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Indirectly Transmitted Charge-Transfer Interactions Multilayered [2.2] Paracyclophane Quinhydrones

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1m.p. 179% 180°C and 217 -218°C) were obtained analogously; they
are precursors of the corresponding [4.4]paracyclophaiie quiiihydrones
(D. Jokristoti, B. Srctrkrr. C . P. Her:. H . A . Srcwh, unpublished).
[7] Elemental analyses and spectroscopic data are in agreement with the
structures suggested.
[8] H . Irngrrrlinger, R.-D. Acker, W Rehufka, H . A. Strioh, Angew. Chem.
86. 705 (1974); Angew. Chem. Int. Ed. Engl. 13, 674 (1974).
The dimethyl ethers ( 1 2 ) and ( 1 3 ) , corresponding to ( 1 )
and ( 2 ) , were formed unexpectedly (5% yield each) on
gas phase pyrolysis of ( 5 ) / ( 6 ) and were separated by chromatography (silica,benzene): ( I 2 ) [ ' l forms dark red needles (from
methylcyclohexane). m.p. 202-203°C;
MS: M + calc. for
CZOH2204 326.1518, obs. 326.1522; 'H-NMR (CDC13):
S= 1.8-3.3 (m, 12H, methylene), 3.73 (s, 6H, iieihoxy), 6.16
(s, 2 H, ring), 6.29 (s, 2 H, ring). (23)"' crystallizes from methylcyclohexane as brick-red needles, m.p. 218-219°C; MS: M +
calc. for C2,,H1204 326.1518, obs. 326.1522; 'H-NMR
(CDC13):6 = 1.65-3.3 (m, 12H. methylene), 3.67 (s, 6H, methoxy), 6.00 (s, 2H, ring), 6.35 (s, 2H, ring). The electronic
spectra of ( 1 2 ) and ( 1 3 ) agree very well with those of the
respective quinhydrones (1) and ( 2 ) : in the 350-650nm
region ( 1 3 ) shows a strong CT absorption [hm,,=475nm
( E = 3000), in chloroform] having about 30-fold greater
intensity than ( 1 2 ) for which, on the other hand, an additional
CT absorption at shorter wave-length is observed
[hmax= 367 nm (E = 1740),shoulder 500nm ( E = loo), in chloroform]. For ( 1 3 ) it was shown by the concentration independence ( I 0-'-10M ) that intermolecular donor-acceptor
interactions d o not contribute detectably to the CT absorption.
Comparison of the electronic spectra of the pairs of diastereomers ( 1 ) / ( 2 )and ( 1 2 ) / ( 1 3 ) reveals an even stronger orientation dependence of the C T absorption for the quinhydrones
of the [3.3]paracyclophane series than was found in the
[2.2]paracyclophane group. For the reasons mentioned in
the introduction. we think that the results now obtained provide a general description of the orientation dependence of
C T interactions in donor-acceptor complexes of the quinhydrone type.
'
Indirectly Transmitted Charge-Transfer Interactions:
Multilayered [2.2]Paracyclophane Quinhydroned
By Heiriz A. Stuub, Udo ZupJ and Anrzeliese Gurke"]
Intramolecular fixation of donor-acceptor systems in the
rigid skeleton of cyclophanes led to information regarding
orientation and distance dependences of charge-transfer (CT)
interactions which is inaccessible by the investigation of regular
intermolecular CT complexes['. *I. Using the same concept
an attempt was made to answer the question whether
an indirect transmission of CT interactions occurs if donor
and acceptor are not in direct spatial contact but are separated
by intercalated aromatic n-electron systems. For this purpose
donor-acceptor cyclophanes were to be synthesized where
the donor and acceptor units are in the external positions
of a multilayered [2.2]paracyclophane. Interesting representatives of this group of compounds would be quinhydrones
of triple- or quadruple-layered [2.2]paracyclophanes like ( ' I )
or (5). As in the case of quinhydrones of simple [2.2]- and
[3.3]paracyclophane~~'~~"],
for these multilayered quinhydrones pairs of stereoisomers with different donor-acceptor
orientation are to be expected ( ( 1 ) / ( 2 ) , for example). The
electronic spectra of these compounds were expected to provide evidence about the problem of indirect transmission of
CT interactions and its orientation dependence.
Received: September 26, 1977 [Z X43a I € ]
German version: Angew. Chem XY. 839 11977)
RO
pon
0
~~
Orientation effects on charge-transfer interactions. Part 13. Part I?:
C. P. / / e r : . If. A . Sr[iah. Angew. Chem. 8Y, 407 (1977); Angew. Chem.
l n t , Fd. t n g l . 16. 394 (1977).
