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Benzo[1 2-h 4 3-h]diquinoline (У1 14-Diaza[5]heliceneФ) Synthesis Structure and Properties.

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BenzoI1,Zh :4,3-h’ldiquinoline
(“1,14-DiazaISlhelicene”): Synthesis, Structure, and
Properties**
By Heinz A . Staab,* Michael A . Zirnstein, and
Clam Krieger
Our synthesis of quino[7,8-h]quinoline 1 provides a
“proton sponge”l’l whose basic centers, as well as the
N . . . H . . . N hydrogen bond (in the cation formed by protonation of l), are not hydrophobically shielded by Nalkyl groups.”’ In the preceding communication, we described the molecular structure of l . I 3 ] In the same way
that 1 is related to 1,8-bis(dimethylamino)naphthaIene, the
actual “proton sponge”[41benzo[l,2-h :4,3-hldiquinoline 2
is related to 4,5-bis(dimethylamino)phenanthrene, whose
synthesis, structure, and “proton-sponge’’ properties we
have also de~cribed.’~]
Whereas a largely planar structure
was found for l , I 3 l compound 2, whose basic structure is
that of a [5]helicene, should display strong helical deformation. This should be reflected in the N ‘ . .N distance,
the preferential orientation of the nitrogen “lone pairs”,
and thus the N...H . . . N hydrogen bond in the monocation 2a derived from 2.
Fig. 3. Molecular structure of 2 as viewed from above the quinoquinoline
plane with bond lengths [pm] and bond angles [“I (standard deviations of the
last decimal place in parentheses). Monoclinic prisms from ethanol/water,
space group P2,/c, a=450.5(1), b=971.7(2), c=1233.5(2) pm, 8=93.29(2)”,
2=2,p,,,,,= 1.418 g cm-’; 1354 reflections, 976 observed with 122.00u(I);
structure solution by direct methods (MULTAN), R =0.037 [8].
-
L
-
w
114
114
ill
1
Fig. 4.Crystal packing of 2
in
the projection along the c axib.
Figure 3 shows the molecular structure of 2 viewed from
above the tetracyclic ring system. The bond lengths and
bond angles of the centrosymmetric molecule d o not deviate significantly from those of other quinoline compounds. The molecule is nearly perfectly planar with maximal deviations of 2 p m [for C(6) and N(4)] for the leastsquares plane formed by the 18 ring atoms. The crystal
packing (Fig. 4) shows the “herring-bone pattern” often
observed for polycyclic aromatic compounds. The molecules are stacked along the a axis, the stacking axis forming an angle of 41.4” with the plane of the molecules; the
interplanar distance between neighboring molecules within
the stack is 339 pm.
Received: August 18, 1988 [Z 2928 IE]
German version: Angew. Chem. I01 (1989) 72
[ I ] Review: H. A. Staab, T. Saupe, Angew. Chem. 100 (1988) 895: Angew.
Chem. Int. Ed. Engi. 2 7 (1988) 865.
[2] M. A. Zirnstein, H. A. Staab, Angew. Chem. 99 (1987) 460; Angew. Chem.
Int. Ed. Engl. 26 (1987) 460.
[3] R. W. Alder, P. S. Bowman, W. R. S. Steele, D. R. Winterman, Chem.
Commun. 1968. 723: further references in [I].
[4] 1. Iwai, S. Hara. J . Pharm. SOC.Jpn. 70(1950) 32.
[ S ] I. Iwai, S. Hara, S. Sayegi, J. Pharm. Soc. Jpn. 71 (1951) 1152.
[6] M. Dufour, N. P. Buu-HoI, P. Jacquignon, J . Chem. SOC.C1967, 1415.
171 A. Edel, P. A. Marnot, J. P. Sauvage, Tetrahedron Left. 26 (1985) 727.
[8] Further details of the crystal structure investigations may he obtained
from the Fachinformationszentrum Energie, Physik, Mathematik GmbH,
D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository
number CSD-53273, the names of the authors, and the journal citation.
