Palladium-catalysed amination of 1,8- and 1,5-dichloroanthracenes and 1,8- and 1,5-dichloroanthraquinones

FULL PAPER

Palladium-Catalysed Amination of 1,8- and 1,5-Dichloroanthracenes and

1,8- and 1,5-Dichloroanthraquinones

Irina P. Beletskaya,*^[a]Alla G. Bessmertnykh,^[a,b]Alexei D. Averin,^[a,b]Franck Denat,^[b]and

Roger Guilard*^[b]

Keywords: Amines / Aromatic substitution / Homogeneous catalysis / Macrocycles / Palladium

Diamino derivatives of anthracene and anthraquinone have

been synthesised by palladium-catalysed coupling of 1,8-

rating anthracene or anthraquinone moieties. The method

has also been employed for the preparation of bismacro-

dichloroanthracene and 1,8-dichloroanthraquinone with a cycles in which two cyclam or azacrown units are linked to-

wide range of aliphatic and aromatic primary and secondary

amines. The use of polyamines gave rise to a large number

of new nitrogen- and oxygen-containing macrocycles incorpo-

gether by an anthracene bridge through C(sp²)−N bonds.

Germany, 2005)

Introduction

important models in studies of photosynthesis.^[7]Their bi-

nuclear metal complexes are also important model catalysts

in oxygen reduction.^[8]Saturated polyazamacrocycles as-

sembled in a face-to-face manner have been extensively

studied in recent years,^[9]and the synthesis of a variety of

such bismacrocyclic molecules linked to the same aryl spa-

cers has recently been described by our group.^[10]Crown

and azacrown ethers combined with anthracene or anthra-

quinone also demonstrate very promising properties. Pro-

ton sensors, for example, were produced by the attachment

either of one or two crown ether cycles to the anthracene

or of a macrocycle to positions 9 and 10 in the anthracene

moiety.^[2b]Crown ethers containing two anthracene moie-

ties generated crown-cryptand photoswitches.^[3c,3d]Anthra-

cene linked to a crown ether has also been used for de-

tecting Cu^2ϩions and d-glucoseamine.^[11]

Amino derivatives of anthracene and anthraquinone have

several applications in academic research and industry.

Aminoanthraquinones have for a long time been used as

dyes,^[1]while in recent decades aminoanthracenes and ami-

noanthraquinones have been widely used in coordination

chemistry, since their complexes possess interesting physical

properties and have found applications as sensors,^[2]photo-

and redox-switchable molecules and multielectron cata-

lysts.^[3]The properties of such complexes are mainly the re-

sult of the interactions that can occur between transition

metal ions and redox-active ligands, which induce different

phenomena including facile redox behaviour^[4]and valence

tautomerism.^[5]Ligands of different architectures have been

synthesised, and among them a significant role is played by

derivatives of anthracene and anthraquinone bearing nitro-

gen- and oxygen-containing macrocycles. In all these

macrocycles, oxygen and nitrogen incorporated in the cycle

are linked to arene moieties through at least one methylene

group. Special attention has been devoted to saturated and

tetrapyrrolic macrocyclic ligands containing anthracene or

anthraquinone fragments either attached to the macrocycle

or acting as a component of a macrocycle. The famous face-

to-face porphyrins containing two tetrapyrrolic cycles

bound through an anthracene spacer^[6]have proved to be

Our goal was to synthesise ligands possessing C(sp²)ϪN

bonds and to study their binding properties. The presence

of such a fragment in the ligand can significantly change its

metal coordination and enhance the measurable response

of the aromatic moiety in a complexation reaction. Litera-

ture data clearly show that the synthesis of such macrocyclic

molecules has been strictly limited, due to the lack of con-

venient and general methods for C(sp²)ϪN bond forma-

tion. Copper-catalysed Ullmann-type reactions have been

extensively used to prepare aminoanthraquinones for de-

cades,^[12]but this synthetic method demands harsh con-

ditions limiting the choice of appropriate substrates and the

reaction yields are often poor. To the best of our knowl-

edge, there is no convenient synthetic approach to ami-

noanthracenes. Finally, bis(dimethylamino)anthracene was

only recently synthesised for the first time by direct nucleo-

philic substitution starting from 1,8-difluoroanthracene.^[13]

Significant progress in the amination of aryl halides was

achieved through the use of palladium catalysis, after

[a]

Department of Chemistry, Lomonosov Moscow State University,

Moscow, 119899, Russia

Fax: (internat.) ϩ 7-095-9393618

E-mail: beletska@org.chem.msu.su

[b]

´

Laboratoire d’Ingenierie Moleculaire pour la Separation et les

´

Applications des Gaz (LIMSAG UMR 5633), Universite de

´

Bourgogne, Faculte des Sciences ‘‘Gabriel’’,

6, Bd Gabriel, 21100, Dijon, France

Fax: (internat.) ϩ 33-3-80396117

E-mail: Roger.Guilard@u-bourgogne.fr

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DOI: 10.1002/ejoc.200400455

281

I. P. Beletskaya, R. Guilard et al.

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pioneering work by Kosugi and Migita and extensive devel-

1,8-Dichloroanthracene 1 was successfully diaminated

opment by Buchwald’s and Hartwig’s groups.^[14]An im- when treated with the different amines 2aϪi, giving the cor-

portant survey on the amination of aryl halides (mainly aryl responding 1,8-diamino derivatives 3aϪi (Scheme 1). In a

chlorides) through the use of electron-rich ligands such as standard procedure, one equivalent of 1,8-dichloroanthra-

2-(di-tert-butylphosphanyl)-1,1Ј-biphenyl and 2-(dicyclo- cene 1 was treated with three equivalents of the correspond-

hexylphosphanyl)-1,1Ј-biphenyl was published by Buch- ing amines 2aϪi in the presence of 4Ϫ8 mol % Pd(dba)₂

wald.^[15]These ligands proved to be more efficient than the and 8Ϫ16 mol % BINAP or dppf in boiling dioxane, with

PtBu₃and PCy₃ligands previously used in amination of NaOtBu used as a base. The amount of the Pd catalyst

aryl chlorides.^[16]‘‘Phosphane mimic’’ ligands were success- was increased from the usual 1Ϫ2 mol % to 2Ϫ4 mol % per

fully used by Nolan for Pd-catalysed amination,^[17]and chlorine atom to promote good diamination, and the use

nickel-mediated coupling of amines with aryl chlorides was of 1.5Ϫ2 equivalents of BINAP with respect to Pd was

described by Fort.^[18]The synthesis of macrocycles contain- found to be best suited. The aromatic primary amines 2aϪc

ing anthracene and anthraquinone fragments being our gave the corresponding diaminated products 3aϪc in good

main goal, we chose commercially available chloro deriva- yields (Table 1, entries 1Ϫ4). In the case of aniline (2a),

tives (part of this work has been already published in pre- similar yields were obtained with both the Pd(dba)₂/dppf

liminary reports^[19]). Attempts to achieve the diamination and the Pd(dba)₂/BINAP systems. The reaction with the

of dichloroanthracene and dichloroanthraquinone face sev- secondary aromatic amine N-methylaniline (2d) showed a

eral serious problems: a) reduction of the second chlorine much higher efficiency of BINAP over dppf. Indeed, the

atom, affording monoamination products, b) the com- diamino anthracene 3d was prepared in good yield with use

plexation of palladium by formed polyazamacrocycles, of BINAP (Table 1, entries 5, 6) while no reaction was ob-

which may hinder amination, c) the formation of the cyclic served with dppf. The primary aliphatic amines 2e and 2f

and linear oligomers through amination reactions, due to gave the diamination products 3e and 3f in good yields

the existence of two reaction sites in both starting com- (Table 1, entries 7, 8), while coupling with propane-1,3-di-

pounds (i.e., polyamines and aryl dichlorides), and d) the amine (2g) gave 3g in moderate yield (Table 1, entry 9). It

polyarylation of polyamines. Here we show how some of is worth noting that only monoarylation of this diamine

these problems have been solved in the course of our in- was observed, as previously discussed.^[21]

vestigations.

We first studied the feasibility of the diamination of 1,8-

dichloroanthracene and 1,8-dichloroanthraquinone, and

this method was then used for the construction of macro-

cycles based on anthracene and anthraquinone skeletons.

Finally, the synthesis of bismacrocyclic molecules starting

from nitrogen and oxygen-containing macrocycles was car-

ried out.

Results and Discussion

Synthesis of 1,8-Diaminoanthracenes and 1,8-Diamino-

anthraquinones

Scheme 1

In the course of our preliminary investigations into the

palladium-catalysed amination reactions of aryl halides,

dramatic differences between the reactivities of primary and

secondary linear and cyclic polyamines were observed. A

suitable choice of catalytic system was crucial for success

of the reactions, and Pd(dba)₂was chosen as a source of

palladium in the catalytic coupling since it is known as a

useful catalyst in a great number of aryl bromide and aryl

chloride amination reactions. In preliminary experiments,

electron-rich monophosphanes such as PtBu₃and PCy₃

surprisingly appeared to be inefficient in the reactions of

1,8-dichloroanthracene and -anthraquinone with amines.

However, BINAP, previously used mainly in the amination

of aryl bromides^[14c]and of some chloro-substituted N-con-

taining heteroarenes,^[20]was found to be readily applicable

to our purpose. Dppf was also used, but was less efficient

than BINAP in most cases.

Scheme 2

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Palladium-Catalysed Amination of Anthracenes

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Table 1. Palladium-catalysed amination of 1,8-dichloroanthracene^[a]

[a]

NaOtBu was used as a base, dioxane as solvent.

