Di(8-hydroxyquinoline) derivatives for supramolecular chemistry: Syntheses and solid state superstructures

Article abstract of DOI:10.1055/s-1999-3599

The synthesis of the di(8-hydroxyquinoline) derivatives 8-14 is described. Hereby, spacers of different length and nature (alkyl or amide) are introduced. The geometric features of the compounds are changed by connection of the bridging groups to different positions of the 8- hydroxyquinoline moiety. The derivatives thus obtained possess a high potential as ligands for metallo-supramolecular chemistry. In the solid state the alkyl-bridged compounds adopt a polymeric structure by formation of hydrogenbridges between self-complementary hydroxyquinoline units. The overall structure of the polymer is controlled by the spacer. Introduction of an amide group in 7-position of the quinoline leads to intramolecular hydrogen bonds and suppresses the formation of 'dimeric' di(8- hydroxyquinoline) units.

Full text of DOI:10.1055/s-1999-3599

FEATURE ARTICLE
1819
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry: Syntheses
and Solid State Superstructures
a
a
a
b
b
b
c
Markus Albrecht,* Oliver Blau, Karen Witt, Elina Wegelius, Maija Nissinen, Kari Rissanen, Roland Fröhlich
a
Institut für Organische Chemie, Universität Karlsruhe, Richard-Willstätter-Allee, D-76131 Karlsruhe, Germany
Fax+49(721)698529; E-mail: albrecht@ochhades.chemie.uni-karlsruhe.de
b
Department of Chemistry, University of Jyväskylä, P.O.Box 35, 40351 Jyväskylä, Finland
c
Organisch-Chemisches-Institut, Universität Münster, Corrensstraße 40, D-48149 Münster, Germany
Received 26 May 1999
Abstract: The synthesis of the di(8-hydroxyquinoline) derivatives
8
–14 is described. Hereby, spacers of different length and nature
(alkyl or amide) are introduced. The geometric features of the com-
pounds are changed by connection of the bridging groups to differ-
ent positions of the 8-hydroxyquinoline moiety. The derivatives
thus obtained possess a high potential as ligands for metallo-su-
pramolecular chemistry. In the solid state the alkyl-bridged com-
pounds adopt a polymeric structure by formation of hydrogen-
bridges between self-complementary hydroxyquinoline units. The
overall structure of the polymer is controlled by the spacer. Intro-
duction of an amide group in 7-position of the quinoline leads to in-
tramolecular hydrogen bonds and suppresses the formation of
“dimeric” di(8-hydroxyquinoline) units.
Key words: 8-hydroxyquinoline, hydrogen bonds, supramolecular
chemistry, hydrogen bonded polymers, chelating ligands
8
-Hydroxyquinoline (1) easily can be prepared either by
the Skraup, the Friedländer or by the Doebner-von Miller
1
reaction. With various metal ions it forms homoleptic co-
ordination compounds (oxinates) which possess low solu-
bility in polar solvents. Thus 1 frequently is used for
analytical purposes or for the extraction of metal ions (e.g.
2
,3
Ga(III)). Just recently the 8-hydroxyquinoline moiety
was introduced in metallo-supramolecular chemistry to
form mono- or dinuclear complexes. Hereby the molecu-
lar recognition of specific metal cations or the self-assem-
bly of defined supramolecular aggregates were of major
4
5
interest. Baret and Hiratami prepared 8-hydroxyquino-
line TRIPODS as complexing agents for different metal
ions. Recently we described the ethylene-linked di(8-hy-
droxyquinoline) ligand 3 and developed an example for
the new principle of “dynamic combinatorial chemis-
6
,7
try”.
In addition to its ability to form coordination compounds,
-hydroxyquinoline (1) shows a further feature which is
8
valuable for supramolecular chemistry. 8-Hydroxyquino-
line (1) possesses a hydrogen bond donor/acceptor motif
which is self-complementary. Consequently, in the solid
state 1 forms a dimer (1) by H-bridges between the oxy-
2
gen atom of one and the nitrogen atom of the other mole-
cule. Hereby a non-covalently linked ten membered ring
8
is obtained. Consequently, di(8-hydroxyquinolines) can
act as monomers to form polymeric structures in the solid
state. The monomers are connected via hydrogen bridges
Figure 1 8-Hydroxyquinoline derivatives 1–14 discussed in this
study
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1
820
M. Albrecht et al.
FEATURE ARTICLE
Biographical Sketches
Markus Albrecht (born 1964) studied Chemistry in
Würzburg and Münster and obtained his Dr. rer. nat. in
1
992 (Prof. G. Erker). After one year as a postdoctoral fel-
low in Berkeley (Prof. K. N. Raymond) he moved to
Karlsruhe and received his habilitation in 1997. His work
on the metal-directed self-assembly of metallo-supramo-
lecular aggregates was honoured with the “ADUC-Jahre-
spreis für Habilitanden” and with a Heisenberg-fellowship
of the DFG.
Oliver Blau was born in 1969 in Karlsruhe. He studied
chemistry in Karlsruhe and obtained his Dr. rer. nat in sum-
mer 1999. For his work on hydroxyquinoline derivatives he
got the “Wolff & Sohn Award” of the University of
Karlsruhe.
Karen Witt was born in 1972 in Berlin. She studied chem-
istry in Karlsruhe and obtained her diploma in 1998. Cur-
rently she is performing research in the group of Dr.
Albrecht to obtain a Dr. rer. nat in chemistry.
Elina Wegelius, born in 1973, studied chemistry in
Jyväskylä (Finland) and finished her diploma thesis on syn-
thetic calixarene ionophores in 1997. She is currently com-
pleting her doctorate on the X-ray crystallography of
organic and organometallic structures under the supervi-
sion of Prof. K. Rissanen. Her work is supported by The
Graduate School of Inorganic Material Chemistry (Minis-
try of Education in Finland).
Maija Nissinen, born in 1974, studied chemistry in
Jyväskylä (Finland). In 1997 she finished her diploma the-
sis on piperazine macrocycles and the synthesis of chiral
piperazines. She is currently completing her doctorate on
the X-ray crystallography of organic structures under the
supervision of Prof. K. Rissanen. Her work is supported by
The Graduate School of Bioorganic Chemistry (Ministry of
Education in Finland).
Kari Rissanen, born in 1959, studied chemistry in
Jyväskylä (Finland) and got his doctorate in 1990 on solid
state structural studies of organic compounds. In 1991 he
was appointed as a Docent (Privat Dozent) in Chemistry at
the University of Jyväskylä. In 1993 he was appointed as an
associate professor (C3 professor) in organic chemistry at
the University of Joensuu. Since 1995 he has worked as a
full professor (C4) and the Head of the Laboratory of Or-
ganic Chemistry at the University of Jyväskylä. His re-
search interest vary from Structural Chemistry into
synthetic Supramolecular and Organic Chemistry.
Roland Fröhlich, born in 1952, studied chemistry in Mün-
ster and Cologne and received his Dr. rer. nat. in 1982. Af-
ter postdoctoral studies in the crystallographic institute of
the University of Karlsruhe he worked as a sales and appli-
cation manager for Enraf Nonius. Since 1993 he is a senior
scientist at the University of Münster and since 1994 a do-
cent for X-ray crystallography at the University of Jyväsky-
lä.
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

FEATURE ARTICLE
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry
1821
1
4
while the structure of the polymeric strand is dictated by coupling of benzyl bromides which was described by Iy-
the nature of the spacer.
oda and Oda15 in the keystep of the reaction sequence.
Therefore appropriate benzyl bromides 17a–d had to be
prepared first.
In preliminary investigations we could show that alkyl-
bridged di(8-hydroxyquinoline) derivatives 3 and 4 form
polymeric superstructures in the solid state. While the
compound 3 forms a “doubly wound” polymer, deriva-
tive 4, which was first synthesized by Hiratami et al,
6
9
7
leads to a zigzag-type structure (Figure 2).
Figure 2 The hydrogen bonded polymeric structure of 3 (“doubly
wound”, (a)) and 4 (“zigzag”, (b)) in the solid state
Scheme 1
However the E-alkene bridged di(8-hydroxyquinoline)
derivative 5 does not show such a polymeric structure.