86
0 VCH VerlagsgeselischaJi mbH, D-6940 Weinheim. 1989
11
5
10
8
7
2
2a
To synthesize 2, 1 , l l -diamino-5,7-dihydrodibenzo[c,e]thiepin 3, synthesized earlier by us,[51was converted into
7,9-dihydrothiepino[3,4-h:6,5-h qdiquinoline 4 (24% yield)
in a double Skraup reaction (glycerol, arsenic acid, conc.
sulfuric acid; 30 min, 145-150°C). Oxidation with trifluoroperoxyacetic acid in trifluoroacetic acid (2 h, 0-20°C) led
to the S,S-dioxide 5 in 72% yield. A variant of the Ramberg-Backlund
with KOH and CCI, in
tBuOH (3-5”C, then 2.5 h, 40°C) resulted in conversion of
5 into the desired 2 (m.p. 271-273°C; 13% yield, 16% re-
isolation of 5 ) . The structure of 2 was established by correct elemental analysis, mass spectrum [ m / z 280 (loo%,
M O ) ,279 (24), 252 (24), 140 (11, M 2 @ ) high-resolution
;
MS:
M a 280.0997 corresponding to C3,,HT2N2]and ’H N M R
data [S=7.59 (dd, J=8.1 and 4.2 Hz, 2 H ; 3,12-H), 8.10
and 8.12 (AB, J=8.5 Hz, 2 H each; 5,lO- and 6,9-H), 8.19
(s, 2 H , 7,8-H), 8.43 (dd, J=8.1 and 1.7 Hz, 2 H ; 4,11-H),
8.56 (dd, J=4.2 and 1.7 Hz, 2 H ; 2,13-H; 500 MHz, [D6]dimethyl sulfoxide (DMSO)].
[*] Prof. Dr. H. A. Staab, DipLChem. M. A. Zirnstein, C. Krieger
Abteilung Organische Chemie
Max-Planck-Institut fur medizinische Forschung
Jahnstrasse 29, D-6900 Heidelberg (FRG)
[**I
New “Proton Sponges”, Pan 9.-Part
0570-0833/89/0101-0086 $ 02.50/0
8: [3].
Angew. Chem. Inr. Ed. Engl. 28 (1989) No. I
The molecular structure of 2, which has C2 symmetry in
the crystal, is shown in Figure 1. Bond lengths and angles
(Fig. I , top) do not reveal any unusual features in comparison to planar 1 or its isomer.[31The middle of Figure 1
shows the considerable helical deviation of the planar arrangement; this is seen even more clearly in the side view
along the central bond C(17)-C(17i) (Fig. 1, bottom). The
consequence of this helical deformation is an increase in
the N . . . N distance to 270.5 pm, which is only slightly
shorter than the N . . . N distance in planar 1 (272.8 pm).
Figure 2 shows the lattice packing of 2, which is present as
a racemate.
114
CISil
\
d
I
I
114
h
P CIS1
119.9
5
119.3
Cl6il
I
114
0
I
1/41
Fig. 2. Crystal lattice packing of 2 (racemate) In the projection d o n g the b
axis.
c
C12il
Fig. I . Molrcuidr structure of 2 viewed from above the average plane of the
central six-membered ring C (top), from the side of and somewhat above the
pentacyclic system (middle), and from the side along the central C(17)C(17i) bond (bottom): bond lengths [pm] and valence angles [“I (standard
deviations of the last decimal place in parentheses) are given above. Crystal
of 2 from ethyl acetate, space group C2/c; a = 1213.0(3), b=905.8(2),
c = 1279.2(3) pm, b = 106.28(2)’; Z=4,p,,,=
1.380 g cm-’: 1613 symmetryindependent reflections to sinO/A=6.8 nm-’, 910 observed with I 2 2 o ( I )
[71. The structure was solved starting from that of [5]helicene [8] by placing
the molecule on the twofold axis and optimizing its position by variation of
they coordinate and rotation around the twofold axis; R=0.039.