The secondary cyclic amines morpholine (2h) and piperi- efficiency of morpholine may be explained by the different

dine (2i) showed different reactivity towards 1,8-dichloroan- basicities of morpholine (pK_aϭ 8.33) and piperidine

thracene. The first gave the corresponding diamino product (pK_aϭ 11.12). It is important to note that no diamination

3h in high yield (Table 1, entry 10), but only a moderate reaction was achieved with the acyclic aliphatic secondary

yield was observed for 3i (Table 1, entry 11). The higher amine diethylamine (2j), only the monoamino derivative 4

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283

I. P. Beletskaya, R. Guilard et al.

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being isolated, in 54% yield (Scheme 2). This compound

may serve as a precursor for the synthesis of an unsym-

metrically substituted anthracene, since the remaining

chlorine atom can be substituted by aniline to form 5 in

48% yield.

The Pd-catalysed coupling of 1,8-dichloroanthraquinone

(6) with amines was performed by the same method as de-

Scheme 3

Table 2. Palladium-catalysed amination of 1,8-dichloroanthraquinone^[a]

[a]

[b]

Cs₂CO₃was used as a base, dioxane as solvent. ϩ15% 1-chloro-8-(4-ethoxyphenylamino)anthraquinone.

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Palladium-Catalysed Amination of Anthracenes

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scribed above, except for NaOtBu being replaced by equimolar amounts of the linear polyamines 8aϪf with an-

Cs₂CO₃, which does not affect anthraquinone (Scheme 3). thracene (1) (Scheme 4) and anthraquinone (6) (Scheme 5).

Treatment with the primary aromatic amines 2aϪc af- The Pd(dba)₂/BINAP catalytic system (4Ϫ8 mol %) was

forded the corresponding products 7aϪc in excellent yields used, in the presence of NaOtBu or Cs₂CO₃when the start-

(95Ϫ98%) (Table 2, entries 1, 2, 4). Dppf was shown to be ing materials were dichloroanthracene and dichloroanthra-

quite efficient in the coupling reaction with aniline (Table 2, quinone, respectively. Diluted solutions of the reagents in

entry 1), and the primary aliphatic amine 2e also gave the dioxane were used (0.017Ϫ0.025 m) to avoid undesirable

diamino derivative 7e in remarkably high yield (Table 2, en- formation of oligomers. Longer heating times (48Ϫ103 h)

try 5). Treatment with propane-1,3-diamine produced com- were required to complete the cyclisation reaction

pound 7g in good yield (Table 2, entry 6), again with only (Table 3).

monoarylation of the diamine being observed. All these re-

actions proceeded more smoothly with dichloroanthraqui-

none than with dichloroanthracene. The reaction pattern

with the cyclic aliphatic amines 2h and 2i was similar to that

seen with 1,8-dichloroanthracene (Table 2, entries 7Ϫ9). In

contrast, both the aromatic and the aliphatic acyclic sec-

ondary amines N-methylaniline (2d) and diethylamine (2j)

proved to be inefficient reactants, since the corresponding

diamino derivatives of anthraquinone were not obtained.

Diamino derivatives of anthracene and anthraquinone were

successfully prepared through Pd-catalysed treatment of

1,8-dichloroanthracene and 1,8-dichloroanthraquinone

with aromatic and aliphatic primary amines and cyclic sec-

ondary amines. The substitution of one chlorine atom by

an amino group does not substantially affect the reactivity

of the remaining halogen atom, unlike in monoamination

Scheme 4

of dihalobenzenes, in which the second amination reaction

The reactions resulted in the formation of polyazamacro-

cycles 9aϪf and 10aϪe as results of intramolecular cycli-

is hindered.^[22]

sation. The macrocycles 9aϪf were prepared in 21 to 36%

yields (Table 3, entries 1Ϫ6), whereas lower yields

(10Ϫ27%, Table 3, entries 7Ϫ14) were generally observed

Polyazamacrocycles Derived from 1,8-Dichloroanthracene

and 1,8-Dichloroanthraquinone

for compounds 10a-e. The macrocycles 9aϪf were obtained

Macrocyclic compounds containing anthracene and as brown solids after chromatography on silica, and com-

anthraquinone moieties were synthesised by treatment of pounds 10a/10b and 10cϪe appeared as red and lilac solids,

Scheme 5

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I. P. Beletskaya, R. Guilard et al.

Table 3. Palladium-catalysed amination of 1,8-dichloroanthracene and 1,8-dichloroanthraquinone by polyamines

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286

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Palladium-Catalysed Amination of Anthracenes

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Table 3. (continued)

[a]

[b]

[c]

[d]

7% of a mixture of 11 ϩ 12 ϩ 13. 8% of a mixture of 16a ϩ 17a. 9% of a mixture of 14d ϩ 15d. 12% of a mixture of 16d ϩ

17d.

respectively. Dichloroanthracene was totally converted in to by MALDI-TOF and NMR spectroscopy: a set of

1

these reactions, whereas the consumption of dichloro- eight singlets in the 8.2Ϫ8.8 ppm region of the H NMR

anthraquinone was not complete (90Ϫ95%). Noticeable re- spectrum attributable to H-9 and H-10 protons of the

duction of the chlorine atoms of dichloroanthraquinone anthracene moiety was observed, together with a set of

was observed, generally resulting in mixtures of anthraqui- four signals in the 143Ϫ144 ppm area of the ¹³C NMR

none, 1-chloroanthraquinone and unchanged 1,8-dichloro- spectrum corresponding to the C1 carbon atom of anthra-

anthraquinone in 1:2:1 mol ratio. Increasing the amount of cene.

catalyst may either enhance (Table 3, entries 10, 13) or

In contrast, treatment of dichloroanthraquinone (6) with

lower the reaction yield (Table 3, entry 8). No oligomeric polyamines resulted in substantial formation of linear com-

or monoaminated anthracenes were detected among the pounds: mixtures of 1-amino- and 1-amino-8-chloroanthra-

products obtained from treatment of dichloroanthracene quinones 14a, 14b and 14d and 15a, 15b and 15d (yields up

with polyamines 8. Only the reaction with 8d produced Ϫ to 30%), as well as some compounds with higher molecular

together with 9d Ϫ a small amount of a mixture of weight and anthraquinone/amine ratios of 2:1 (16a, 16d,

bis(anthracenyl)substituted tetraamines 11؊13, as attested 17a, 17d). Only primary nitrogen atoms were arylated in all

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287

I. P. Beletskaya, R. Guilard et al.

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these reactions, as also reported for treatment of aryl ha-

lides with triamines.^[21a]

Treatment of 6 with dioxa- and trioxadiamines 18aϪc re-

sulted in higher ratios of cyclic oligomers 26aϪc (Figure 2).

It has been demonstrated above that 1,8-dichloroanthra- It is interesting to note that dioxadiamine 18a generated

quinone reacts more easily than 1,8-dichloroanthracene only a tiny quantity (about 2%) of a mixture of cyclic tetra-

with monoamines, due to its more pronounced electron-de- and pentamers, while arylation of diamines 18b and 18c

ficient character. The opposite behaviour towards poly- yielded significant amounts of cyclic and linear oligomers

amines is surprising, but is probably due to the formation of type 26, 27 and 28. The cyclic dimers 26b and 26c (x ϭ

of intramolecular hydrogen bonds between NH protons and 2), as well as the cyclic trimer 26c (x ϭ 3), were isolated,

the oxygen in the anthraquinone. The formation of linear while mixtures of higher mass oligomers were also ob-

species and the partial reduction of the chlorine atom may tained. The formation of cyclic oligomers with n ϭ 9Ϫ10

have the same origin. This is not the case for anthracene or and molecular weights over 4000 was observed in the

for the reactions with di- and trioxadiamines (vide infra).

MALDI-TOF spectra.

As expected, the compositions of the reaction mixtures

strongly depended on the concentrations of the reagents.

With dilution from 0.025 m to 0.017 m, the yield of the

desired adduct 20c was increased from 29% to 37%, while

the amount of higher-mass oligomers was decreased.

Diazacrown Ethers Based on Anthracene and

Anthraquinone Moieties

A new family of diazacrown ethers incorporating anthra-

cene or anthraquinone moieties was synthesised by the

same method of Pd-catalysed amination of 1,8-dichloroan-

thracene and 1,8-dichloroanthraquinone, through the em-

ployment of 3,6-dioxa-1,8-diaminooctane (18a), 4,9-dioxa-

1,12-diaminododecane (18b) and 4,7,10-trioxa-1,13-di-

aminotridecane (18c). The experimental procedure defined

for the synthesis of tetraazamacrocycles 9 and 10 was

successfully used for the synthesis of diazacrown ethers

19aϪc and 20aϪc (Scheme 6, Table 4).

Tetraaza and Diazapolyoxamacrocycles Derived from 1,5-

Disubstituted Anthracene

The conditions described above for the catalytic amin-

ation of aryl halides were used for the synthesis of macro-

cycles based on 1,5-disubstituted anthracene. All four tetra-

amines 8aϪd were treated with 1,5-dichloroanthracene

(29) (Scheme 7).

The geometry of the starting compound 29 suggests that

the aliphatic chain should be long enough to be involved in

a cyclisation reaction. Indeed, tetraamine 8a was unable to

form the desired macrocycle 30a in a reasonable yield. Only

traces of 30a were detected, together with the cyclic dimer

31a (x ϭ 2), which was isolated in 18% yield, and trimer

31a (x ϭ 3). Higher selectivity was observed with the tetra-

amine 8b, the chain of which is only one carbon atom

longer than that of 8a. In this case the monomeric cycle

30b was obtained in 20% yield (Table 5, entry 2), together

with a very small amount of a mixture of cyclic dimer and

trimer (31b, x ϭ 2,3). The cyclic dimer 31b (x ϭ 2) was also

isolated in 10% yield as a separate fraction containing small

amounts of the cyclic trimer and tetramer (x ϭ 3,4). In

addition, a mixture of the target macrocycle 30b together

Scheme 6

The yields of the anthracene-based macrocycles 19aϪc with cyclic oligomers and linear compounds 32b (x ϭ 1Ϫ3)

ranged from 20 to 29% (Table 4, entries 1Ϫ3), while the was isolated by column chromatography in 15% yield. The

anthraquinone-based crown ethers 20aϪc were obtained in same reaction was successfully carried out with tetraamine

higher yields 29Ϫ37% (Table 4, entries 4Ϫ7). Complete 8c to provide 30c in 34% yield, together with traces of cyclic

conversion of starting aryl halides was observed in all dimer and trimer 31c (x ϭ 2, 3) (Table 5, entry 3). Tetraaza-

cases. The target macrocycles were isolated by column cyclophane 30d was obtained in 22% yield (Table 5, entry

chromatography as either brown (19aϪc) or red (20aϪc) 4).

solids.

