in the plane of naphthalene. The
+
+
Fig. 2. Molecular structure of 5b.
Selected distances [A] and angles
['I: N1-Bl 1.615(6), N1-B2
1.613(5). Bl-Cl 1.606(6), B2C81.609(6). B1-Ht 1.25(3), B2-HI
1.35(3), C1-CY 1.424(5). C8-C9
1.419(5); BI-Nl-B? 75.8(3). N I B1-C1 111.8 (3). NI-B2-C8
112.3(3), BI-Cl-C9 114.3(3). B2C8-C9
114.0(3).
CI-C9-C8
116.1(3).
['I
[**I
Prof. Dr. W. Siebert. Dr. A. Hergel, Dr. H. Pritzkow
Anorganisch-chemisches lnstitut der Universitit
Im Neuenheimer Feld 270. D-69120 Heidelberg (FRG)
Telefax : Int. code + (6221)56-4197
This work h a s supported by the Deutsche Forschungsgemeinschaft (Sonderforschungsbereich 247). the Fonds der Chemischen Industrie. and BASF AG.
An,qew. Chon. Inr. E d Engl. 1994, 33. No. 12
U
c4
C J
B-N-B angle (75.5(3)")is remarkably small, and the atoms B-NH form approximately a right angle.
Compound 5 a displays temperature-dependant molecular dynamics; the 'H N M R spectrum at 220K confirms the constitu-
VCH Yerluxsgrsellschufr mhH, 0-69451 Weinherni, 1994
0570-0833,'94!1212-1?47J 10.00 + .2SW
1247
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containing, nonaromatic, benziporphyrin, porphyrio, benzenes, analogues
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