Probably due to steric reasons only hydrogen bonding be-
tween the phenolic units occurs.10
The syntheses of 8-acetoxyquinolines which bear bro-
momethyl substituents in 2- (17a), 4- (17b) or 5-position
Herein we describe the syntheses of a number of alkyl- (17c) were performed starting from the hydroxyquinoline
bridged di(8-hydroxyquinoline) derivatives 8–13 and of derivatives 15.3
,16,17
After quantitative acylation of the hy-
an analogous compound 14 with an amide linkage in the droxy function, the bromo substituent was introduced by
spacer. Related derivatives were described earlier by us Wohl-Ziegler reaction with N-bromosuccinimide (NBS)
6
9-11
(
3,7) and others (4–6).
The X-ray structure of the and a,a’-azabisisobutyronitrile (AIBN) in CCl . The com-
4
amide substituted 8-hydroxyquinoline 2 shows that the pounds were obtained in 34% (17a), 38% (17b), and 73%
possibility of intramolecular hydrogen bonding suppress- (17c) respectively. The corresponding methyl-substituted
es the intermolecular formation of hydrogen bridged ten derivative 17d was prepared starting from chinaldine (18).
membered rings. Additionally two representative X-ray A Mannich-type reaction of 18 with formaline and mor-
structures of the polymeric strands of 6 and 8 are dis- pholine in 18% yield introduces a N-morpholinomethyl
cussed, which lead to a concept for the control of the poly- group in 7-position of 19. By reaction with acetic anhy-
meric superstructure in the solid state.
dride the N-morpholinomethyl substituent is quantitative-
ly transformed into an acetoxymethyl group.
Simultaneously the hydroxy function is protected as an
acetate. The diacetate 20 reacts with HBr in glacial acetic
acid to obtain bromide 17d after workup in 36% yield.13
However, 19d easily can be obtained over three steps
Results and Discussion
Syntheses of Di(8-hydroxyquinoline) Derivatives
(
starting from 18) without purification of the intermedi-
The structure of (metallo)-supramolecular aggregates ates 19 or 20.
highly depends on the geometric features of the molecular
The benzyl bromides 17 are coupled in a mild homocou-
1
2
components. To introduce different geometries in
CH ) -linked di(8-hydroxyquinoline) derivatives we
15
pling procedure following the protocol of Iyoda and Oda
(
14
2
2
by using the (Ph P) NiBr /Zn/Et NI system. However
3 2 2 4
synthesized the compounds 8–10. The spacers are con-
nected to different positions of the hydroxyquinoline moi-
ety. In derivative 11 additional methyl groups are present
which should introduce steric constraints during the self-
assembly of supermolecules. For the preparation of the
ethylene-linked compounds 8–11 we followed a route
due to solubility problems the yields of the acetyl protect-
ed hydroxyquinoline derivatives 21a–d are low (11–
2
4%). Deprotection is performed by reaction with trifluo-
roacetic acid followed by workup under basic conditions.
In the case of 8, 9 and 11 this reaction proceeds quantita-
tively while 10 (low solubility) is obtained in only 49%
yield.
1
3
which was developed by us using a Ni-catalyzed homo-
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

1
822
M. Albrecht et al.
FEATURE ARTICLE
Scheme 2
Scheme 4
To introduce a (CH ) -spacer, we started from 7-allyl-8-
2
4
hydroxyquinoline (22) (which can be easily prepared by
1
8
Claisen rearrangement of 8-allyloxyquinoline) and pro- bridged di(8-hydroxyquinoline) compounds opens a way
tected the hydroxy functionality by reaction with acetic to prepare analogous derivatives with even longer spacer
anhydride. In the following step a C4-spacer was obtained length.
1
9
by metathesis reaction with Grubbs catalyst. Derivative
4 was prepared in 70% yield as a mixture of the double
bond isomers (ratio of 6:1).
For comparison we additionally synthesized one di(8-hy-
droxyquinoline) derivative 14 with amide units in the
spacer. Compound 14 was obtained in 85% yield by reac-
tion of 7-carboxy-8-hydroxyquinoline (28) with ethylene-
diamine in the presence of carbonyl diimidazole as
2
4
coupling reagent. By analogous reaction of 28 with hex-
ylamine the mono(8-hydroxyquinoline) derivative 2 was
prepared in 89% yield.
Scheme 5
The Solid State Structures of 2–4, 6 and 8
Scheme 3
As already described, 8-hydroxyquinoline (1) forms a
8
dimeric structure in the solid state. In the amide substitut-
In the final step the alkene moiety of 24 was reduced with
hydrogen in the presence of platinum dioxide and the
protecting groups were removed subsequently to obtain
ed compound 2 an additional functionality, which can
form hydrogen bonds, is introduced and should influence
the structure of the compound in the solid state.
2
0
1
2 in 20% yield. Here the low yields are due to the sensi-
tivity of the hydroxyquinoline unit. As a side reaction re-
duction of the heterocyclic portion could be observed.
2
1
Establishment of a (CH ) -spacer 2to obtain 13 is
2
6
In the crystal, 2 forms an intramolecular hydrogen bond
between the phenolic OH group and the amide carbonyl
2
achieved by a double Suzuki reaction.
Hexa-1,5-diene can be hydroborated twice by reaction function leading to a favorable six membered ring (Figure
2
2
with 9-BBN. The resulting diboron compound 26 in situ 3a). Similar intramolecular interactions were already ob-
2
3
24
is coupled with 7-bromo-8-methoxyquinoline (25) in the served in e.g. related catechol amide derivatives.
presence of sodium hydroxide and (dppf)PdCl as cata-
2
Additional intermolecular hydrogen bonding occurs be-
tween the nitrogen atom of the quinoline moiety and the
amide proton of 2. This shows that in derivatives like 2 (or
lyst. The derivative 27 which by this procedure is obtained
in 31% yield is deprotected by ether cleavage with HBr to
yield the di(hydroxyquinoline) derivative 13 in 85% yield.
This Suzuki coupling strategy for the synthesis of alkyl-
1
4) no hydrogen bonded ten membered rings are formed.
The OH group is blocked by intramolecular bridging with
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

FEATURE ARTICLE
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry
1823
are in the spacer while an odd number should prefer the
V”-type structure. Consequently the “Z”-type monomers
should form polymers as it is shown in Figure 4a while the
V”-type monomers should lead to polymers as depicted
in Figure 4b. To check this perception we crystallized the
CH ) -bridged derivative 8 and the CH -bridged 6 and
“
“
(
2
2
2
performed additional X-ray structural analyses.
Figure 3 Representations of the molecular structure of the mono-
meric 2 (a) and of the hydrogen bonded network (b) in the solid state
the carbonyl oxygen atom and the resulting H-donor/ac-
ceptor functions are able to undergo other interactions
(
Figure 3b).
In case of the alkyl bridged derivatives no such intramo-
lecular binding can occur. Therefore polymeric strands
are formed which possess as connecting units doubly hy-
2
5
drogen bridged ten membered rings.
Figure 5 The solid state structure of 8 (monomer: top view (a), side
view (b); polymeric strand (c)).
Figure 4 Schematic representation of a “doubly wound” polymer
a) and of a “zigzag” polymer (b)
(
Figure 4 shows schematic representations of the structures
of the polymeric chains of the already described X-ray
structures of 3 (a) and 4 (b) (see Figure 2). In the case of
3
the ethylene spacer leads to a “Z”-type structure of the
monomer. Hydrogen bridging between monomers results
in a polymeric chain which is “doubly wound”. This
means that the polymeric chain contains alternating left
and right turns as it is depicted in Figure 4a (left: side
Figure 6 The solid state structure of 6 (monomer (a), polymeric
strand (b))
6
view; right: view along the polymer chain).
Compound 4 on the other hand adopts a “V”-type mono-
Derivative 8 possesses an ethylene spacer which is at-
tached to the 2-positions of the two 8-hydroxyquinoline
moieties. Figure 5 shows the structure of the monomeric
mer structure which in the polymer leads to a zigzag chain
7
as it is shown in Figure 4b.
Our assumption was, that the structure of the polymer is
controlled by the nature of the spacer. In case of alkyl
spacers the preferred zigzag conformation should lead to
(
a: top view, b: side view) and polymeric structure (c) in
the solid state. As expected the monomer adopts a “Z”-
type structure and forms a polymeric chain which is “dou-
bly wound” as shown in Figure 4a.
“
Z”-type monomers if an even number of carbon atoms
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M. Albrecht et al.