Treatment of 1,5-dichloroanthracene (29) with dioxadi-

The by-products formed in these reactions were identified amine 18a, with a chain length identical to that in 8a, did

as cyclic and linear oligomers. Treatment of 1 with diamines not result in the formation of the macrocycle of type 33 but

provided rather small amounts (not exceeding 10%) of cy- rather afforded a cyclic dimer 34a in a low 8% yield and a

clic dimers 21aϪc (x ϭ 2) (Figure 1). The cyclic trimer and mixture of linear oligomers 35aϪ37a in 18% yield

tetramer 21c (x ϭ 3 and 4) were formed in 9% yield when (Scheme 8, Table 5, entry 5). Both reactions starting from

the starting diamine was 18c, while the linear compounds the diamines 18b and 18c resulted in the formation of the

22aϪ24a were obtained in 3% yield when 1 was treated with corresponding oxaazacyclophanes 33b and 33c in reason-

18a. In the course of the amination by 18b, 1-amino-8-chlo- able 20Ϫ24% yields (Table 5, entries 6, 7).

roanthracene 25 was isolated in 18% yield and fully charac-

terised.

Linear by-products of the type 35؊37b/37c were formed

in significant quantities (7Ϫ10%) while the cyclic dimer 34c

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Palladium-Catalysed Amination of Anthracenes

Table 4. Palladium-catalysed amination of 1,8-dichloroanthracene and 1,8-dichloroanthraquinone by dioxa- and trioxadiamines^[a]

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Table 4. (continued)

[a]

[b]

[d]

[c]

Pd(dba)₂/BINAP 8/9 mol %.

A mixture of 22aϩ23aϩ24a (x ϭ 1) isolated in 3% yield. A mixture of 23b, 24b (x ϭ 1) and 21b

[e]

(x ϭ 2, 3) isolated in 4% yield. A mixture of trimer and tetramer 21c (x ϭ 3, 4) isolated in 9% yield. Tetramer and pentamer 26a

(x ϭ 4, 5) obtained in 2% yield. Higher mass cyclic (26b) and linear (27b, 28b) oligomers isolated in 20% yield. Higher mass cyclic

(26c, x Ͼ 1) and linear (27c, 28c) oligomers isolated in 48% yield.

isolated in 25% yield.

[f]

[g]

[h]

Higher mass cyclic (26c, x Ͼ 2) and linear (27c, 28c) oligomers

(x ϭ 2) was isolated only in a tiny 4% yield, with dimer 34b upfield by 1.7Ϫ1.8 ppm from the shifts observed in cyclic

(x ϭ 2) and trimer 34b (x ϭ 3) being detected only by mass dimers or in linear oligomers. A similar upfield shift was

spectrometry (m/z ϭ 755.96, 1134.63, respectively).

observed for methylene protons in polyazamacrocycles con-

The ¹H NMR spectra of the macrocycles 30bϪd and 33b/ structed from 9,10-anthracene.^[23]

33c each present a similar feature: all the methylene protons

Amination of 1,5-Dichloroanthraquinone

of the aliphatic chain are diastereotopic. The closer the

methylene group is to the centre of the chain (i.e., the closer

The amination of 1,5-dichloroanthraquinone (38) with

it is located to the centre of the aromatic system), the lower tetraamines 8aϪd and di- and trioxadiamines 18aϪc pro-

the chemical shift of the corresponding protons. Typically, duced results substantially different from those observed

the protons of the central methylene group(s) are shifted with 1,5-dichloroanthracene (Scheme 9). The diazacrown

290

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Palladium-Catalysed Amination of Anthracenes

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Figure 1. By-products formed upon treatment of 1 with dioxa- and

trioxadiamines 18aϪc

Scheme 7

the shift is weaker than those observed for the anthracene-

based cyclophanes and no higher than 1.2 ppm.

Surprisingly, the amination of 1,5-dichloroanthraquinone

(38) by tetraamines 8aϪd did not result in the formation of

the corresponding tetraazamacrocycles (Scheme 10). Only

the 1-amino-5-chloro-substituted anthraquinones 44aϪd

were obtained, in 16Ϫ28% yields, together with the bis-

(aryl)substituted tetraamines 45aϪd and 46aϪd, which

were formed in 5Ϫ26% yields (Table 6, entries 4Ϫ9). The

consumption of 1,5-dichloroanthraquinone was not

quantitative, as had already been found when 1,8-dichloro-

anthraquinone was treated with tetraamines (Scheme 5).

Two attempts to promote cyclisation were undertaken. The

first involved the use of double the amount of the Pd(dba)₂/

BINAP catalytic system, the second the use of the new li-

gand 2-di-tert-butylphosphanylbiphenyl.^[15]These attempts

were unsuccessful, however, the formation of the desired

cycle 47d being observed only spectrally, together with 45d;

moreover, the latter ligand, which has proved efficient in

other amination reactions of aryl halides, was found to be

less active in our case.

Figure 2. By-products formed upon treatment of 6 with dioxa- and

trioxadiamines 18aϪc

ethers 39b and 39c (Table 6, entries 2,3) were obtained in

good yields, provided that Cs₂CO₃was employed as a base

instead of NaOtBu. The amination of the dioxadiamine

18a, with the shorter chain, afforded not the target macro-

cycle 39a, but the cyclic dimer 40a in 18% yield (Table 6,

entry 1). The higher linear oligomers 41a and 42a were also

identified by MALDI-TOF spectrometry. In the case of

18b, the target macrocycle 39b was obtained in 30% yield

and the cyclic dimer 40b (x ϭ 2) and trimer (x ϭ 3) were

isolated in 10% and 6% yields, respectively. In contrast,

when 38 was treated with 18c, besides the monomeric cycle

39c (isolated in 28% yield), mixtures of other higher mass

cyclic 40c (x ϭ 2Ϫ9) and linear oligomers 41c and 43c

Synthesis of Anthracene Derivatives Containing Two

Macrocycles

were collected.

1,4,8,11-Tetraazacyclotetradecane (cyclam) plays an out-

1

The H NMR spectra of the oxoazacyclophanes 39b and standing role among the numerous saturated tetra-

39c show the same feature as described previously for azamacrocycles, due to its versatility in the complexation of

30bϪd and 33b/33c: methylene protons located above the metal ions. The synthesis of molecules with two cyclam

anthraquinone moiety are again shifted upfield, although rings arranged in a face-to-face manner is of great interest

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Table 5. Palladium-catalysed amination of 1,5-dichloroanthracene by tetraamines and di- and trioxadiamines^[a]

FULL PAPER

[a]

[b]

[c]

Pd(dba)₂/BINAP 8/9 mol %, c ϭ 0.01 m. A mixture of 31a (x ϭ 3), 32a (x ϭ 1, 2), traces of 30a. 15% of 31b (x ϭ 2Ϫ4) ؉32b

[d]

[e]

[f]

[g]

[h]

(x ϭ 1Ϫ3).

35cϪ37c (x ϭ 0), 4% of dimer 34c (x ϭ 2).

Traces of 31c (x ϭ 2, 3). 5% of 31d (x ϭ 2, 3). 18% of 35aϪ37a (x ϭ 0, 1). 10% of 35bϪ37b (x ϭ 0).

7% of

to chemists, because of the intriguing properties of their presence of 4Ϫ8 mol % of Pd(dba)₂/BINAP and NaOtBu

bimetallic complexes. Recently we have observed the Pd- gave only unsubstituted anthracene 49, the reduction prod-

catalysed arylation of cyclam 48 by p-bromobiphenyl and uct of the starting dichloride (Scheme 11).

p-bromobenzonitrile.^[19c]We chose 1,8-disubstituted an-

The same reaction with the less basic cyclen 50 in the

thracene as a spacer to prepare a biscyclam. The Pd(dba)₂/ presence of 5 mol % Pd(dba)₂/BINAP successfully yielded

BINAP catalytic system was initially preferred to the ex- a mixture of monocyclen-substituted anthracenes 51 (26%)

pensive PPF-OMe ligand^[24]utilised for cyclam amination. and 52 (13%), together with anthracene 49 (Scheme 12).

Treatment of 1,8-dichloroanthracene with cyclam in the Heating of the reaction mixture for a longer time and ad-

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Palladium-Catalysed Amination of Anthracenes

FULL PAPER

In order to avoid undesirable reduction, N,NЈ,NЈЈ-trisub-

stituted cyclams Ϫ tritosyl and triBoc derivatives Ϫ were

used instead of free cyclam, which contains four secondary

amino groups capable of reducing dichloroanthracene.

Nevertheless, no arylation occurred.^[25]Another trimethyl

derivative of cyclam Ϫ N,NЈNЈЈ-trimethylcyclam 53 Ϫ ap-

peared to be appropriate for our purpose, with BINAP and

PtBu₃as supporting ligands. Reactions promoted by Pd

precursor [Pd(dba)₂, 16 mol %] with PtBu₃produced the

monocyclam derivative of anthracene 54 in 45% yield, but

only traces of the desired biscyclam 56 were detected in the

mass spectrum (Scheme 13). The first attempt to synthesise

56 with the aid of the Pd(dba)₂/BINAP catalytic system (8

mol %) also yielded monocyclam-substituted anthracenes

54 and 55 (each in ca. 20% yield), the target compound 56

being detected only as a mixture with 54 and 55 (10% yield

of the mixture). A twofold increase in the amount of the

catalyst and ligand (16 mol %] resulted in the formation of

the target biscyclam-substituted anthracene 56 in 10% yield,

while the monosubstituted anthracene 54 was obtained in

35% yield. In all cases longer heating times in dioxane (ca.