Angew. Chem. Inl. Ed. Engl. 28 (1989) No. I
Upon addition of 70% perchloric acid in excess to 2 in
dichloromethane, a perchlorate is formed which can be recrystallized from methanollwater (3 : 1) (64% yield;
m.p.L32O0C, dec.). The elemental analysis and the ’H
NMR spectrum [6=8.28 (dd, J=7.8 and 4.7 Hz, 2 H ; 3,12H), 8.44 and 8.49 (AB, J=8.4 Hz, 2 H each; 5,10-H and
6,9-H), 8.59 (s, 2 H ; 7,8-H), 9.15 (dd, J=8.0 and 1.6 Hz,
2H; 4,11-H), 9.59 (dd, J=4.6 and 1.6 Hz; 2,13-H), 23.89
(br. s, I H , N . - . H - . . N ) ; 500 MHz, [D,]DMSO] confirm
the expected presence of the monocation 2a. Compared to
2, all signals in 2a are shifted downfield by the protonation. Most noteworthy is the chemical shift of the hydrogen-bond proton (to almost 6=24!). Although we find a
strong downfield shift for all N . .H . . .N hydrogen bonds
in the “proton sponges”, the value found for 2a shows that
here the anisotropy effect of the helical aromatic bonding
system is additionally important.
‘H NMR spectroscopic determination of the signal intensities in transprotonation experiments with 1,8-bis(dimethylamino)naphthalene[’] gave a pK, value of 10.3 & 0.2
for 2. In these experiments, only averaged signals were
found for 2 and 2a, so that, in this case, the rate of proton
transfer is rapid relative to the time scale of the NMR
method. This is not true for typical “proton sponges”,
whose basic centers and N . . .H . ‘ .N hydrogen bonds are
hydrophobically shielded by N-alkyl groups.[’I The behavior of 2/2a is in complete agreement, however, with that of
l / l a . Thus, 2 is also an example of a kinetically active
“proton sponge”. That the basicity constant of 2 is nearly
two powers of ten smaller than that of 1JZ1although the
N . . .N distance in 2 (270.5 pm) is somewhat shorter than
0 VCH VeriagsgesellschaJi mbH, 0-6940 Weinheim, 1989
0570-0833/89/0101-0087 $ 02.50/0
87
in 1 (272.8 pm)l3], is presumably due to the helical structure of 2 (see Fig. 1, middle). This structure nearly removes
the destabilizing “lone-pair’’ interaction of the nitrogen
atoms in the free base and, for 2a, hinders the formation
of an N . . . H . . .N hydrogen bond along the favored direction of the nitrogen “lone pairs”.
ences determined from a highly-correlated calculation according to the algebraic diagrammatic construction(3) procedure (ADC(3) procedure).I’ ’]
Received: August 18, 1988 [Z 2929 IE]
German version: Angew. Chem. 101 (1989) 73
[ I ] Review on “Proton Sponges”: H. A. Staab, T. Saupe, Angew. Chem. 100
(1988) 895; Angew. Chem. Int. Ed. Engl. 27 (1988) 865.
121 M. A. Zirnstein, H. A. Stdab, Anyrw. Chern. 99 (1987) 460; Angew. Chem.
In/.Ed. Engl. 26 (1987) 460.
131 C. Krieger, M. A. Zirnstein, 1. Newsom, H. A. Staab, Angew. Chem. 101
(1989) 72; Angew. Chem. Int. Ed. Engl. 28 (1989) 84.
[4] R. W. Alder, M. R. Bryce, N. C. Goode, N. Miller, J. Owen, J. Chem. SOC.
Perkin Trans. I 1981. 2840; the name “Proton Sponge” was introduced by
Aldrich Chemicals Co., Milwaukee, as the commercial name of this compound.
151 T. Saupe, C. Krieger, H. A. Staab, Angew. Chem. 98 (1986) 460; Angew.
Chem. I n / . Ed. Engl. 25 (1986) 451; for the X-ray structure analysis see
[I].
161 C. Y. Meyers, A. M. Malte, W. S. Matthews, J. Am. Chem. SOC.91 (1969)
7510; C . Y. Meyers, W. S. Matthews, G. J. McCollum, J. C. Branca, Terrahedron Lett. 1974, 1105.
[7] Further details of the crystal structure investigation may be obtained from
the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository
number CSD-53274, the names of the authors, and the journal citation.