FEATURE ARTICLE
In contrast to 8 the derivative 6 which is depicted in Figure 13C NMR (CDCl
): d = 170.0 (C), 159.4 (C), 146.9 (C), 140.6 (C),
3
1
36.0 (CH), 127.7 (C), 125.5 (CH), 125.2 (CH), 122.6 (CH), 121.3
6
possesses only one methylene group in the spacer.
(
CH), 25.7 (CH ), 21.0 (CH ).
3 3
Therefore 6 adopts a “V”-type structure leading to a “zig-
zag” polymer (Figure 4b).
IR (KBr): n = 3390, 3053, 2922, 1771, 1601, 1502, 1431, 1368,
1
-
1
203, 1082, 761 cm .
Thus, for polymeric 6 a structure is observed which is
closely related to the one of compound 4.
+
+
MS: m/z (%) = 201 (2) [M] , 159 (100) [M–C H O] .
2
2
HRMS (EI, 70 eV): C H NO (201.23): requires: M 201.0790;
1
2
11
2
+
found M 201.0779.
Conclusion
4-Methylquinolin-8-yl Acetate (16b)
Yield: Quant.; brown solid; mp 83-85 °C.
1
We described the preparation of a number of di(8-hy-
H NMR (CDCl ): d = 8.75 (d, J = 4.0 Hz, 1 H), 7.84 (dd, J = 1.0,
3
droxyquinoline) derivatives which are potential candi- 8.3 Hz, 1 H), 7.49 (dd, J = 7.6, 8.3 Hz, 1 H), 7.42 (dd, J = 1.0, 7.6
Hz, 1 H), 7.21 (d, J = 4.0 Hz, 1 H), 2.64 (s, 3 H), 2.49 (s, 3 H).
dates as building blocks for supramolecular as well as
metallo-supramolecular chemistry.26 The compounds 13C NMR (CDCl
): d = 169.7 (C), 150.0 (CH), 147.6 (C), 144.4 (C),
40.9 (C), 129.5 (C), 125.7 (CH), 122.4 (CH), 121.9 (CH), 121.1
CH), 20.9 (CH ), 18.7 (CH ).
3
1
(
show a broad variation in their geometry, the spacer
length and the nature of the spacer (alkyl versus amide
3
3
linkage). As key steps in the reaction sequences different IR (KBr): n = 3062, 3041, 2986, 2936, 1763, 1508, 1370. 1222,
-
1
1
206, 1172, 1156, 836, 757 cm .
transition metal catalysed coupling reactions were per-
+
+
formed. At the moment investigations towards the coordi- MS: m/z (%) = 201 (2) [M] , 159 (100) [M–C H O] .
2
2
nation behavior and the formation of supramolecular
coordination compounds are going on in our laboratories. found M 201.0797.
HRMS (EI, 70 eV): C H NO (201.23): requires: M 201.0790;
1
2
11
2
+
In the second part of this paper we showed that our alkyl
bridged compounds by hydrogen bonding are able to form
polymeric strands in the solid state. The structure of the
polymers highly depends on the length of the spacer.
Compounds with an even number of atoms in the spacer
lead to a “doubly wound” kind of polymer while deriva-
tives with an odd number of spacer atoms result in a “zig-
zag” polymer chain. A similar structural control
mechanism was observed earlier by us in the formation of
dinuclear helicates from alkyl-bridged ligands with an
even number of atoms in the spacer. An odd number on
the other hand favours the formation of the corresponding
C
12
H
11NO
2
(201.23): calc.
found C 71.32 H 5.63 N 6.47
-Methylquinolin-8-yl Acetate (16c)
C 71.63 H 5.51 N 6.96
5
Yield: Quant.; brown solid; mp 77–78 °C.
1
H NMR (CDCl ): d = 8.98 (dd, J = 1.6, 4.2 Hz, 1 H), 8.33 (dd,
3
J = 1.6, 8.5 Hz, 1 H), 7.47 (dd, J = 4.2, 8.5 Hz, 1 H), 7.35 (s, 2 H),
2
.65 (s, 3 H), 2.50 (s, 3 H).
1
3
C NMR (CDCl ): d = 170.1 (C), 149.9 (CH), 145.4 (C), 141.0 (C),
3
1
33.2 (CH), 132.8 (C), 128.7 (C), 126.5 (CH), 121.4 (CH, double
intensity), 21.0 (CH ), 18.4 (CH )
3
3
IR (KBr): n = 3037, 2931, 1756, 1501, 1371, 1210, 1063, 902, 795
cm .
-1
2
7
meso-helicate.
+
+
MS: m/z (%) = 201 (2) [M] , 159 (100) [M–C H O] .
2
2
If an amide group is connected to the 7-position of the
quinoline, intramolecular hydrogen bonding takes place
and suppresses the formation of ten membered rings.
HRMS (EI, 70 eV): C H NO (201.23): requires: M 201.0790;
1
2
11
2
+
found M 201.0800.
C H NO ⋅ ½ H O: calc.
C 68.56 H 5.75 N 6.66
found C 68.55 H 5.68 N 6.44
1
2
11
2
2
1H NMR and 13C NMR spectra were recorded on a Bruker DRX
5
00, AM 400, or WM 250 NMR spectrometer using DEPT tech-
(Bromomethyl)quinolin-8-yl Acetate (17a–c); General Proce-
dure
8-Acetoxymethylquinoline (16, approx. 10 mmol) is dissolved in
niques for the assignment of the multiplicity of carbon atoms. FT-
IR spectra were recorded by diffuse reflection (KBr) on a Bruker
IFS spectrometer. Mass spectra (EI, 70 eV or FAB(+), 3-NBA as
matrix) were taken on a Finnigan MAT 90 mass spectrometer. Ele-
mental analyses were obtained with a Heraeus CHN-O-Rapid ana-
lyzer. Solvents were purified by standard methods. Melting points:
Büchi 535 (uncorrected). Air sensitive compounds were prepared
and handled under Ar using Schlenk techniques.
CCl (15 mL) under Ar, 1 equiv. of NBS (N-bromosuccinimide) and
4
of AIBN (50 mg) are added and the mixture is refluxed overnight.
Solvent is evaporated and the residue is dissolved in CH Cl (150
2
2
mL), washed with aq NaHCO (3 x 50 mL), dried (MgSO ) and sol-
3
4
vent is removed in vacuo. The crude product is purified by column
chromatography (silica gel, hexane / EtOAc 5:1).
2
-(Bromomethyl)quinolin-8-yl Acetate (17a)
Methylquinolin-8-yl Acetates (16); General Procedure
Yield: 34%; yellow solid; mp 71–73 °C.
3
,16,17
8
1
-Hydroxymethylquinoline 15
5 h. The mixture is evaporated and the residue is dissolved in
is refluxed in Ac O (50 mL) for
2
1
H NMR (CDCl ): d = 8.15 (d, J = 8.6 Hz, 1 H), 7.68 (dd, J = 1.4,
3
8
.2 Hz, 1 H), 7.58 (d, J = 8.6 Hz, 1 H), 7.52 (dd, J = 7.6, 8.2 Hz, 1
CH Cl , washed with aq NaHCO , dried (MgSO ) and taken to dry-
2
2
3
4
H), 7.45 (dd, J = 1.4, 7.6 Hz, 1 H), 4.69 (s, 2 H), 2.52 (s, 3 H).
ness to obtain methylquinolin-8-yl acetates 16.
1
3
C NMR (CDCl ): d = 169.8 (C), 156.9 (C), 147.4 (C), 140.2 (C),
2
-Methylquinolin-8-yl Acetate (16a)
3
1
37.2 (CH), 128.5 (C), 126.7 (CH), 125.6 (CH), 121.9 (CH), 34.5
Yield: Quant.; yellow oil.
(CH ), 21.0 (CH ).
2 3
1
H NMR (CDCl ): d = 8.02 (d, J = 8.4 Hz, 1 H), 7.65 (dd, J = 1.5,
3
-
1
IR (KBr): n = 3060, 1768, 1502, 1370, 1204, 1077, 827, 690 cm .
8
.0 Hz, 1 H), 7.44 (t, J = 8.0 Hz, 1 H), 7.44 (d, J = 1.5 Hz, 1 H), 7.27
+
+
(
d, J = 8.4 Hz, 1 H), 2.72 (s, 3 H), 2.51 (s, 3 H).