100 h) were required to complete the reaction. Attempts to

increase the yield of 56 by use of 2-(di-tert-butylphos-

phanyl)-1,1Ј-biphenyl were unsuccessful. The relatively

good results obtained with N,NЈ,NЈЈ-trimethylcyclam, in re-

lation to those involving the free cyclam, may also be due

to stronger complexation of palladium by cyclam than by

its trimethyl derivative.

Scheme 8

The same methodology was used for the synthesis of bis-

azacrown-substituted anthracene. We investigated the syn-

thesis of face-to-face ring systems containing two azacrown

moieties starting from 1-aza-15-crown-5 (57) and 1,8-di-

chloroanthracene in the presence of the Pd(dba)₂/BINAP

catalytic system (Scheme 14). The target bisazacrown-sub-

stituted anthracene 58 was obtained in 11% yield. We also

observed the formation of the monosubstituted anthracene

59 in 44% yield, as the product of monoarylation and chlo-

rine reduction. It is clear that the formation of the mono-

amination product with the reduced second chlorine atom

is the main hindrance on the pathway to the target bisaza-

crown molecule. However, monoamination by azacrown

ethers can be performed under mild conditions. Arylation

of azacrown ethers by aryl bromides was previously studied

by Witulski and Buchwald.^[2c,26]Very recently a non-cata-

lytic method for the arylation of diazacrown ethers by di-

fluoroanthraquinones has been put forward.^[27]

Conclusion

In conclusion, we have shown that Pd-catalysed amin-

ation of dichloroanthracene and dichloroanthraquinone is

a convenient method to synthesise the otherwise not readily

accessible corresponding diamino derivatives. Linear poly-

Scheme 9

dition of a larger amount of catalyst did not provide any amines and polyoxapolyamines may be used for the one-pot

biscyclen-substituted anthracene. The use of an electron- synthesis of macrocycles of different sizes and possessing

rich tri-tert-butylphosphane in this reaction was also unsuc- various numbers of nitrogen and oxygen atoms, and new

cessful.

types of nitrogen- and oxygen-containing macrocycles con-

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Table 6. Palladium-catalysed amination of 1,5-dichloroanthraquinone by tetraamines and di- and trioxadiamines^[a]

FULL PAPER

[a]

[b]

[c]

[d]

Pd(dba)₂/BINAP 8/9 mol %, c ϭ 0.01 m. A mixture of 41a, 42a (x ϭ 1, 2). 6% of trimer 40b (x ϭ 3). 43% of a mixture of 40c

[e]

[f]

(x ϭ 2Ϫ9), 41c (x ϭ 1Ϫ8), 43c (x ϭ 1Ϫ7) (4 fractions). Pd(dba)₂/BINAP 16/18 mol %. Pd(dba)₂/L 10/10 mol %, L ϭ 2-(di-tert-

butylphosphanyl)biphenyl. Contains 44d. Contains 47d.

[g]

[h]

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Palladium-Catalysed Amination of Anthracenes

FULL PAPER

Scheme 14

taining anthracene and anthraquinone moieties were thus

obtained. Palladium-catalysed amination of 1,8-dichloroan-

thracene proved to be an useful tool for the synthesis of

novel bistetraazamacrocycles and bisazacrown ethers in

face-to-face arrangements. The capabilities of all these new

macrocycles for complexation with transition metals are

currently being studied.

Scheme 10

Scheme 11

Experimental Section

1

General Remarks: H and ¹³C NMR spectra were recorded at 200

and 50 MHz, respectively, on a Bruker AM200 spectrometer, or at

500 and 125 MHz, respectively, on a Bruker DRX500 spectrometer,

and referenced to the residual protons or carbon signals of the

deuterated solvent. Infrared spectroscopy was carried out on a

PerkinϪElmer 1600 Series FT-IR spectrometer. MALDI-TOF

spectra were recorded on a Bruker Daltonics Proflex III device with

dithranol as a matrix. Elemental analyses were carried out with a

Fisons EA 1108 CHNS instrument. Gas chromatography analyses

were carried out on a HewlettϪPackard HP-5890 Series II gas

chromatograph fitted with a HP-1 capillary column (25 m,

0.20 mm, 0.11 mm). Thin-layer chromatography was carried out on

E. Merck TLC plates (Silica Gel 60F-254).

Reactions under argon atmosphere were carried out by standard

Schlenk techniques. All reagents were used directly as obtained

commercially unless otherwise noted. Dioxane purchased from

SDS Chemical Co. was distilled under argon from sodium benzo-

phenone ketyl. Sodium tert-butoxide was purchased from Aldrich

Chemical Co. and stored under nitrogen. Small amounts were

taken as needed, stored in a Schlenk tube up to 2 weeks, and

quickly weighed at the air. Cesium carbonate was purchased from

Acros Chemical Co., dried in vacuo at 120Ϫ150 °C for several

hours, stored in a Schlenk tube, and weighed in an argon-flushed

vessel. Aniline (2a), 4-methylaniline (2b), 4-ethoxyaniline (2c), N-

methylaniline (2d), n-hexylamine (2e), benzylamine (2f), propane-

1,3-diamine (2g), morpholine (2h), piperidine (2i), diethylamine

(2j), 1,8-dichloroanthraquinone (6), triethylenetetraamine (8a),

Scheme 12

N,NЈ-bis(2-aminoethyl)propane-1,3-diamine

(8b),

N,NЈ-bis(3-

aminopropyl)ethane-1,2-diamine (8c), tetraethylenepentaamine

(8e), pentaethylenehexaamine (8f), 2,2Ј-(ethylenedioxy)bis(ethyl-

amine) (9a), 4,9-dioxadodecane-1,12-diamine (9b), 4,7,10-trioxatri-

decane-1,13-diamine (9c), 1,5-dichloroanthraquinone (38), 1-aza-

15-crown-5 (57), BINAP, tri-tert-butylphosphane, tricyclohexyl-

phosphane and PPF-OMe were purchased from Aldrich Chemical

Co. N,NЈ-Bis(3-aminopropyl)propane-1,3-diamine was purchased

Scheme 13

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295

I. P. Beletskaya, R. Guilard et al.

FULL PAPER

from Avocado Chemical Co. 2-(Di-tert-butylphosphanyl)-1,1Ј-bi-

8.2 Hz, 2 H), 7.96 (d, J ϭ 8.6 Hz, 2 H), 8.42 (s, 1 H), 8.59 (s, 1 H).

phenyl was purchased from Strem Chemical Co. Pd(dba)₂,^[28]1,8- ¹³C NMR (CDCl₃, ppm): δ ϭ 40.3 (2 C), 114.6 (4 C), 117.7 (2 C),

and 1,5-dichloroanthracenes 1 and 29,^[29]cyclam 48,^[30]cyclen

50,^[31]and N,NЈ,NЈЈ-trimethylcyclam 54^[32]were synthesised by the

described procedures.

120.3 (1 C), 124.2 (2 C), 126.1 (2 C), 126.4 (4 C), 127.8 (1 C), 128.9

(2 C), 129.2 (2 C), 133.5 (2 C), 146.1 (2 C), 150.3 (2 C). C₂₈H₂₄N₂

(388.50): calcd. C 86.56, H 6.23, N 7.23; found C 86.11, H 6.27,

N 7.17.

General Procedure for the Palladium-Catalysed Reactions of 1,8-Di-

chloroanthracene: A two-necked, argon-flushed flask fitted with a

magnetic stirrer and condenser was charged with dioxane (10 mL),

the indicated amount of Pd(dba)₂, the ligand (Table 1), 1,8-di-

chloroanthracene (1 mmol), the amine (3 mmol) and NaOtBu

(3 mmol). The reaction mixture was heated at reflux with stirring

for 24 h. After cooling down to room temperature it was concen-

trated in vacuo, and the residue was taken up with a mixture of

dichloromethane and water. The organic layer was separated and

washed with water (10 mL) and then dried over anhydrous sodium

sulfate, and the solvents were evaporated in vacuo. The crude mate-

rial was purified by column chromatography on silica. The follow-

ing compounds were prepared by this procedure; the results are

summarised in Table 1.

N,NЈ-Dihexylanthracene-1,8-diamine (3e): See Table 1, entry 7. The

reaction mixture was chromatographed with toluene/pentane 1:1 to

1

yield a dark brown solid: m.p. 83Ϫ85 °C. Yield 297 mg (79%). H

NMR (CDCl₃, ppm): δ ϭ 0.99 (t, J ϭ 7.3 Hz, 6 H), 1.33 (m, 12

H), 1.80 (m, 4 H), 3.28 (t, J ϭ 7.3 Hz, 4 H), 5.50 (br. s, 2 H), 6.53

(d, J ϭ 5.6 Hz, 2 H), 7.36 (m, 4 H), 8.24 (s, 1 H), 8.30 (s, 1 H). ¹³

C

NMR (CDCl₃, ppm): δ ϭ 14.2 (2 C), 22.7 (2 C), 27.2 (2 C), 29.5

(2 C), 31.8 (2 C), 44.6 (2 C), 102.4 (2 C), 110.6 (1 C), 117.3 (2 C),

122.8 (1 C), 126.3 (2 C), 128.4 (2 C), 132.5 (2 C), 143.6 (2 C). IR

(KBr): ν˜ ϭ 3403 cm^Ϫ1, 3054, 1616, 1569, 1500, 1466, 1284, 886,

773, 727. MS (EI): m/z ϭ 376 [M^ϩ]. C₂₆H₃₆N₂(376.58): calcd. C

82.93, H 9.64, N 7.44; found C 82.60, H 9.96, N 7.23.