[8] R. Kuroda, J. Chem. Soc. Perkin Trans. 2 1982. 789; cf. also A. 0. Mclntosh, J. M. Robertson, V. Vand, J . Chem. SOC.1954, 1661.
1100 K
I
I
I
I
I
I
spectra
I stripping
I
Methylboron Oxide, H,C-B=O* *
By Hans Bock,* Lorenz Cederbaum,* W. von Niessen,
Peter Paetzold, * Pave1 Rosmus, and Bahman Soiouki
Dedicated to Professor Heinz Georg Wagner on the
occasion of his 60th birthday
I
I
I
I
I
-
12
1L
16
18 lEIeV1
0.19 eV 91500 cm”
H,C--BIO
Organoboron oxides (organo(ox0)boranes) RBO are kinetically unstable with respect to their cyclic t r i m e r ~ [ ~ - ~ ]
and, therefore, in contrast to the isoelectronic iminoboranes RBNRI’] and methyleneboranes RBCR2,I6]they were
previously unknown. The title compound is of particular
interest with regard to its electron distribution; containing
16 valence electrons, it should thus have a linear CBO
ADC 13)
IeVl
f r a m e w ~ r k ”and
~ can be compared with numerous wellknown compounds, such as H,C-C=CH
and
Fig. I . H q l ) Pt spectra 0 1 2-methyl-l,.i,2-d1uhaburul~n~-4,5-d10n~
at 33U K
H , S ~ - C G C H [ ~as~ well as H3C-C=N.I9]
(top), of its pyrolysis products at 1100 K (middle), and-after digital subtraction of the ionization patterns of C O and C02-of methylboron oxide (botMethylboron oxide was generated by pyrolysis of 2-metom) [lo]. Assignment of the six radical cation states in the measuring range
thyl-l,3,2-dioxaborolane-4,5-dione
at 1100 K, optimized by
on the basis of ADC(3) total energy differences [Ill.
PE-spectroscopic real-time gas analysis[’] (Fig. I), and the
PE spectrum of the “pure” compound (Fig. 1, bottom) was
obtained by digital subtraction (“spectra stripping”) of the
A comparison of the radical cation states of H3C-B=0
ionization patterns of the thermodynamically favored fragwith equivalent
of the iso(valence)electronic molmentation molecules C O and C02.11”1
The radical cation
ecules CI-B=SJ4] H3Si-C=CH,ISJ H3C-C=CH,@1 and
states were assigned on the basis of the total energy differH3C-C=N[91 (Scheme 1) corroborates the ADC(3) assignment (Fig. 1) and furthermore provides, on the basis of
[*] Prof. Dr. H. Bock, Dr. P. Rosmus, Dr. B. Solouki
first- and second-order perturbation arguments, insights
Institut fur Anorganische Chemie der Universitat
into its electron distribution (JT: center of gravity of JahnNiederurseler Hang, D-6000 Frankfurt am Main 50 (FRG)
Teller-split bands).
Prof. Dr. L. S . Cederbaum, Prof. Dr. W. von Niessen
Physikalisch-chemisches lnstitut der Universitat
The sequences of the radical cation states of the iso(vaIm Neuenheimer Feld, D-6900 Heidelberg (FRG)
1ence)electronic molecules H3C-Bm0 and CI-B=S are,
Prof. Dr. P. Paetzold
as expected, in agreement and therefore support the indeInstitut fur Anorganische Chemie der Technischen Hochschule
pendently made a~signrnents.~~.
’I The lower a(e) ionization
Templergraben 55, D-5 100 Aachen (FRG)
energies
can
be
explained
by
the
differences in the effec[**I Gas-Phase Reactions, Part 70. This work was supported by the Deutsche
tive nuclear charges Z,,,(S) <Z,,,(O), and the larger 71 and
Forschungsgemeinschaft, the Fonds der chemischen Industrie, and the
State of Hessen. Part 69: [I].
CT splittings by the differences Z,,,(CI-S) < Z,,,(O-C)
as
88
0 VCH Verlagsgesellschafr mbH, 0-6940 Weinheim. 1989
0570-0833/89/0101-0088 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 28 (1989) N o . I
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benz, structure, synthesis, properties, heliceneф, diquinoline, diaz
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