MS: m/z (%) = 279 (1) [M] , 158 (100) [M–C H OBr] .
2 2
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

FEATURE ARTICLE
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry
1825
1
3
HRMS (EI, 70 eV): C H NO Br (280.12): requires: M 278.9895;
found M 278.9875.
C NMR (CDCl ): d = 170.5 (C), 129.3 (C), 159.4 (C), 145.2 (C),
1
2
10
2
3
+
140.2 (C), 135.6 (CH), 127.8 (C), 127.3 (C), 125.9 (CH), 125.0
(
CH), 122.6 (CH), 61.1 (CH ), 25.4 (CH ), 20.6 (CH ), 20.5 (CH ).
2 3 3 3
C H NO Br:
calc.
found C 51.91 H 3.70 N 5.04
-(Bromomethyl)quinolin-8-yl Acetate (17b)
C 51.45 H 3.60 N 5.00
1
2
10
2
IR (KBr): n = 3366, 2965, 2927, 2859, 2586, 1770, 1742, 1609,
1
-
1
513, 1431, 1368, 1233, 1199, 1085, 1028 cm .
4
+
+
MS: m/z (%) = 273 (5) [M] , 231 (100) [M–C H O] , 189 (13) [M–
C H O ] .
2
2
Yield: (38%); green solid (containing approx. 15% of 16b).
+
4
4
2
1
H NMR (CDCl ): d = 8.86 (d, J = 4.4 Hz, 1 H), 8.01 (dd, J = 1.2,
3
HRMS (EI, 70 eV): C H NO (273.29): requires: M 273.1001;
found M 273.1015.
1
5
15
4
8
.5 Hz, 1 H), 7.63 (dd, J = 7.6, 8.5 Hz, 1 H), 7.47 (dd, J = 1.2, 7.6
+
Hz, 1 H), 7.43 (d, J = 4.4 Hz, 1 H), 4.81 (s, 2 H), 2.51 (s, 3 H).
1
3
C NMR (CDCl ): d = 170.0 (C), 150.2 (CH), 147.9 (C), 142.6 (C),
3
7
7
9
-(Bromomethyl)-2-methylquinolin-8-yl Acetate (17d)
1
41.7 (C), 127.3 (C), 126.8 (CH), 122.0 (CH), 121.9 (CH), 121.6
-[(Acetyloxy)methyl]-2-methylquinolin-8-yl acetate (20) (2.50 g,
.58 mmol) is dissolved in CH Cl (25 mL) and a 30% solution of
(
CH), 28.2 (CH ), 21.0 (CH ).
2 3
2
2
+
+
MS: m/z (%) = 281 (1) [M] , 158 (100) [M–C H OBr] .
HBr in glacial acetic acid (75 mL) is added. After 3 days at r.t. Ac O
2
2
2
(
9.5 ml) is added. Volatile components are removed in vacuo and
HRMS (EI, 70 eV): C H NO Br (280.12): requires: M 278.9895;
1
2
10
2
+
the residue is purified by column chromatography (silica gel, hex-
ane/EtOAc 1:2); yield: 1.00 g (36%); yellow solid; mp 162–164 °C.
found M 278.9881.
-(Bromomethyl)quinolin-8-yl acetate (17b) is used without further
purification.
-(Bromomethyl)quinolin-8-yl Acetate (17c)
4
1
H NMR (CDCl ): d = 8.01 (d, J = 8.4 Hz, 1H), 7.64 (d, J = 8.5 Hz,
3
1
H), 7.49 (d, J = 8.5 Hz, 1 H), 7.29 (d, J = 8.4 Hz, 1 H), 4.62 (s, 2
5
H), 2.73 (s, 3 H), 2.57 (s, 3 H).
1
Yield: 73%; light brown solid; mp 134–135 °C.
3
C NMR (CDCl ): d = 169.3 (C), 159.9 (C), 145.2 (C), 140.3 (C),
3
1
H NMR (CDCl ): d = 8.95 (dd, J = 1.6, 4.2 Hz, 1 H), 8.47 (dd,
3
136.1 (CH), 129.7 (C), 127.6 (C), 126.9 (CH), 125.6 (CH), 123.0
CH), 27.2 (CH ), 25.6 (CH ), 20.9 (CH ).
J = 1.6, 8.6 Hz, 1 H), 7.58 (d, J = 7.7 Hz, 1 H), 7.54 (dd, J = 4.2, 8.6
Hz, 1 H), 7.36 (d, J = 7.7 Hz, 1 H), 4.88 (s, 2 H), 2.50 (s, 3 H).
(
2
3
3
IR (KBr): n = 3047, 2986, 1769, 1444, 1428, 1372, 1213, 1204,
1176, 1081, 842 cm .
MS: m/z (%) = 293 (1) [M] , 251 (7) [M–C H O] , 158 (100) [M–
1
3
C NMR (CDCl ): d = 169.6 (C), 150.6 (CH), 148.3 (C), 141.7 (C),
-1
3
1
32.5 (CH), 131.8 (C), 127.8 (CH), 127.6 (C), 121.9 (CH), 121.8
+
+
2
2
(
CH), 121.0 (CH), 29.7 (CH ), 21.0 (CH ).
2 3
+
C H OBr] .
2
2
IR (KBr): n = 3492, 1759, 1505, 1227, 1207, 1151, 1063, 907, 788,
-
1
HRMS (EI, 70 eV): C13
found M 293.0065.
H12NO
2
Br (294.15): requires: M 293.0052;
C 53.08 H 4.11 N 4.76
7
04 cm .
+
+
+
MS: m/z (%) = 279 (1) [M] , 158 (100) [M–C H OBr] .
2
2
C H NO Br (294.15):calc.
1
3
12
2
HRMS (EI, 70 eV): C H NO Br (280.12): requires: M 278.9895;
1
2
10
2
+
found C 52.57 H 4.31 N 4.14
found M 278.9883.
C H NO Br ⋅ ½ H O: calc.
C 49.85 H 3.83 N 4.84
found C 49.79 H 3.91 N 4.76
1
2
10
2
2
1
,2-Di(8-acetoxyquinolinyl)ethane (21); General Procedure
Dibromobis(triphenylphosphane)nickel (350 mg, 0.47 mmol), tet-
raethylammonium iodide (2.43 g, 9.43 mmol) and activated zinc
(
925 mg, 14.1 mmol) are suspended in anhyd THF (20 mL) under
2
2
-Methyl-7-(morpholin-4-ylmethyl)quinolin-8-ol (19)
-Methylquinolin-8-ol 18 (5.00 g, 31.4 mmol) is dissolved in EtOH
1
5
Ar. The mixture is stirred for 3 h and a solution of (bromometh-
yl)quinolin-8-yl acetate 17 (3.14 mmol) in THF (20 mL) is added.
After 3 h the solvent is removed in vacuo and the residue is chro-
matographed (silica gel, hexane / EtOAc 1:2).
(90 ml) and morpholine (2.73 ml, 31.4 mmol) and formaline (3.70
ml, 53.4 mmol) are added. The mixture is stirred for 15 h at r.t. and
solvent is removed in vacuo. The crude product is purified by col-
umn chromatography (gradient: CH Cl → CH Cl /MeOH 49:1);
yield: 1.45 g (18%); yellow oil.
2
2
2
2
1,2-Di(8-acetoxyquinolin-2-yl)ethane (21a)
Yield: 17%; yellow solid; mp 130 °C.
1
H NMR (CDCl ): d = 7.88 (d, J = 8.4 Hz, 1 H), 7.17 (d, J = 8.4 Hz,
1
3
H NMR (CDCl ): d = 7.99 (d, J = 8.5 Hz, 2 H), 7.63 (dd, J = 1.7,
3
1
H), 7.14 (d, J = 8.4 Hz, 1 H), 7.12 (d, J = 8.4 Hz, 1 H), 3.77 (s, 2
7
.9 Hz, 2 H), 7.44 (dd, J = 7.5, 7.9 Hz, 2 H), 7.41 (dd, J = 1.7, 7.5
H), 3.70 (t, J = 4.7 Hz, 4 H), 2.68 (s, 3 H), 2.54 (br s, 4 H).
Hz, 2 H), 7.27 (d, J = 8.5 Hz, 2 H), 3.55 (s, 4 H), 2.51 (s, 6 H).