N,NЈ-Dibenzylanthracene-1,8-diamine (3f): See Table 1, entry 8. The

reaction mixture was chromatographed with toluene/pentane 1:1 to

yield a yellow solid: m.p. 170Ϫ172 °C. Yield 241 mg (62%). ¹H

NMR (CDCl₃, ppm): δ ϭ 4.57 (s, 4 H), 4.91 (br. s, 2 H), 6.55 (d,

J ϭ 6.2 Hz, 2 H), 7.35 (m, 14 H), 8.34 (s, 1 H), 8.36 (s, 1 H). ¹³C

NMR (CDCl₃, ppm): δ ϭ 48.7 (2 C), 103.2 (2 C), 110.9 (1 C), 117.9

(2 C), 122.7 (1 C), 126.3 (2 C), 127.4 (4 C), 128.8 (4 C), 132.5 (4

N,NЈ-Diphenylanthracene-1,8-diamine (3a): See Table 1, entries 1, 2.

The reaction mixture was chromatographed with toluene to yield a

brown solid: m.p. 110Ϫ112 °C. Yield 200 mg (56%, using dppf),

240 mg (67%, with BINAP). ¹H NMR (CDCl₃, ppm): δ ϭ 5.94 (br.

s, 2 H), 6.97 (br. t, J ϭ 7.2 Hz, 2 H), 7.10 (br. d, J ϭ 7.2 Hz, 4 H),

7.34 (m, 8 H), 7.68 (d, J ϭ 7.2 Hz, 2 H), 8.41 (s, 1 H), 8.76 (s, 1

H). ¹³C NMR (CDCl₃, ppm): δ ϭ 113.1 (2 C), 114.2 (4 C), 118.4

(1 C), 121.1 (2 C), 122.5 (2 C), 125.9 (2 C), 126.2 (1 C), 127.9 (2

C), 129.6 (4 C), 133.0 (2 C), 139.4 (2 C), 144.3 (2 C). IR (KBr):

ν˜ ϭ 3376 cm^Ϫ1, 3050, 1618, 1599, 1560, 1497, 1453, 1320, 1297,

869, 782, 738. MS (EI): m/z ϭ 360 [M^ϩ]. C₂₆H₂₀N₂(360.45): calcd.

C 86.64, H 5.59, N 7.77; found C 86.31, H 5.24, N 7.48.

C), 132.6 (2 C), 139.2 (2 C), 143.1 (2 C). IR (KBr): ν˜ ϭ 3431 cm^Ϫ1

,

3057, 1617, 1568, 1502, 1467, 1452, 1356, 1276, 891, 836, 738, 727.

N,NЈ-Bis(3-aminopropyl)anthracene-1,8-diamine (3g): See Table 1,

entry 9. The reaction mixture was chromatographed with 10:3:1

CH₂Cl₂/CH₃OH/NH₃to yield a brown solid: m.p. 81Ϫ82 °C. Yield

1

155 mg (48%). H NMR (CDCl₃ϩ CH₃OH(5%), ppm): δ ϭ 1.88

N,NЈ-Di-p-tolylanthracene-1,8-diamine (3b): See Table 1, entry 3.

The reaction mixture was chromatographed with toluene to yield a

dark brown solid: m.p. 118Ϫ120 °C. Yield 167 mg (43%). ¹H NMR

(CDCl₃, ppm): δ ϭ 2.38 (s, 6 H), 5.98 (br. s, 2 H), 7.06 (d, J ϭ

8.6 Hz, 4 H), 7.17 (d, J ϭ 8.6 Hz, 4 H), 7.27 (d, J ϭ 7.9 Hz, 2 H),

7.37 (br. t, J ϭ 7.7 Hz, 2 H), 7.65 (d, J ϭ 8.2 Hz, 2 H), 8.40 (s, 1

H), 8.77 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 20.9 (2 C), 111.5

(2 C), 113.7 (1 C), 119.4 (4 C), 121.7 (2 C), 125.7 (3 C), 125.9 (2

C), 127.4 (2 C), 130.1 (4 C), 132.9 (2 C), 140.2 (2 C), 141.4 (2 C).

IR (KBr): ν˜ ϭ 3380 cm^Ϫ1, 3021, 1612, 1587, 1563, 1513, 1453,

1319, 1290, 812, 736. MS (EI): m/z ϭ 388 [M^ϩ].

(q, J ϭ 6.7 Hz, 4 H), 2.80 (br. s, 4 H), 2.91 (t, J ϭ 6.6 Hz, 4 H),

3.34 (t, J ϭ 6.7 Hz, 4 H), 5.60 (br. s, 2 H), 6.41 (m, 2 H), 7.30 (m,

4 H), 8.24 (s, 1 H), 8.47 (s, 1 H). ¹³C NMR (CDCl₃ϩ CH₃OH(5%),

ppm): δ ϭ 31.7 (2 C), 41.1 (2 C), 43.3 (2 C), 101.4 (2 C), 112.0 (1

C), 116.7 (2 C), 122.6 (1 C), 126.5 (2 C), 126.8 (2 C), 132.5 (2 C),

144.1 (2 C). IR (KBr): ν˜ ϭ 3449 cm^Ϫ1, 3048, 1614, 1566, 1521,

1466, 1285, 887, 778, 730. MS (EI): m/z ϭ 322 [M^ϩ].

1,8-Dimorpholinoanthracene (3h): See Table 1, entry 10. The reac-

tion mixture was chromatographed successively with pentane/di-

chloromethane 1:1 and dichloromethane to yield a yellow-green

1

solid: m.p. 220 °C (dec.). Yield 271 mg (78%). H NMR (CDCl₃,

N,NЈ-Bis(4-ethoxyphenyl)anthracene-1,8-diamine (3c): See Table 1,

entry 4. The reaction mixture was chromatographed with toluene

to yield a red-brown solid: m.p. 185Ϫ186 °C. Yield 242 mg (54%).

¹H NMR (CDCl₃, ppm): δ ϭ 1.41 (t, J ϭ 7.3 Hz, 6 H), 4.02 (q,

J ϭ 7.3 Hz, 4 H), 5.90 (br. s, 2 H), 6.88 (d, J ϭ 8.8 Hz, 4 H), 7.01

(d, J ϭ 6.8 Hz, 2 H), 7.12 (d, J ϭ 8.8 Hz, 4 H), 7.30 (br. t, J ϭ

7.3 Hz, 2 H), 7.54 (d, J ϭ 8.2 Hz, 2 H), 8.38 (s, 1 H), 8.75 (s, 1 H).

¹³C NMR (CDCl₃, ppm): δ ϭ 15.1 (2 C), 64.0 (2 C), 109.4 (2 C),

113.0 (1 C), 115.6 (4 C), 120.8 (2 C), 122.5 (4 C), 125.0 (1 C), 127.4

(2 C), 128.5 (2 C), 132.9 (2 C), 136.5 (2 C), 141.5 (2 C), 154.8 (2

C). IR (KBr): ν˜ ϭ 3366 cm^Ϫ1, 1597, 1563, 1513, 1441, 1283, 820,

732. MS (EI): m/z ϭ 448 [M^ϩ]. C₃₀H₂₈N₂O₂(448.56): calcd. C

80.33, H 6.29, N 6.25; found C 79.81, H 6.25, N 5.98.

ppm): δ ϭ 3.20 (m, 8 H), 4.07 (m, 8 H), 7.02 (d, J ϭ 6.8 Hz, 2 H),

7.35 (br. t, J ϭ 8.1 Hz, 2 H), 7.70 (d, J ϭ 8.8 Hz, 2 H), 8.38 (s, 1

H), 9.19 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 53.8 (4 C), 67.9 (4

C), 113.6 (2 C), 118.3 (1 C), 123.9 (2 C), 125.6 (2 C), 127.3 (1 C),

127.5 (2 C), 133.1 (2 C), 149.8 (2 C). IR (KBr): ν˜ ϭ 1617 cm^Ϫ1

1561, 1448, 1240, 888, 741. MS (EI): m/z ϭ 348 [M^ϩ].

,

1,8-Dipiperidin-1-ylanthracene (3i): See Table 1, entries 11, 12. The

reaction mixture was chromatographed with pentane/dichloro-

methane 1:1 to yield a yellow-green solid: m.p. 229Ϫ231 °C. Yield

1

107 mg (31%, BINAP). H NMR (CDCl₃, ppm): δ ϭ 1.73 (br. s, 4

H), 1.95 (m, 8 H), 3.14 (br. s, 8 H), 6.98 (d, J ϭ 7.3 Hz, 2 H), 7.32

(t, J ϭ 8.3 Hz, 2 H), 7.64 (d, J ϭ 8.3 Hz, 2 H), 8.34 (s, 1 H), 9.17

(s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 25.0 (2 C), 27.1 (4 C), 55.0

(4 C), 113.1 (2 C), 119.1 (1 C), 123.0 (2 C), 125.6 (2 C), 126.9 (1

N,NЈ-Dimethyl-N,NЈ-diphenylanthracene-1,8-diamine (3d): See

Table 1, entries 5,6. The reaction mixture was chromatographed

with toluene to yield a yellow-green solid: m.p. 140Ϫ142 °C. Yield C), 127.5 (2 C), 133.0 (2 C), 151.6 (2 C). IR (KBr): ν˜ ϭ 1614 cm^Ϫ1

,

217 mg (56%, using BINAP). ¹H NMR (CDCl₃, ppm): δ ϭ 3.18 (s, 1562, 1448, 1243, 896, 742. MS (EI): m/z ϭ 344 [M^ϩ]. C₂₄H₂₈N₂

6 H), 6.69 (d, J ϭ 7.2 Hz, 4 H), 6.80 (t, J ϭ 7.2 Hz, 2 H), 7.21 (br. (344.49): calcd. C 83.68, H 8.19, N 8.13; found C 83.51, H 8.29,

t, J ϭ 7.6 Hz, 4 H), 7.40 (d, J ϭ 6.2 Hz, 2 H), 7.52 (br. t, J ϭ N 7.96.

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FULL PAPER

(8-Chloroanthracen-1-yl)diethylamine (4): 1,8-Dichloroanthraqui-

IR (KBr): ν˜ ϭ 3236 cm^Ϫ1, 3073, 1659, 1620, 1593, 1568, 1511,

none (277 mg, 1 mmol), diethylamine (74 mg, 1.05 mmol), and Na- 1445, 1300, 1237, 749. MS (EI): m/z ϭ 390 [M^ϩ].