W R c h f h c t . H . .4.Srorrh. Ansew. Chem. 8j. 831 (1973): 86, 234 (1974):
Angew. Chem. Int. Ed. Engl. 12. 776 (1973): 13, 203 (1974): Chem.
Ber. 1 1 0 . 3333 (1977); H . A . Sraoh. C . P. Her:. H : E . Herihe. ; h i d f l f J ,
3351 (1977): H . A . Stctuh, H . H<rffiier. ihid. 110. 3358 (1977): H . A .
Srtroh. I: Ei<q/i&w.ibid. 110. 3366 (1977): D. Schiwtser. X . H . Hmtsser,
I! Tmgllrhrr. H . .A. Srtlrth. Chem. Phys. 1 4 , 183 (1976): cf. the MO calculations of /f. Lhgkr. G . Eye. If. A . S l r i d ~ .Tetrahedron 31. 1441 (1975):
M o l . Phys. 33. 913 (19771.
Diethyl 2.5-dimsthoxybenrene-I .I-diacctate as treated with LiAIHj in
trti-ahydrofuran to give l.Cbis(~-tiydroxyeIhyI)-2.5-dimelhoxybenreiie
1m.p 130°C. 87 ",,) which with phosphorus tribromide;benzene yielded
1.4-bia(1-bromocthyl)-2.5-dimethoxybenrene(m. p. 112-123 "C.XO",,) (I.:
X I ~ ~ / I C Pli.
~ W .D. Thesis. Univ. Heidelberg 1976).
hloroform) of the ( 3 ) ( 4 ) mixture gave the
taodiastcreomerainapurcstatelm.p. 185°C and 216°C). theassignment
t o ( 3 ) and ( 4 1 has n o t yet been possible.
IM. H<wiw/. H . 4 . Sfaiih. Tetrahedron Lett. IY70. 3 5 8 5 : Chcm Ber.
1 0 6 2190. 2203 (1973): M. H ~ t m d .4 . f ' i r i r o i l - . V 7&q/irher. H . .4 S r d .
Tctrahedron Lett. 1977, 1733.
St:irtiiig from 7.1 0.1 8.2 I -tetramethoxy-2.15-dithia[5.5]paracyclophane
tlic two diastercomeric 6.').16.19-tetramerhoxy[4.4]paracyclophanes
IZI, R = H
141, R -Me
Ill, R =H
131, R =Me
CAS Regiatry numbers:
( 1 ). 64474-72-2: ( 2 ) . 64425-70-3; (3). 64519-32-0; ( 4 1 . 64425-69-0; ( 5 ) .
64519-31-9: 1 6 ) . 64425-68-9; (71, 64425-67-8; ( 8 ) . 64519-30-X; (Y). 6447471-1. (101.64425-66-1: (11).64425-65-6;(12), 64474-70-0; ( 1 3 ) . 64425-64-5:
1.4-bis~?-bromoetliyl~-2.5-dimethoxyben~ene,
64425-63-4; 1.4-b1s(mercaptomethyl)-2.5-dimethoxybenrene3 disodium salt. 59416-85-2: tetrahydroxy[3.3]parec)cli,phane. 64440-84-2
~
HO-I
I51
0
/61
As in the previous syntheses of cyclophane quinhy-
the corresponding tetramethoxy compounds ( 7 )
and (8) were key intermediates for the preparation of ( I )
and ( 2 ) . By analogy with the syntheses of other multilayered
cyclophane~[~J.