1
3
C NMR (CDCl ): d = 157.4 (C), 151.7 (C), 138.2 (C), 135.7 (CH),
13
3
C NMR (CDCl ): d = 169.8 (C), 161.7 (C), 147.2 (C), 140.5 (C),
3
1
26.8 (CH), 126.3 (C), 122.1 (CH), 117.3 (C), 117.1 (CH), 66.9
1
36.0 (CH), 128.0 (C), 125.5 (CH), 125.3 (CH), 122.4 (CH), 121.1
(
CH ), 60.0 (CH ), 52.9 (CH ), 25.2 (CH ).
2 2 2 3
(CH), 37.4 (CH ), 20.9 (CH ).
2
3
+
+
MS: m/z (%) = 258 (1) [M] , 73 (100) [M–C H NO] .
4
7
IR (KBr): n = 3391, 3062, 2913, 1756, 1503, 1433, 1208, 1076,
1
-
8
35, 755 cm .
HRMS (EI, 70 eV): C H N O (258.32): requires: M 258.1368;
1
5
18
2
2
+
found M 258.1355.
+
+
MS: m/z (%) = 400 (1) [M] , 159 (100) [M–C H NO ] .
1
4
11
3
HRMS (EI, 70 eV): C H N O (400.43): requires: M 400.1423;
found M 400.1415.
2
4
20
2
4
7
2
-[(Acetyloxy)methyl]-2-methylquinolin-8-yl Acetate (20)
-Methyl-7-(morpholin-4-ylmethyl)quinolin-8-ol (19) (1.45 g, 5.74
+
1
C H N O ⋅ / H O: calc.
C 71.19 H 5.10 N 6.92
found C 70.83 H 5.20 N 6.96
,2-Di(8-acetoxyquinolin-4-yl)ethane (21b)
Yield: 18%; yellow solid; mp 206–208 °C.
mmol) is refluxed for 15 h in Ac O (20 mL). After evaporation of
the solvent, the remaining oil is dissolved in CH Cl (50 mL),
washed with aq NaHCO (3 times), dried (MgSO ), and the CH Cl
is removed in vacuo; yield: 1.57 g (quant.); brown oil.
24 20
2
4
4
2
2
2
2
3
4
2
2
1
1
H NMR (CDCl ): d = 7.93 (d, J = 8.5 Hz, 1 H), 7.57 (d, J = 8.5 Hz,
3
1
H), 7.45 (d, J = 8.5 Hz, 1 H), 7.20 (d, J = 8.5 Hz, 1 H), 5.23 (s, 2
H), 2.64 (s, 3 H), 2.47 (s, 3 H), 2.04 (s, 3 H).
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

1
826
M. Albrecht et al.
FEATURE ARTICLE
1
H NMR (CDCl ): d = 8.79 (d, J = 4.3 Hz, 2 H), 7.91 (dd, J = 1.0,
HRMS (EI, 70 eV): C H N O (316.36): requires: M 316.1212;
found M 316.1198.
3
20 16
2
2
+
8
.5 Hz, 2 H), 7.57 (dd, J = 7.5, 8.5 Hz, 2 H), 7.47 (dd, J = 1.0, 7.5
Hz, 2 H), 7.20 (d, J = 4.3 Hz, 2 H), 3.52 (s, 4 H), 2.52 (s, 6 H).
C H N O ⋅ H O:
calc.
C 71.84 H 5.43 N 8.38
2
0
16
2
2
2
1
3
C NMR (CDCl ): d = 169.9 (C), 150.2 (CH), 148.2 (C), 146.6 (C),
3
found C 72.28 H 5.12 N 8.14
1
41.5 (C), 128.6 (C), 126.4 (CH), 121.5 (CH), 121.4 (CH), 121.2
X-ray Structural Analysis of 1,2-Di(8-hydroxyquinolin-2-
yl)ethane (8)
(
CH), 32.3 (CH ), 21.1 (CH ).
2 3
-
1
IR (KBr): n = 1767, 1593, 1507, 1221, 1199, 1175, 856, 756 cm .
X-ray quality crystals of 8 were obtained from CH Cl . C H N O ,
2
2
20 16
2
2
+
+
-1
MS: m/z (%) = 400 (1) [M] , 316 (100) [M–C H O ] .
M = 316.35 gmol , monoclinic, a = 13.242(3), b = 11.454(3),
4
4
2
3
c = 10.442(2) Å, β = 107.49(2)°, V = 1510.6(6) Å , C2/c,
HRMS (EI, 70 eV): C H N O (400.43): requires: M 400.1423;
2
4
20
2
4
-1
-3
+
µ(CuK ) = 0.732 mm , Z = 4, D = 1.391 g cm , F(000) = 664,
α
c
found M 400.1399.
C H N O ⋅ ½ H O: calc.
T = 223(2) K. Data were recorded with a Enraf Nonius CAD4 dif-
fractometer. 1618 collected reflections, 1530 unique reflections
C 70.40 H 5.17 N 6.84
found C 70.09 H 5.17 N 6.74
,2-Di(8-acetoxyquinolin-5-yl)ethane (21c)
2
4
20
2
4
2
[
999 I > 2σ(I)] were used for refinement. Lp correction. Psi scan ab-
sorption correction used (Tmin = 92.7, Tmax = 99.7%). Structure so-
1
28
2
lution by direct methods (SHELXS97 ), refinement on F
Yield: 11%; yellow solid; mp 231–233 °C.
29
(
SHELXL97 ). The hydrogen positions are of riding model with
1
2
H NMR (CDCl ): d = 8.92 (dd, J = 1.5, 4.2 Hz, 2 H), 8.24 (dd,
fixed isotropic U. R = 0.0430, wR = 0.1055 [I > 2σ(I)],
3
2
J = 1.5, 8.5 Hz, 2 H), 7.41 (dd, J = 4.2, 8.5 Hz, 2 H), 7.35 (d, J = 7.8
Hz, 2 H), 7.32 (d, J = 7.8 Hz, 2 H), 3.45 (s, 4 H), 2.51 (s, 6 H).
R = 0.0891, wR = 0.1232 (all data) for 110 parameters. The crys-
tallographic data have been deposited with the Cambridge Crystal-
lographic Data Centre as supplementary publication no. CCDC
1
3
C NMR (CDCl ): d = 169.9 (C), 150.1 (CH), 146.2 (C), 141.4 (C),
3
1
20867.
1
35.9 (C), 132.1 (CH), 127.9 (C), 126.0 (CH), 121.5 (CH), 121.1
(
CH), 29.7 (CH ), 21.1 (CH ).
1,2-Di(8-hydroxyquinolin-4-yl)ethane (9)
2
3
Yield: 49%; white solid; m.p. 270 °C.
IR (KBr): n = 3430, 2925, 2855, 1762, 1365, 1213, 1065, 902, 786,
-
1
1
7
00 cm .
H NMR (CDCl ): d = 9.72 (s, 2 H), 8.71 (d, J = 4.4 Hz, 2 H), 7.59
3
FAB(+) MS: m/z (%) = 401 (10) [MH]+.
(d, J = 8.3 Hz, 2 H), 7.46 (dd, J = 7.7, 8.3 Hz, 2 H), 7.40 (d, J = 4.4
Hz, 2 H), 7.08 (d, J = 7.7 Hz, 2 H), 3.49 (s, 4 H).
1
,2-Di(8-acetoxy-2-methylquinolin-7-yl)ethane (21d)
1
3
C NMR (CDCl ): d = 153.8 (C), 147.6 (CH), 147.0 (C), 138.5 (C),
3
Yield: 24%; white solid; mp 158–160 °C.
1
27.8 (C), 127.5 (CH), 121.5 (CH), 113.5 (CH), 110.8 (CH), 31.5
1
H NMR (CDCl ): d = 7.97 (d, J = 8.4 Hz, 2 H), 7.53 (d, J = 8.4 Hz,
3
(CH2).
2
H), 7.27 (d, J = 8.4 Hz, 2 H), 7.24 (d, J = 8.4 Hz, 2 H), 3.11 (s, 4
-
1
IR (KBr): n = 3307, 1516, 1406, 1270, 1220, 1168, 743 cm .
MS: m/z (%) = 316 (100) [M]+.
H), 2.72 (s, 6 H), 2.57 (s, 6 H).