OtBu (144 mg, 1.5 mmol) were added to a solution of Pd(dba)₂

1,8-Bis(p-tolylamino)anthraquinone (7b): See Table 2, entry 2. The

(11 mg, 0.02 mmol) and BINAP (18 mg, 0.03 mmol) in dioxane (10

mL) in an argon-flushed flask. The mixture was heated at reflux

with stirring until 1 had been consumed (GC analysis of the reac-

tion mixture). After the reaction mixture had been cooled to room

temperature and concentrated in vacuo, the residue was taken up

with a mixture of dichloromethane and water. The organic layer

was washed with water and dried over anhydrous sodium sulfate,

and the solvents were evaporated in vacuo. The crude material was

purified by column chromatography on silica with toluene as an

eluent to provide the pure product (153 mg, 54%) as a yellow-green

reaction mixture was chromatographed with toluene to yield a vi-

olet solid: m.p. 203Ϫ205 °C. Yield 398 mg (95%). ¹H NMR

(CDCl₃, ppm): δ ϭ 2.35 (s, 6 H), 7.17 (br. s, 8 H), 7.39 (m, 4 H),

7.62 (dd, J ϭ 6.3, 2.3 Hz, 2 H), 11.19 (br. s, 2 H). ¹³C NMR

(CDCl₃, ppm): δ ϭ 21.1 (2 C), 115.3 (2 C), 117.2 (2 C), 120.1 (2

C), 124.4 (2 C), 130.2 (2 C), 134.0 (4 C), 134.4 (2 C), 134.7 (2 C),

137.2 (2 C), 149.3 (2 C), 183.9 (1 C), 188.8 (1 C). MS (EI): m/z ϭ

418 [M^ϩ].

1,8-Bis(4-ethoxyphenylamino)anthraquinone (7c): See Table 2, en-

tries 3, 4. The reaction mixture was chromatographed with toluene

to yield a violet solid: m.p. 190Ϫ192 °C. Yield 467 mg (98%, BI-

1

oil. H NMR (CDCl₃, ppm): δ ϭ 1.20 (t, J ϭ 7.4 Hz, 6 H), 3.32

(q, J ϭ 7.4 Hz, 4 H), 7.11 (d, J ϭ 7.4 Hz, 1 H), 7.33 (br. t, J ϭ

7.2 Hz, 1 H), 7.46 (br. t, J ϭ 7.6 Hz, 1 H), 7.54 (d, J ϭ 7.4 Hz, 1

H), 7.71 (d, J ϭ 8.4 Hz, 1 H), 7.89 (d, J ϭ 8.6 Hz, 1 H), 8.40 (s, 1

H), 9.34 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 12.8 (2 C), 47.8 (2

C), 116.7 (1 C), 120.7 (1 C), 122.9 (1 C), 124.9 (1 C), 125.2 (1 C),

126.2 (1 C), 127.1 (1 C), 127.4 (1 C), 128.6 (1 C), 130.4 (1 C), 132.4

(1 C), 133.4 (1 C), 133.6 (1 C), 148.5 (1 C). MS (EI): m/z ϭ 283,

285 [M^ϩ].

1

NAP), 268 mg (56%, dppf). H NMR (CDCl₃, ppm): δ ϭ 1.44 (t,

J ϭ 7.3 Hz, 6 H), 4.03 (q, J ϭ 7.3 Hz, 4 H), 6.92 (d, J ϭ 8.8 Hz,

4 H), 7.19 (d, J ϭ 8.8 Hz, 4 H), 7.26 (br. d, J ϭ 7.2 Hz, 2 H), 7.37

(br. t, J ϭ 7.4 Hz, 2 H), 7.62 (dd, J ϭ 7.0, 1.4 Hz, 2 H), 11.11 (br.

s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 15.0 (2 C), 63.8 (2 C), 115.0

(2 C), 115.5 (4 C), 116.9 (2 C), 120.0 (2 C), 126.8 (4 C), 132.4 (2

C), 134.1 (2 C), 134.4 (2 C), 150.2 (2 C), 156.8 (2 C), 184.2 (1 C),

189.0 (1 C). IR (KBr): ν˜ ϭ 3222 cm^Ϫ1, 1657, 1612, 1566, 1511,

1479, 1289, 747. MS (EI): m/z ϭ 478 [M^ϩ]. C₃₀H₂₆N₂O₄(478.54):

calcd. C 75.30, H 5.48, N 5.85; found C 75.16, H 5.55, N 5.95.

N,N-Diethyl-NЈ-phenylanthracene-1,8-diamine

(5):

(8-Chlo-

roanthracen-1-yl)diethylamine (4; 283 mg, 1 mmol), aniline

(102 mg, 1.1 mmol), and NaOtBu (144 mg, 1.5 mmol) were added

to a solution of Pd(dba)₂(11 mg, 0.02 mmol) and BINAP (18 mg,

0.03 mmol) in dioxane (10 mL) in an argon-flushed flask. The mix-

ture was heated at reflux with stirring until 4 had been consumed

(GC analysis of the reaction mixture). After cooling down to room

temperature the mixture was concentrated in vacuo, and the residue

was taken up with a mixture of dichloromethane and water. The

organic layer was washed with water and dried over anhydrous so-

dium sulfate, and the solvents were evaporated in vacuo. The crude

material was purified by column chromatography on silica with

toluene as an eluent to provide the pure product (163 mg, 48%) as

a yellow-green oil. ¹³C NMR (CDCl₃, ppm): δ ϭ 12.5 (2C), 47.8

(2 C), 112.7 (1 C), 116.6 (1 C), 117.1 (1 C), 118.4 (2 C), 120.9 (1

C), 122.5 (1 C), 123.2 (1 C), 125.6 (3 C), 126.0 (1 C), 127.1 (1 C),

129.5 (2 C), 132.8 (1 C), 133.4 (1 C), 139.4 (1 C), 144.7 (1 C). MS

(EI): m/z ϭ 340 [M^ϩ]. C₂₄H₂₄N₂(340.46): calcd. C 84.67, H 7.11,

N 8.23; found C 84.45, H 7.33, N 7.96.

1,8-Bis(hexylamino)anthraquinone (7e): See Table 2, entry 5. The re-

action mixture was chromatographed with toluene to yield a violet

solid: m.p. 182Ϫ184 °C. Yield 398 mg (98%). ¹H NMR (CDCl₃,

ppm): δ ϭ 0.92 (t, J ϭ 7.3 Hz, 6 H), 1.38 (m, 12 H), 1.76 (m, 4 H),

3.28 (m, 4 H), 6.92 (d, J ϭ 8.5 Hz, 2 H), 7.44 (br. t, J ϭ 7.2 Hz, 2

H), 7.51 (d, J ϭ 7.6 Hz, 2 H), 9.60 (br. s, 2 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 14.3 (2 C), 22.8 (2 C), 27.1 (2 C), 29.3 (2 C), 31.8 (2 C),

43.5 (2 C), 114.9 (2 C), 115.1 (2 C), 118.0 (2 C), 134.3 (2 C), 134.5

(2 C), 151.2 (2 C), 184.8 (1 C), 189.1 (1 C). IR (KBr): ν˜ ϭ 3276

cm^Ϫ1, 1660, 1620, 1596, 1567, 1516, 1299, 835, 742. MS (EI):

m/z ϭ 406 [M^ϩ]. C₂₆H₃₄N₂·CH₃OH (406.56·CH₃OH): calcd. C

73.94, H 8.73, N 6.39; found C 74.14, H 8.63, N 6.45.

1,8-Bis[(3-aminopropyl)amino]anthraquinone (7g): See Table 2, entry

6. The reaction mixture was chromatographed with CH₂Cl₂/

CH₃OH/NH₃10:3:1 to yield a violet solid: m.p. 164Ϫ166 °C. Yield

1

169 mg (48%). H NMR (CDCl₃, ppm): δ ϭ 1.26 (br. s, 4 H), 1.88

(q, J ϭ 6.8 Hz, 4 H), 2.86 (t, J ϭ 6.8 Hz, 4 H), 3.28 (q, J ϭ 6.8 Hz,

4 H), 6.89 (dd, J ϭ 7.2, 1.8 Hz, 2 H), 7.36 (br. t, J ϭ 7.6 Hz, 2 H),

7.44 (dd, J ϭ 8.4, 1.8 Hz, 2 H), 9.49 (br. s, 2 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 33.0 (2 C), 40.1 (2 C), 40.7 (2 C), 114.4 (2 C), 114.9 (2

C), 117.6 (2 C), 134.1 (2 C), 134.3 (2 C), 151.1 (2 C), 184.6 (1 C),

188.9 (1 C). IR (KBr): ν˜ ϭ 3287 cm^Ϫ1, 1658, 1620, 1568, 1514,

1472, 1285, 835, 743. MS (EI): m/z ϭ 352 [M^ϩ].

General Procedure for the Palladium-Catalysed Reactions of 1,8-Di-

chloroanthra-9,10-quinone: Dioxane (10 mL), the indicated

amounts of Pd(dba)₂and ligand (Table 2), Cs₂CO₃(3 mmol), 1,8-

dichloroanthraquinone (277 mg, 1 mmol) and the amine (3 mmol)

were placed in an argon-flushed two-neck flask fitted with a mag-

netic stirrer and condenser. The reaction mixture was heated at

reflux for 24 h, cooled down to room temperature and concentrated

in vacuo. The residue was taken up with a mixture of dichlorometh-

ane and water, the organic layer was washed with water and dried

over anhydrous sodium sulfate, and the solvents were evaporated

in vacuo. The crude material was purified by column chromatogra-

phy on silica. The following compounds were prepared by the

above procedure; the results are summarised in Table 2.