crossed 1,6-Hofmann elimination of (2,5dimethoxy-4-methylbenzyl)trimethylammonium bromide[2b'
and pseudo-ortho-4,7-dimethoxy-l2-methyl-l5-trimethylammoniomethyl[2.2]paracyclophane bromide ( 9 ) seemed to be
a suitable approach for the syntheses of ( 7 ) and ( 8 ) . The
reaction of pseudo-orrho-4,7-dimethoxy-12.15-di1nethyl[t.2]--
~
[*] Prof. Dr. H. A. Staab, Dip].-Chem. U. Zapf. A. Giirhc
Max-Planck-lnstitut fiir medirinische Forschung
Abteilung Organische Chemie
Jahnstrasae 29. D-6900 Heidelberg ICiermaiiyI
801
para~yclophane[~]
with N-bromosuccinimide (90 "/, of the
equivalent amount, CCI4) resulted in pseudo-ortho-4-bromomethyl-7-methyl- 12,15-dimethoxy[2.2]paracyclophane which
yielded (9)[61(dec. >230"C, about 50% overall yield) with
trimethylamine in ether. Equimolar amounts of (9) and (2,5dimethoxy-4-methylbenzyl)trimethylammonium bromide
were converted into the hydroxides (silver oxide, water) which
were heated 12 h in boiling xylene (water separator, addition
of phenothiazine). The reaction product separated from insoluble polymers yielded, by chromatography (silica, benzene), a
mixture of the two diastereomeric tetramethoxy[2,2]paracyclophanes[2a,bland the quadruple-layered tetramethoxy[2.2]paracyclophanes (10) and ( I 1 ) (total yields 14,5 %)and subsequently in 15.5 "/, yield ( 7 ) / ( 8 ) which were separated by
fractional crystallization from acetone or by chromatography
(silica, benzene, n-hexane, 3 : 2): ( 7)l6] forms colorless needles,
m.p. 204-205 "C (from methanol), (8)16] colorless needles,
m.p. 226-228°C (from acetone). The assignment to ( 7 ) and
( 8 ) , respectively, is possible on the basis of 'H-NMR: Whereas
for the pseudo-ortholpseudo-ortho linked ( 7 ) all four methoxy
groups and all four protons of the two external rings are
equivalent, this is not true for ( 8 ) since here the pseudo-ortho/
pseudogeminal linkage leads for the methoxy groups and
the protons of the two external rings to different orientations
with regard t o the methylene bridges between the neighboring
[2.2]paracyclophane unit. Indeed, for ( 8 ) a doubling of the
'H-NMR signals for the methoxy groups and the protons
for the external rings is observed: ( 7 ) : 6=2.15-3.6 (m, 16H,
methylene),3.32(~,
12H,methoxy),5.51 (s,4 H,external ring),6.13
(s, 2H, internal ring); (8): 6=2.1-3.65 (m, 16H, methylene),
3.30 (s, 6H, methoxy), 3.33 (s, 6H, methoxy), 5.45 (s, 2H,
external ring), 5.50 (s, 2H, external ring), 5.61 (s, 2H, internal
ring); in C6D6['1 (80 MHz).
Me@
Q
'OM.
Me0
I81
171
Q
CHZ NMe3JBr
Me0
191
The quadruple-layered tetramethoxy[2.2]paracyclophanes
( 1 0 ) / ( 1 1 ) were also obtained when (9) alone was subjected
to 1,6-Hofmann elimination (14 % yield). The separation of
the diastereomers which would be necessary for the syntheses
of the quinhydrones ( 5 ) and (6) has not yet proved possible
by chromatography because of the extremely similar properties
of ( 1 0 ) and ( 1 1 ) ; a partial separation has been achieved
by fractional crystallization from acetone/carbon tetrachloride
(3 : 1).
Me0
OMe
OMe
Ether cleavage of ( 7 ) with methylmagnesium iodide (1 h,
160--190"C, under nitrogen) and subsequent oxidation with
silver oxide in acetone led, after chromatography on silica
from chloroform, in 60 2,yield to the benzoquinonophane
( I ? ) [ ' ] : orange needles. dec. >250"C; MS: M + calc. for
C26H2204 398.1518; obs. 398.1517; 'H-NMR (CDC13):
802
6=2.0-3.3 (m, 16H, methylene), 5.70 (s, 4H, quinonoid), 6.26
(s, 2H, internal ring). Analogously, compound ( 8 ) gave the
diastereomeric benzoquinonophane ( I 3)t6]: orange needles,
dec. >260"C; yield 40%; MS: M + calc. for C26H2204
398.1518, obs. 398.1517; 'H-NMR (CDC13): 6=2.05-3.15
(m, 16H, methylene), 5.69 (s, 2H, quinone), 5.74 (s, 2H,
quinone), 6.1 8 (s, 2H, internal ring). In contrast to the preparation of the simple [2.2]- and [3.3]paracyclophane quinhycatalytic hydrogenation of ( 1 2 ) and ( 1 3 ) gave
mixtures of the tetrahydroxy compound and unreacted benzo-
:0
I 121
Ogo
1131
quinonophme-probably due to the smaller stabilization of
the quinhydrone stage-together
with quinhydrone which
could not yet be isolated from these mixtures.