1
3
C NMR (CDCl ): d = 170.0 (C), 159.3 (C), 144.7 (C), 140.7 (C),
3
1
35.9 (CH), 133.4 (C), 127.4 (CH), 126.3 (C), 125.0 (CH), 122.0
HRMS (EI, 70 eV): C H N O (316.36): requires: M 316.1212;
2
0
16
2
2
+
(
CH), 31.1 (CH ), 25.8 (CH ), 20.9 (CH ).
found M 316.1201.
C H N O ⋅ ¾ H O: calc.
2
3
3
-
1
IR (KBr): n = 3404, 1770, 1509, 1368, 1201, 1170, 1077, 841 cm .
C 72.82 H 5.35 N 8.49
found C 72.86 H 5.34 N 8.09
,2-Di(8-hydroxyquinolin-5-yl)ethane (10)
2
0
16
2
2
2
+
+
MS: m/z (%) = 428 (2) [M] , 386 (18) [M–C H O] , 344 (7) [M–
2
2
+
+
C H O ] , 172 (100) [M–C H NO ] .
4
4
2
15 14
3
1
HRMS (EI, 70 eV): C H N O (428.49): requires: M 428.1736;
found M 428.1724.
Yield: Quant.; yellow solid; mp >285 °C.
2
6
24
2
4
+
1
H NMR (CDCl ): d = 8.82 (dd, J = 1.4, 4.1 Hz, 2 H), 8.43 (dd,
3
C H N O :
calc.
C 72.88 H 5.65 N 6.54
J = 1.4, 8.6 Hz, 2 H), 7.53 (dd, J = 4.1, 8.6 Hz, 2 H), 7.25 (d, J = 7.8
Hz, 2 H), 6.96 (d, J = 7.8 Hz, 2 H), 3.27 (s, 4 H).
2
6
24
2
4
found C 72.41 H 5.80 N 6.51
1
3
C NMR (CDCl ): d = 151.8 (C), 147.6 (CH), 138.7 (C), 132.6
3
1
,2-Di(8-hydroxyquinolinyl)ethane; General Procedure
(CH), 127.7 (C), 127.3 (CH), 127.0 (C), 121.6 (CH), 110.6 (CH),
32.7 (CH ).
1
,2-Di(8-acetoxyquinolinyl)ethane 21 (approx. 0.5 mmol) is dis-
2
solved in MeOH (10 mL) and 10 drops of TFA are added. The mix-
ture is stirred for 3 days at r.t. and then the solvent is evaporated.
The residue is dissolved in CH Cl (30 mL), washed with aq
IR (KBr): n = 3345, 2546, 1923, 1670, 1622, 1507, 1477, 1370,
-1
8
37, 698 cm .
FAB(+) MS: m/z (%) = 317 (7) [M+H]+.
C H N O ⋅ ½ H O: calc. C 73.83 H 5.27 N 8.61
found C 74.04 H 4.89 N 9.46
,2-Di(8-hydroxy-2-methylquinolin-7-yl)ethane (11)
2
2
NaHCO (3 times), dried (MgSO ) and solvent is removed in vacu-
3
4
um.
2
0
16
2
2
2
1
,2-Di(8-hydroxyquinolin-2-yl)ethane (8)
Yield: Quant.; yellow solid; mp 164 °C.
1
1
H NMR (CDCl ): d = 8.20 (br s, 2 H), 8.05 (d, J = 8.4 Hz, 2 H),
Yield: Quant.; white solid; mp 177–178 °C.
3
7
.39 (pseudo t, J = 7.7 Hz, 2 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.28 (dd,
1
H NMR (CDCl ): d = 8.46 (br s, 2 H), 7.98 (d, J = 8.3 Hz, 2 H),
3
J = 1.0, 7.7 Hz, 2 H), 7.14 (dd, J = 1.0, 7.7 Hz, 2 H), 3.58 (s, 4 H).
7
.29 (d, J = 8.3 Hz, 2 H), 7.24 (d, J = 8.3 Hz, 2 H), 7.18 (d, J = 8.3
1
3
C NMR (CDCl ): d = 159.4 (C), 151.8 (C), 137.7 (C), 136.4 (CH),
Hz, 2 H), 3.26 (s, 4 H), 2.73 (s, 6 H).
3
1
26.9 (CH), 122.5 (CH), 117.7 (CH), 109.9 (CH), 37.0 (CH ); one
2
13
C NMR (CDCl ): d = 156.7 (C), 148.8 (C), 137.4 (C), 136.1 (CH),
3
C is not observed.
1
29.0 (CH), 125.1 (C), 123.7 (C), 121.8 (CH), 116.8 (CH), 30.3
IR (KBr): n = 2939, 1570, 1509, 1455, 1443, 1273, 1247, 839, 752,
(CH ), 24.9 (CH ).
2 3
-
1
6
99 cm .
-
1
IR (KBr): n = 3362, 1511, 1455, 1443, 1250, 839, 688, 613 cm .
MS: m/z (%) = 316 (100) [M]+.
+
+
MS: m/z (%) = 344 (40) [M] , 127 (100) [M–C H NO] .
1
1
10
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

FEATURE ARTICLE
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry
1827
1
HRMS (EI, 70 eV): C H N O (344.41): requires: M 344.1525;
H NMR (CDCl ): d = 8.74 (d, J = 3.2 Hz, 2 H), 8.28 (br s, 2 H),
2
2
20
2
2
3
+
found M 344.1537.
C H N O ⋅ ½ H O: calc.
8.11 (d, J = 8.1 Hz, 2 H), 7.37 (dd, J = 3.2, 8.1 Hz, 2 H and d, J = 8.5
Hz, 2 H), 7.27 (d, J = 8.5 Hz, 2 H), 2.93 (m, 4 H), 1.84 (m, 4 H).
C 74.77 H 5.99 N 7.93
found C 75.54 H 6.05 N 7.92
2
2
20
2
2
2
1
3
C NMR (CDCl ): d = 149.1 (C), 147.7 (CH), 138.1 (C), 135.9
3
(
2
CH), 129.9 (CH), 126.8 (C), 124.3 (C), 120.9 (CH), 117.1 (CH),
9.8 (CH ), 29.7 (CH ).
2
2
7
7
-Allylquinolin-8-yl Acetate (23)
-Allylquinolin-8-ol (22) (6.93 g, 37.5 mmol) is refluxed in Ac O
1
8
IR (KBr): n = 3333, 2859, 1504, 1470, 1405, 1371, 1283, 1239,
1
2
-
1
118, 832, 825, 673 cm .
(50 mL) for 15 h. Solvent is removed in vacuum and the residue is
dissolved in CH Cl , washed with H O, dried (MgSO ) and the
+
+
2
2
2
4
MS: m/z (%) = 344 (75) [M] , 159 (100) [M–C H NO] .
1
2
11
CH Cl is evaporated; yield: 8.50 g (quant.); green oil.
2
2
HRMS (EI, 70 eV): C H N O (344.41): requires: M 344.1525;
found M 344.1511.
2
2
20
2
2
1
H NMR (CDCl ): d = 8.90 (dd, J = 1.6, 4.2 Hz, 1 H), 8.10 (dd,
+
3
J = 1.6, 8.3 Hz, 1 H), 7.64 (d, J = 8.5 Hz, 1 H), 7.42 (d, J = 8.5 Hz,
1
3
H), 7.36 (dd, J = 4.2, 8.3 Hz, 1 H), 5.97 (m, 1 H), 5.15 (m, 2 H),
.54 (m, 2 H), 2.52 (s, 3 H).
1
,2-Di(8-methoxyquinoline-7-yl)hexane (27)
At 0 °C a 0.5 M solution of 9-BBN in THF (4.88 mL, 2.44 mmol)
is added to hexa-1,5-diene (0.15 ml, 1.22 mmol) in anhyd THF (2
mL). The mixture is allowed to warm to r.t. and is stirred for 4.5
1
3
C NMR (CDCl ): d = 169.5 (C), 150.4 (CH), 144.8 (C), 141.3 (C),
3
2
2
1
35.9 (CH), 135.4 (CH), 132.3 (C), 128.3 (CH), 128.1 (C), 125.4
(
CH), 121.1 (CH), 116.7 (CH ), 34.8 (CH ), 20.9 (CH ).
h. A mixture of aq 3 M NaOH (2.5 mL), THF (10 mL), PdCl (dppf)
2
2
3
2
(
116 mg, 0.15 mmol) and 25 (580 mg, 2.44 mmol) is added to the
IR (KBr): n = 1762, 1501, 1463, 1365, 1203, 1173, 1078, 914, 836,
-
1
in situ prepared 26 and the solution is refluxed for 15 h. Solvents are
evaporated and the residue is chromatographed (silica gel, hexane /
ethyl acetate 5:1); yield: 150 mg (31%); beige solid; mp 94–96 °C.