1,8-Dimorpholinoanthraquinone (7h): See Table 2, entry 7. The reac-

tion mixture was chromatographed with pentane/ethyl acetate 1:2

to yield a dark crimson solid: m.p. 206Ϫ208 °C. Yield 299 mg

1

(79%). H NMR (CDCl₃, ppm): δ ϭ 3.13 (m, 8 H), 3.94 (m, 8 H),

7.31 (d, J ϭ 6.1 Hz, 2 H), 7.54 (br. t, J ϭ 7.4 Hz, 2 H), 7.81 (d,

J ϭ 7.6 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 53.5 (4 C), 67.3

(4 C), 120.7 (2 C), 125.1 (2 C), 127.4 (2 C), 133.4 (2 C), 135.1 (2

1,8-Bis(phenylamino)anthraquinone (7a): See Table 2, entry 1. The

reaction mixture was chromatographed with toluene to yield a vi-

olet solid: m.p. 230Ϫ232 °C. Yield 382 mg (98%). ¹H NMR

C), 152.3 (2 C), 183.7 (1 C), 184.9 (1 C). IR (KBr): ν˜ ϭ 1661 cm^Ϫ1

1638, 1583, 1425, 892, 747. MS (EI): m/z ϭ 378 [M^ϩ].

,

(CDCl₃, ppm): δ ϭ 7.31 (m, 14 H), 7.69 (dd, J ϭ 7.0, 1.8 Hz, 2 H), 1,8-Dipiperidinoanthraquinone (7i): See Table 2, entries 8, 9. The re-

11.20 (br. s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 115.6 (2 C), 117.6 action mixture was chromatographed with pentane/ethyl acetate 9:1

(2 C), 120.3 (2 C), 124.0 (4 C), 124.9 (2 C), 129.7 (4 C), 134.2 (2 to yield a dark crimson solid: m.p. 182Ϫ184 °C. Yield 135 mg

1

C), 134.3 (2 C), 139.9 (2 C), 148.9 (2 C), 184.0 (1 C), 189.1 (1 C). (36%, dppf), 116 mg (31%, BINAP). H NMR (CDCl₃, ppm): δ ϭ

Eur. J. Org. Chem. 2005, 281Ϫ305

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297

I. P. Beletskaya, R. Guilard et al.

FULL PAPER

1.62 (br. s, 4 H), 1.82 (m, 8 H), 3.01 (br. s, 8 H), 7.34 (d, J ϭ

7.2 Hz, 2 H), 7.48 (br. t, J ϭ 7.4 Hz, 2 H), 7.75 (d, J ϭ 7.6 Hz, 2

(1 mmol). The reaction mixture was chromatographed with

CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield a brown solid. Yield 75 mg

1

H). ¹³C NMR (CDCl₃, ppm): δ ϭ 24.4 (2 C), 26.4 (4 C), 54.6 (4 (21%). H NMR* (CDCl₃, ppm): δ ϭ 1.63 (q, J ϭ 5.6 Hz, 2 H),

C), 119.5 (2 C), 125.4 (2 C), 127.4 (2 C), 132.7 (2 C), 135.1 (2 C), 1.95 (br. q, J ϭ 4.9 Hz, 4 H), 2.71 (t, J ϭ 5.6 Hz, 4 H), 2.81 (t,

153.4 (2 C), 183.9 (1 C), 185.4 (1 C). IR (KBr): ν˜ ϭ 1666 cm^Ϫ1

,

J ϭ 5.0 Hz, 4 H), 3.42 (t, J ϭ 4.8 Hz, 4 H), 6.46 (dd, J ϭ 5.9,

1649, 1584, 1558, 1468, 1448, 887, 841, 790, 752. MS (EI): m/z ϭ 2.4 Hz, 2 H), 7.34 (m, 4 H), 8.28 (s, 1 H), 8.56 (s, 1 H). ¹³C NMR

374 [M^ϩ].

(CDCl₃, ppm): δ ϭ 27.5 (2 C), 29.8 (1 C), 44.7 (2 C), 48.9 (2 C),

50.1 (2 C), 101.8 (2 C), 112.5 (1 C), 116.8 (2 C), 123.1 (1 C), 126.3

(2 C), 126.4 (2 C), 132.5 (2 C), 144.2 (2 C). MALDI-TOF: m/z ϭ

362.78 [M^ϩ]. * NH signals are not indicated.

General Procedure for the Palladium-Catalysed Synthesis of the

Macrocycles Derived from Anthracene and Anthraquinone: A two-

necked flask fitted with a magnetic stirrer and condenser and

flushed with argon was charged with 1,8-(or 1,5-)dichloroanthra-

cene or 1,8- (or 1,5-)dichloroanthraquinone (1Ϫ2 mmol), the indi-

cated amount of Pd(dba)₂, BINAP, absolute dioxane (40Ϫ120 mL),

polyamine (1Ϫ2 mmol), and the appropriate base (NaOtBu or

Cs₂CO₃, 2Ϫ4 mmol). The reaction mixture was heated at reflux

with stirring (times are indicated in Tables 3Ϫ6), and after the mix-

ture had cooled down to room temperature the reaction solvents

were evaporated in vacuo, the residue was treated with dichloro-

methane (30Ϫ40 mL) and washed once with water (10Ϫ20 mL),

the water layer was extracted with dichloromethane (3 ϫ 20 mL),

the combined organic fractions were dried over anhydrous sodium

sulfate, and the solvents were evaporated in vacuo. The crude prod-

uct was chromatographed on silica.

Anthraceno-1,4,7,10,13-pentaazacyclooctadecane (9e): See Table 3,

entry 5. This compound was synthesised from 1,8-dichloroanthra-

cene (1; 2 mmol) and pentaamine 8e (2 mmol). The reaction mix-

ture was chromatographed with CH₂Cl₂/CH₃OH/NH₃30:6:1 to

yield a brown-green solid. Yield 190 mg (26%). ¹H NMR*^,**

(CDCl₃, ppm): δ ϭ 2.82 (m, 12 H), 3.30 (br. s, 4 H), 6.50 (br. s, 2

H), 7.30 (m, 4 H), 7.98 (br. s, 1 H), 8.40 (br. s, 1 H). ¹³C NMR**

(CDCl₃, ppm): δ ϭ 41.3 (2 C), 47.1 (2 C), 51.5 (4 C), 101.2 (2 C),

113.0 (1 C), 116.0 (2 C), 121.8 (1 C), 125.6 (2 C), 127.7 (2 C), 131.7

(2 C), 143.1 (2 C). MALDI-TOF: m/z ϭ 363.30 [M^ϩ]. * NH signals

are not indicated. ** Broad signals, multiplets were not resolved.

Anthraceno-1,4,7,10,13,16-hexaazacycloheneicosane

(9f):

See

Table 3, entry 6. This compound was synthesised from 1,8-di-

chloroanthracene (1; 2 mmol) and hexaamine 8f (2 mmol). The re-

action mixture was chromatographed with CH₂Cl₂/CH₃OH/NH₃

30:6:1 to yield a brown-green solid. Yield 180 mg (22%). ¹H NMR*

^,** (CDCl₃, ppm): δ ϭ 2.72 (m, 16 H), 3.30 (br. s, 4 H), 6.40 (br.

s, 2 H), 7.28 (m, 4 H), 7.95 (br. s, 1 H), 8.30 (br. s, 1 H). ¹³C

NMR** (CDCl₃, ppm): δ ϭ 41.4 (2 C), 45.7 (4 C), 50.2 (4 C), 100.0

(2 C), 112.9 (1 C), 115.8 (2 C), 121.8 (1 C), 125.6 (2 C), 127.7 (2

C), 131.7 (2 C), 143.5 (2 C). MALDI-TOF: m/z ϭ 406.91 [M^ϩ]. *

NH signals are not indicated. ** Broad signals, multiplets were

not resolved.

Compound 9a: See Table 3, entry 1. This compound was synthesised

from 1,8-dichloroanthracene (1; 1 mmol) and triethylenetetraamine

8a (1 mmol). The reaction mixture was chromatographed with

CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield a dark yellow-brown solid.

1

Yield 105 mg (33%). H NMR* (CDCl₃, ppm): δ ϭ 2.74 (s, 4 H),

2.87 (dd, J ϭ 5.7, 5.3 Hz, 4 H), 3.25 (dd, J ϭ 5.7, 5.3 Hz, 4 H),

6.59 (d, J ϭ 6.9 Hz, 2 H), 7.29 (dd, J ϭ 8.3, 6.9 Hz, 2 H), 7.42 (d,

J ϭ 8.3 Hz, 2 H), 8.25 (s, 1 H), 9.16 (s, 1 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 46.5 (2 C), 48.1 (2 C), 48.9 (2 C), 106.9 (2 C), 114.8 (1

C), 118.5 (2 C), 124.1 (1 C), 126.1 (2 C), 126.3 (2 C), 132.7 (2 C),

145.2 (2 C). MALDI-TOF: m/z ϭ 320.65 [M^ϩ]. * NH signals are

not indicated.