The dimethyl ethers ( 3 ) and ( 4 ) of the quinhydrones ( 1 )
and ( 2 ) , however, were obtained-obviously due to incomplete demethylation-as by-products (ca. 2 % yields) of the
syntheses of ( 1 2 ) and (13), respectively, and were separated
by chromatography (silica, chloroform): ( 3 ) forms red needles,
m.p. 224-226°C
(from methanol); MS: M + calc. for
C28H2804 428.1987, obs. 428.1960; 'H-NMR (CDC13):
6=2.0-3.5 (m, 16H, methylene), 3.61 (s, 6H, methoxy), 5.60
(s, 2H, external ring), 5.66 (s, 2H, external ring), 6.16 (s, 2H,
internal ring); ( 4 ) forms dark red crystals (from ethanol,
dec. >260"C); MS: M + calc. for C28H2804 428.1987, obs.
428.1981; 'H-NMR (CDCI,): 6=1.8-3.5 (m, 16H, methylene), 3.58 (s, 6H, methoxy), 5.56 (s, ZH, external ring), 5.65
(s, 2H, external ring), 5.85 (s, 2H, internal ring).
In the 350-550nm region ( 3 ) and ( 4 ) show a broad
CT absorption [ ( 3 ) : hm,,=437nm ( ~ = 2 2 7 0 ) (; 4 ) : h,,,=415
( E = 201O), chloroform]. Since this band is concentration-independent it must be due to an intramolecular CT transition
which in "vertical conjugation" is transmitted through the
n-system intercalated between donor and acceptor[8! As is
shown by comparison of (3) and ( 4 ) , however, the orientation
dependence of C T absorptions, observed for simple donoracceptor [2.2]paracyclophanes, is almost completely lost in
this type of CT interactions.
Received: September 26, 1977 [Z843b IE]
German version: Angew. Chem. X9. 841 (1977)
CAS Registry numbers:
( I 1. 64474-67-5;( 2 ) . 64474-66-4;( 3 ) . 64474-65-3:(4),64425-54-3;(S),
64474-69-7;(6),64425-62-3:(7 1,64425-61-2;(8).64519-29-5;( 9 I, 64425-60-1;
( 1 0 ) . 64519-28-4;( I l ) , 64425.594; ( I Z ) , 64474-68-6;( 1 3 ) , 64425-58-7;
(2,5-dimethoxy-4-methylbenzyl)trimethyl
ammoniumbromide. 64425-57-6:
pseudo-o-4,7-dimethoxy-l2,15-dimethyl[2.2]paracyclophane, 64425-56-5;
pseudo-o-4-bromomethyl-7-methyl12,15-dimethoxy[2.2]paracyclophane.
64425-55-4
"I
Orientation dependence of charge-transfer interactions, Part 14.-Part
13: H . A. Sruuh. C. P . Hcwz, Angew. Chem. 89. 839 (1977); Angew.
Chem. Int. Ed. Engl. 16. 799 (1977).
121 a) W Rehrrfku, H . A . Slriuh, Angew. Chem. 85. 831 (1973):86. 234
(1974):Angew. Chem. Int. Ed. Engl. 12. 776 (1973): 13. 203 (1974):
Chem. Bcr. 110. 3333 (1977):b ) H. A . Staub, C. P. Hrrz. H . - E . H n i k r .
Chem. Ber. 110, 3351 (1977):c) H . A . Sruuh, H . Huffiwr, Tetrahedron
Lett. IY74, 4397: Chem. Ber. 110, 3358 (1977):H.A . Sfuuh. V. Tuglirher.
hid. 110, 3366 11977); D. Sc/nw;r=w, K . H . Huussrr, V Tuqlirhei. H .
A. Srrinh, Chem. Phys 14, I83 (1976): d) cf. M O calculations of H .
N i g h , G . E g c , H . 4. Sruuh. Tetrahedron 31, 2441 (1977):Mol Phys.
33, 923 (1977).
Aiigrn. C h m . Int. E d . Engl. 16 (1977) No. 11
[3] H . A . Sfooh. C. P. Her-, Angew. Chem. 8Y, 406, 407 (1977); Angew.
Chem. Int Ed. Enpl. 16, 392, 394 (1977).
[4] D. 7: Loriyonr, H . S. Chox, J. Am. Chem. Soc. 86, 3898 (1964): Y2,
994 (1970): T Otsuho, S. Mizoquini. I . Otsubo, 2. To:uRrr. A . Sukuqumi.
Y. Sakuro. S. Miaurni. Bull. Chem. SOC.Japan 46, 3519 (1973).
[ 5 ] C . P. Her_, unpublished.
[6] Analyses. molecular weights, and spectral data are in agreement with
the structures claimed.