1
8
04 cm .
+
+
MS: m/z (%) = 227 (3) [M] , 170 (100) [M–C HO ] .
2
2
HRMS (EI, 70 eV): C H NO (227.26): requires: M 227.0946;
1
9
27
H NMR (CDCl ): d = 8.91 (d, J = 3.5 Hz, 2 H), 8.10 (d, J = 8.3 Hz,
3
+
found M 227.0936.
2
H), 7.49 (d, J = 8.3 Hz, 2 H), 7.37 (d, J = 8.3 Hz, 2 H), 7.34 (dd,
J = 3.5, 8.3 Hz, 2 H), 4.10 (s, 6 H), 2.85 (t, J = 7.8 Hz, 4 H), 1.70
(m, 4 H), 1.47 (m, 4 H).
1
,4-Di(8-acetoxyquinolin-7yl)but-2-ene (24)
A solution of 7-allylquinolin-8-yl acetate (23) (850 mg, 3.75 mmol)
1
3
C NMR (CDCl ): d = 153.3 (C), 149.3 (CH), 142.7 (C), 136.2
3
in CH Cl (5 mL) under Ar slowly is added to the metathesis cata-
2
2
(
6
CH), 135.4 (C), 129.0 (CH), 128.3 (C), 122.9 (CH), 120.4 (CH),
2.4 (CH ), 30.7 (CH ), 30.1 (CH ), 29.5 (CH ).
lyst benzylidene dichlorobis(tricyclohexylphosphane)rutheni-
um(II)19 (100 mg, 0.12 mmol) in CH Cl (5 mL). The mixture is
3
2
2
2
2
2
IR (KBr): n = 3417, 2941, 2922, 2855, 1499, 1465, 1435, 1230,
1111, 1086, 830, 809, 705 cm .
MS: m/z (%) = 400 (100) [M]+.
refluxed for 15 h and solvent is removed in vacuo. The crude prod-
uct can be used without further purification or can be purified by
column chromatography (silica gel, gradient: hexane / EtOAc 1:1
-
1
→
EtOAc); yield: 560 mg (70%); brown solid; two isomers:1:6.
HRMS (EI, 70 eV): C H N O (400.52): requires: M 400.2151;
found M 400.2135.
C H N O ⋅ ½ H O: calc.
2
6
28
2
2
1
H NMR (CDCl ): d = 8.84 (d, J = 4.3 Hz, 2 H), 7.99 (d, J = 7.9 Hz,
+
3
2
H), 7.56 (d, J = 8.4 Hz, 2 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.24 (dd,
J = 4.3, 7.9 Hz, 2 H), 5.76 / 5.72 (m, Σ 2 H), 3.71 / 3.51 (d, J = 4.7
Hz (each), Σ 4 H), 2.48 (s, 6 H).
C 76.25 H 7.14 N 6.84
found C 76.09 H 7.25 N 6.38
2
6
28
2
2
2
1
3
C NMR (CDCl ): d (major isomer) = 169.6 (C), 150.4 (CH), 144.8
3
1
,2-Di(8-hydroxyquinoline-7-yl)hexane (13)
(
C), 141.3 (C), 135.9 (CH), 132.5 (C), 129.4 (CH), 128.4 (CH),
1
,2-Di(8-methoxyquinoline-7-yl)hexane (27) (110 mg, 0.27 mmol)
1
28.1 (C), 125.5 (CH), 121.1 (CH), 33.6 (CH ), 20.9 (CH ); d(mi-
2
3
for 2 h is refluxed in 48% HBr (8 mL). The solution is neutralized
by addition of NaHCO and extracted with CH Cl (3 x 50 mL).
The organic layer is dried (MgSO ) and evaporated to drieness;
nor isomer) = 150.5 (CH), 144.7 (CH), 132.7 (C), 128.2 (CH),
27.9 (C), 125.6 (CH), 121.2 (CH), 28.4 (CH2).
1
3
2
2
4
IR (KBr): n = 3041, 2934, 1762, 1499, 1463, 1365, 1205, 1172,
1
MS: m/z (%) = 426 (1) [M]+.
yield: 90 mg (85%); grey solid; mp 138 °C.
-
1
081, 837 cm .
1
H NMR (CDCl ): d = 8.75 (d, J = 3.1 Hz, 2 H), 8.15 (d, J = 8.0 Hz,
3
2
H), 7.39 (d, J = 3.1, 8.0 Hz, 2 H), 7.36 (d, J = 8.3 Hz, 2 H), 7.28
HRMS (EI, 70 eV): C H N O (426.47): requires: M 426.1580;
found M 426.1596.
(d, J = 8.3 Hz, 2 H), 2.86 (t, J = 7.7 Hz, 4 H), 1.73 (m, 4 H), 1.47 (t,
J = 6.8 Hz, 4 H).
2
6
22
2
4
+
1
3
C H N O ⋅ H O:
calc.
C 70.26 H 5.44 N 6.30
C NMR (CDCl ): d = 148.8 (C), 147.2 (CH), 157.3 (C), 136.6
3
2
6
22
2
4
2
(
3
CH), 130.1 (CH), 126.9 (C), 125.4 (C), 120.7 (CH), 117.2 (CH),
0.0 (CH ), 29.9 (CH ), 29.4 (CH ).
found C 70.39 H 5.15 N 6.18
2
2
2
1
,4-Di(8-hydroxyquinolin-7yl)butane (12)
Platinum dioxide (150 mg) is added to a solution of 24 (750 mg,
.76 mmol) in CH Cl /EtOH (20 mL, 1:1) and the mixture is stirred
IR (KBr): n = 3312, 2926, 2861, 2850, 1506, 1466, 1407, 1288,
1
-
1
231, 823, 715 cm .
1
+
+
2
2
MS: m/z (%) = 372 (27) [M] , 159 (100) [M–C H NO] .
1
4
15
under an atmosphere of H for 4.5 h. The solvent is removed in vac-
2
HRMS (EI, 70 eV): C H N O (372.47): requires: M 372.1838;
2
4
24
2
2
uo and the residue is applied to column chromatography (silica gel,
gradient: hexane/EtOAc 1:2 → MeOH). The obtained 1,4-di(8-ace-
toxyquinoline)butane immediately is dissolved in MeOH and 10
drops of TFA are added. After 3 days at r.t. the solvent is removed
and the residue is dissolved in CH Cl , washed with aq NaHCO ,
+
found M 372.1853.
C H N O ⋅ H O:
calc.
C 73.20 H 6.20 N 6.39
2
4
24
2
2
2
found C 73.82 H 6.71 N 7.17
2
2
3
dried and the solvent is removed; yield: 110 mg (20%); green solid;
mp 172–174 °C.
N-Hexyl-8-hydroxyquinoline-7-carboxamide (2)
-Hydroxyquinoline-7-carboxylic acid (28) (500 mg, 2.64 mmol)
and carbonyl diimidazole (470 mg, 2.91 mmol) are refluxed in an-
8
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

1
828
M. Albrecht et al.
FEATURE ARTICLE
hyd THF (50 ml) for 1 h under Ar. Hexylamine (350 mL, 2.64
mmol) in THF (4 mL) is added to the refluxing mixture, which after
completion of the addition is heated overnight. Solvent is removed
and the residue is dissolved in CH Cl , washed with aq NH Cl and
X-ray Structural Analysis of Di(8-hydroxyquinolin-2-yl)meth-
ane (6)
1
1
Compound 6 was prepared as described in the literature. X-ray
quality crystals of 6 were obtained from CH Cl . C H N O ,
2
2
4
2
2
19 14
2
2
-
1
brine, dried (MgSO ) and evaporated in vacuum; yield: 604 mg
M = 302.32 gmol , triclinic, a = 8.591(2), b = 13.237(3),
c = 14.479(3) Å, α = 67.38(3), β = 87.37(3), γ = 87.94(3)°,
4
(
89%); yellow solid; mp 94 °C.
3
-1
1
V = 1518.0(6) Å , P-1, µ(CuK
α
) = 0.704 mm , Z = 4, D
c
= 1.323 g
H NMR (CDCl ): d = 8.82 (d, J = 3.8 Hz, 1 H), 8.45 (br s, 1 H),
3
-3
cm , F(000) = 632, T = 223(2) K. Data were recorded with an En-
raf Nonius CAD4 diffractometer. 6626 collected reflections, 6192
unique reflections [2996 I > 2σ(I)] were used for refinement. Lp
8
.12 (d, J = 8.5 Hz, 2 H), 7.90 (s, 1 H), 7.45 (dd, J = 3.8, 8.5 Hz, 1
H), 7.32 (d, J = 8.5 Hz, 1 H), 3.52 (m, 2 H), 1.66 (m, 2 H), 1.41 (m,
H), 1.31 (m, 4 H), 0.88 (m, 3 H).
2
correction. Psi scan absorption correction used (Tmin = 72.0, T
max
1
3
C NMR (CDCl ): d = 166.2 (C), 152.7 (C), 148.5 (CH), 138.7 (C),
28
3
= 93.3%). Structure solution by direct methods (SHELXS97 ), re-
1
36.1 (CH), 130.1 (C), 127.0 (CH), 123.2 (CH), 117.5 (CH), 113.8
2
29
finement on F (SHELXL97 ). The hydrogen positions are of
(
C), 40.0 (CH ), 31.5 (CH ), 29.6 (CH ), 26.8 (CH ), 22.6 (CH ),
2
2
2
2
2
2
riding model with fixed isotropic U. R = 0.0581, wR = 0.1644 [I >
2σ(I)], R = 0.1551, wR = 0.2000 (all data) for 419 parameters. The
1
4.0 (CH3).
2
crystallographic data have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC 120866.
IR (KBr): n = 3276, 2927, 1598, 1497, 1406, 1328, 1288, 1212,
-
1
1
106, 931, 796, 744 cm .
+
MS: m/z (%) = 272 (42) [M] , 172 (100).
HRMS (EI, 70 eV): C H N O (272.35): requires: M 272.1525;
found M 272.1512.
1
6
20
2
2
+
Acknowledgement
C H N O :
calc.
C 70.56 H 7.40 N 10.29
This work was supported by the Fonds der Chemischen Industrie
and the Deutsche Forschungsgemeinschaft. Financial support from
Finnish Ministry of Education, Finnish Academy and DAAD (Ger-
many) are gratefully acknowledged by E. W. and M. N.
1
6
20
2
2
found C 70.09 H 7.51 N 10.19
X-ray Structural Analysis of N-Hexyl-8-hydroxyquinoline-7-
carboxamide (2)
-
1
C H N O , M = 272.34 gmol , monoclinic, a = 10.021(1),
1
6
20
2
2
References
3
b = 11.996(1), c = 12.257(1) Å, β = 103.44(1)°, V = 1433.1(2) Å ,
-
1
-3
P2 /n, µ(MoK ) = 0.084 mm , Z = 4, D = 1.262 g cm ,
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1
α
c
F(000) = 584, T = 173(2) K. Data were recorded with a Nonius
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unique reflections [2131 I > 2σ(I)] were used for refinement. The
3
0
data were processed with Denzo. Lp correction. No absorption
correction was applied. Structure solution by direct methods
28
2
29
(
SHELXS97 ), refinement on F (SHELXL97 ). The hydrogen
positions are of riding model with fixed isotropic U. R = 0.0457,
2
2
wR = 0.1067 [I > 2σ(I)], R = 0.0700, wR = 0.1193 (all data) for
86 parameters. The crystallographic data have been deposited with
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the Cambridge Crystallographic Data Centre as supplementary pub-
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1
8
,2-N,N’-Di(8-hydroxyquinolin-7-carboxamide)ethane (14)
-Hydroxyquinoline-7-carboxylic acid (28) (500 mg, 2.64 mmol)
(6) Albrecht, M.; Blau, O. Chem. Commun. 1997, 345.
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(7) Albrecht, M.; Blau, O.; Wegelius, E.; Rissanen, K. New J.
Chem. 1999, 23, 667.
and carbonyl diimidazole (470 mg, 2.91 mmol) are refluxed in an-
hyd THF (50 ml) for 1 h under Ar. Ethylenediamine (80 mg, 1.32
mmol) in anhyd THF (5 mL) is added to the refluxing mixture,
which after completion of the addition is refluxed overnight. Sol-
vent is removed and the residue is washed with H O and MeOH and
dried in vacuo; yield: 341 mg (64%); beige solid; mp >280 °C.
(8) Roychowdhury, P.; Das, P. N.; Basak, B. S. Acta Crystallogr.
Sect. B 1978, 34, 1047.
(
9) Hiratami, K.; Takahashi, T.; Kasuga, K.; Sugihara, H.;
Fujiwara, K.; Ohashi, K. Tetrahedron Lett. 1995, 36, 5567.
2
(
10) Yoneda, A.; Hakushi, T.; Newkombe, G. R.; Matsushita, T.
Acta Cryst. 1996, C52, 172.
11) Ozawa, T.; Shibuya, K. Yakugaku Zasshi 1963, 83, 498;
Chem. Abstr. 1963, 59, 7481.
1
H NMR (DMSO-d ): d = 9.07 (m, 2 H), 8.91 (m, 2 H), 8.34 (m, 2
6
H), 7.97 (m, 2 H), 7.63 (m, 2 H), 7.41 (m, 2 H), 3.32 (br, 4 H).
(
1
3
C NMR (DMSO-d ): d = 168.7 (C), 157.1 (C), 149.1 (CH), 139.2
6
(
1
C), 135.0 (CH), 130.7 (C), 125.0 (CH), 123.5 (CH), 116.8 (CH),
12.4 (C), 38.9 (CH2).
Matsumara, Y. Bull. Soc. Chem. Jpn. 1976, 49, 3093.
(12) Lehn, J.-M. Supramolecular Chemistry, VCH: Weinheim
995.
1
IR (KBr): n = 3335, 3068, 2943, 1598, 1559, 1434, 1384, 1224,
1
-
1
Olenyuk, B.; Fechtenkötter, A.; Stang, P. J. J. Chem. Soc.
Dalton Trans. 1978, 1707.
Saalfrank, R. W.; Bernt, I. Curr. Op. Solid State Mat. Sci.
1998, 3, 407.
127, 941, 747 cm .
+
MS: m/z (%) = 402 (2) [M] , 145 (100).
HRMS (EI, 70 eV): C H N O (402.41): requires: M 402.1328;
found M 402.1305.
C H N O ⋅ ½ H O: calc.
2
2
18
4
4
+
(13) Albrecht, M.; Blau, O. Synthesis 1997, 213.
(
(
14) Albrecht, M.; Blau, O. J. Prakt. Chem. 1998, 340, 683.
15) Iyoda, M.; Sakaitani, M.; Otsuka, H.; Oda, M. Chem. Lett.
1985, 127.
C 64.23 H 4.65 N 13.62
found C 63.92 H 4.77 N 13.60
2
2
18
4
4
2
(
(
16) Koenigs, W. Chem. Ber. 1890, 23, 2679.
17) Noelting, E.; Trautmann, E. Chem. Ber. 1890, 23, 3654.
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York

FEATURE ARTICLE
Di(8-hydroxyquinoline) Derivatives for Supramolecular Chemistry
1829
(
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18) Pene, C. Bull. Soc. Chim. Fr. 1966, 586.
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Metals, Academic: New York 1967.
(
(
(
(
(
21) Tobinaga, K.; Mukaino, M.; Inazu, T.; Yoshino, T. Bull. Soc.
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22) Miyaura, N.; Ishiyama, T.; Sasaki, H.; Ishikawa, M.; Satoh,
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989, 28, 128.
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1
1
Karpishin, T. B.; Stack, T. D. P.; Raymond, K. N. J. Am.
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Article Identifier:
(
25) Beijer, F. H.; Kooijman, H.; Spek, A. L.; Sijbesma, R. P.;
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1437-210X,E;1999,0,10,1819,1829,ftx,en;Z04499SS.pdf
Synthesis 1999, No. 10, 1819–1829 ISSN 0039-7881 © Thieme Stuttgart · New York