[7] This doubling of signals is not observed in CDCl3 and CCIJ (80 MHz).
[8] Cf. H. 7hremirsu. 7: Orsuho, Y Sukiira. S. Misumi, Tetrahedron Lett.
1975. 3059.
ABSTRACTS
The synthesis of 6H-pyrido[4,3-b]carbazole ( I ) and its derivatives is treated in a review by M. Sainsbury. ( I ) is the basic
molecular framework of the alkaloids (e.9. ellipticin, olivacin,
guatambin) which are found in the plant family Apocjunaceue.
These substances are of biogenetic interest and their derivatives
seem to be promising drugs for the treatment of cancer. The
already known routes for the synthesis of the skeleton ( 1 )
Thioethers (sulfides) have attracted increasing interest as reagents for organic syntheses in recent years, for they are stable
towards acids and bases, can form sulfur-stabilized carbanions,
and can be transformed into compounds having different substitution patterns by reductive or oxidative cleavage of the
C-S bond. A comprehensive survey of methods of synthesis
of thioethers, the physical and chemical properties of these
compounds, and their reactions has been written by W Tagaki.
[Sulfides in S . Our: Organic Chemistry of Sulfur. Plenum
Press, New York 1977, pp. 231-302; 210 references]
[Rd 966 IE]
Control at the level of substrate supply in the synthesis of
phenylpropanoids in plants is proposed by U . Margnu.
This offers an alternative to regulation at the level of enzyme
activity. The activity of the key enzyme, phenylalanine
ammonia lyase, often bears no relationship to the accumulation of phenylpropanoids; the actual enzyme activity usually
exceeds by far that which is necessary for the measured rate
of synthesis. Addition of exogenous phenylalanine also causes
the synthesis ofphenylpropanoids to increase. Protein metabolism and the synthesis of flavonoids and cinnamic acid derivatives in plants are however in a well balanced ratio. [Control
at the Level of Substrate Supply-an Alternative in the Regulation of Phenylpropanoid Accumulation in Plant Cells. Phytochemistry 16, 419-426 (1977); 120 references]
[Rd 982 IE]
The coordination of lipid degradation with the Krebs cycle
is discussed by P . W Hochachku, J . R. Neely. and W R.
Driedzic. The essential links between these two metabolic
pathways are their mutual requirements for coenzyme A,
NAD' and the oxidation capacity of FADH2. The cell can
thus maintain a precise coordination between fatty acid activation in the cytosol, the 0-oxidation of fatty acids in the mitochondria, and the complete oxidation of acetyl coenzyme
A to CO2 viu the Krebs cycle for a wide range of energy
requirements and oxygen supply. [Integration of Lipid Utilization with Krebs Cycle Activity in Muscle. Federation Proc.
36, 2009-2014 (1977); 57 references]
[Rd 983 IE]
.4riyw'. Chrr~i.I I I ~E.d Eliyl. 16 ( 1 9 7 7 ) N o . I 1
can be divided into three groups: 6-isoquinolone derivatives
(rings C and D) are reacted with arylhydrazines according
to the Fischer indole synthesis to give arylhydrazones which
are subsequently cyclized. The framework ( I ) is synthesized
from carbazoles (rings A, B and C) by Vilsmeier formylation,
condensation with 2,2-diethoxyethylamine, hydrogenation,
cyclization, and dehydrogenation. Other syntheses start with
indoles, e.9. gramin derivatives, (rings A and B) which are
condensed with substituted pyridines. Derivatives of ( I ) are
formed by cyclization (ring C). [The Synthesis of 6H-Pyrido[4,3-b]carbazoles. Synthesis 1977,437-448; 33 references]
[Rd 984 IE]
Di- and polyalkali metal derivatives of organic compounds
with functional groups are treated in a review by E . M. Kaiser,
J . D. Petty, and P. L. A . Kntctson. Di- and polyalkali metal
derivatives, which give valuable compounds with electrophilic
reagents, are formed from numerous organic compounds by
the action of two or more equivalents of strong alkali metal
bases (alkali metal amides, organolithium compounds). The
K
K
multiple metalation proceeds according to the following
scheme: metalation of the most strongly acidic proton to give
a weakly nucleophilic intermediate, subsequent metalation
of a second proton producing a more strongly nucleophilic
compound which usually reacts regiospecifically in the condensation with the electrophile at this anionic center. [Di- und
Polyalkali Metal Derivatives of Heterofunctionally Substituted Organic Molecules. Synthesis 1977,509---550; 306 references]
[Rd 985 IE]
803
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