Compound 10a: See Table 3, entries 7, 8. This compound was syn-

thesised from 1,8-dichloroanthraquinone (4; 1 mmol) and triethyl-

enetetraamine 8a (1 mmol). The reaction mixture was chromato-

graphed with CH₂Cl₂/CH₃OH 10:1 to yield 10a as a red solid: yield

48 mg (14%, entry 7) or 33 mg (9%, entry 8), together with com-

pound 17a (25 mg, 8%, red solid). Further chromatography with

CH₂Cl₂/CH₃OH/NH₃30:6:1 gave a red solid, which was identified

as a mixture of compound 14a and compound 15a in 1:3 ratio: yield

91 mg (24%, entry 7) or 113 mg (30%, entry 8). 10a: ¹H NMR

(CDCl₃, ppm): δ ϭ 1.90 (br. s, 2 H), 2.70 (s, 4 H), 2.74 (t, J ϭ

5.3 Hz, 4 H), 3.45 (br. q, J ϭ 5.2 Hz, 4 H), 7.05 (dd, J ϭ 7.1,

2.4 Hz, 2 H), 7.42 (m, 4 H), 9.19 (t, J ϭ 5.0, 2 H). ¹³C NMR

(CDCl₃, ppm): δ ϭ 45.7 (2 C), 48.8 (2 C), 49.4 (2 C), 115.7 (2 C),

118.3 (2 C), 120.8 (2 C), 133.9 (2 C), 134.8 (2 C), 151.5 (2 C), 185.2

(1 C), 188.9 (1 C). MALDI-TOF: m/z ϭ 350.81 [M^ϩ]. 14a: ¹H

NMR (CDCl₃, ppm): δ ϭ 1.95 (br. s, 4 H), 2.68 (m, 2 H), 2.77 (m,

6 H), 3.00 (t, J ϭ 5.8 Hz, 2 H), 3.43 (br. q, J ϭ 5.5 Hz, 2 H), 7.04

(d, J ϭ 8.9 Hz, 1 H), 7.52 (m, 4 H), 7.74 (d, J ϭ 8.0 Hz, 1 H), 8.24

(d, J ϭ 7.7 Hz, 1 H), 9.86 (t, J ϭ 4.6 Hz, 1 H). ¹³C NMR***

(CDCl₃, ppm): δ ϭ 42.1 (1 C), 43.1 (1 C), 48.7 (1 C), 49.3 (1 C),

49.6 (1 C), 52.8 (1 C), 114.4 (1 C), 116.1 (1 C), 118.3 (1 C), 126.8

(1 C), 127.1 (1 C), 132.9 (1 C), 134.1 (1 C), 137.3 (1 C), 152.0 (1

C), 184.1 (1 C), 185.0 (1 C). MALDI-TOF: m/z ϭ 352.80 [M^ϩ].

Compound 9b: See Table 3, entry 2. This compound was synthesised

from 1,8-dichloroanthracene (1; 1 mmol) and tetraamine 8b

(1 mmol). The reaction mixture was chromatographed with

CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield a brown solid. Yield 121 mg

(36%). ¹H NMR (CDCl₃, ppm): δ ϭ 1.59 (q, J ϭ 6.4 Hz, 2 H),

2.58 (br. s, 2 H), 2.76 (t, J ϭ 6.4 Hz, 4 H), 2.91 (t, J ϭ 5.3 Hz, 4

H), 3.20 (t, J ϭ 5.3 Hz, 4 H), 5.35 (br. s, 2 H), 6.50 (d, J ϭ 7.4 Hz,

2 H), 7.34 (dd, J ϭ 8.5, 7.4 Hz, 2 H), 7.40 (dd, J ϭ 8.5 Hz, 2 H),

8.27 (s, 1 H), 8.49 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 31.1 (1

C), 44.9 (2 C), 48.6 (2 C), 49.4 (2 C), 103.2 (2 C), 112.2 (1 C), 117.2

(2 C), 123.2 (1 C), 126.5 (2 C), 126.6 (2 C), 132.6 (2 C), 144.4 (2

C). MALDI-TOF: m/z ϭ 333.91 [M^ϩ]. C₂₁H₂₆N₄(334.22): calcd.

C 75.41, H 7.84, N 16.75; found C 75.51, H 7.86, N 16.24.

Compound 9c: See Table 3, entry 3. This compound was synthesised

from 1,8-dichloroanthracene (1; 1 mmol) and tetraamine 8c

(1 mmol). The reaction mixture was chromatographed with

CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield a brown solid. Yield 82 mg

(24%). ¹H NMR* (CDCl₃, ppm): δ ϭ 1.93 (br. q, J ϭ 5.4 Hz, 4

H), 2.78 (s, 4 H), 2.87 (dd, J ϭ 5.1, 4.9 Hz, 4 H), 3.41 (dd, J ϭ

5.8, 5.2 Hz, 4 H), 6.41 (m, 2 H), 7.31 (m, 4 H), 8.26 (s, 1 H), 8.45

(s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.9 (2 C), 46.2 (2 C), 50.9

(2 C), 51.5 (2 C), 101.0 (2 C), 112.9 (1 C), 116.5 (2 C), 122.9 (1 C),

126.5 (2 C), 126.8 (2 C), 132.6 (2 C), 145.0 (2 C). * NH signals are

not indicated.

1

15a: H NMR (CDCl₃, ppm): δ ϭ 1.95 (br. s, 4 H), 2.68 (m, 2 H),

2.77 (m, 6 H), 2.99 (t, J ϭ 6.0 Hz, 2 H), 3.44 (t, J ϭ 5.8 Hz, 2 H),

7.07 (dd, J ϭ 7.0, 2.5 Hz, 1 H), 7.49 (m, 2 H), 7.54 (br. t, J ϭ

7.7 Hz, 1 H), 7.72 (dd, J ϭ 8.0, 1.4 Hz, 1 H), 8.20 (dd, J ϭ 7.4,

1.4 Hz, 1 H), 9.70 (t, J ϭ 4.9 Hz, 1 H). ¹³C NMR (CDCl₃, ppm):

δ ϭ 42.1 (1 C), 43.3 (1 C), 48.7 (1 C), 49.4 (1 C), 49.6 (1 C), 52.7

Compound 9d: See Table 3, entry 4. This compound was synthesised

from 1,8-dichloroanthracene (1; 1 mmol) and tetraamine 8d

298

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Palladium-Catalysed Amination of Anthracenes

FULL PAPER

(1 C), 115.6 (1 C), 118.8 (1 C), 124.7 (1 C), 126.2 (1 C), 126.8 (1 entry 12; 10%, entry 13), and 10d as a violet solid: yield 39 mg

C), 133.1 (1 C), 134.4 (1 C), 135.5 (1 C), 135.7 (1 C), 136.0 (1 C), (12%, entry 13). 10d: ¹H NMR (CDCl₃, ppm): δ ϭ 1.59 (br. s, 2

138.4 (1 C), 151.9 (1 C), 183.5 (1 C), 184.5 (1 C). MALDI-TOF: H), 1.80 (q, J ϭ 7.1 Hz, 2 H), 1.91 (br. q, J ϭ 6.0 Hz, 4 H), 2.79

1

m/z ϭ 386.89 [M^ϩ]. 17a: H NMR (CDCl₃, ppm): δ ϭ 1.90 (br. s,

(t, J ϭ 7.1 Hz, 4 H), 2.79 (t, J ϭ 6.2 Hz, 4 H), 3.42 (br. q, J ϭ

2 H), 2.93 (s, 4 H), 3.07 (t, J ϭ 5.7 Hz, 4 H), 3.40 (br. q, J ϭ 5.8 Hz, 4 H), 7.01 (dd, J ϭ 7.8, 1.6 Hz, 2 H), 7.46 (br. t, J ϭ 7.7 Hz,

5.2 Hz, 4 H), 6.81 (dd, J ϭ 8.0, 1.6 Hz, 2 H), 7.49 (m, 6 H), 7.58

2 H), 7.53 (dd, J ϭ 7.6, 1.6 Hz, 2 H), 9.83 (br. s, 2 H). ¹³C NMR

(dd, J ϭ 8.0, 1.5 Hz, 2 H), 8.07 (dd, J ϭ 7.3, 1.5 Hz, 2 H), 9.71 (t, (CDCl₃, ppm): δ ϭ 28.6 (2 C), 30.8 (1 C), 42.0 (2 C), 47.9 (2 C),

J ϭ 4.8 Hz, 2 H). MALDI-TOF: m/z ϭ 626.59 [M^ϩ]. 17a contained

48.1 (2 C), 115.1 (2 C), 115.3 (2 C), 118.1 (2 C), 134.5 (2 C), 134.8

a small amount of compound 16a: MALDI-TOF: m/z ϭ 592.71 (2 C), 151.5 (2 C), 185.3 (1 C), 189.2 (1 C). MALDI-TOF: m/z ϭ

[M^ϩ]. *** Some quaternary carbon signals of the anthraquinone

system were not unambiguously determined.

392.65 [M^ϩ]. 16d: ¹H NMR (CDCl₃, ppm): δ ϭ 1.81 (q, J ϭ 6.2 Hz,

2 H), 1.94 (br. q, J ϭ 6.6 Hz, 4 H), 2.72 (br. s, 2 H), 2.82 (br. t,

J ϭ 6.4 Hz, 8 H), 3.37 (br. q, J ϭ 6.0 Hz, 4 H), 6.95 (m, 1 H), 7.07

(m, 1 H), 7.46 (m, 6 H), 7.50 (t, J ϭ 7.6 Hz, 1 H), 7.67 (dd, J ϭ

7.6, 1.3 Hz, 1 H), 7.70 (dd, J ϭ 8.0, 1.3 Hz, 1 H), 8.12 (dd, J ϭ

7.6, 1.3 Hz, 1 H), 8.17 (dd, J ϭ 7.6, 1.6 Hz, 1 H), 9.58 (t, J ϭ

5.1 Hz, 1 H), 9.59 (t, J ϭ 5.0 Hz, 1 H). MALDI-TOF: m/z ϭ

634.87 [M^ϩ]. 17d: ¹H NMR (CDCl₃, ppm): δ ϭ 1.81 (q, J ϭ 6.2 Hz,

2 H), 1.94 (br. q, J ϭ 6.6 Hz, 4 H), 2.72 (br. s, 2 H), 2.82 (br. t,

J ϭ 6.4 Hz, 8 H), 3.37 (br. q, J ϭ 6.0 Hz, 4 H), 6.95 (m, 2 H), 7.46

(m, 4 H), 7.50 (t, J ϭ 7.6 Hz, 2 H), 7.67 (dd, J ϭ 7.6, 1.3 Hz, 2

H), 8.12 (dd, J ϭ 7.6, 1.3 Hz, 2 H), 9.58 (t, J ϭ 5.1 Hz, 2 H).

MALDI-TOF: m/z ϭ 668.73 [M^ϩ].

Compound 10b: See Table 3, entries 9, 10. This compound was syn-

thesised from 1,8-dichloroanthraquinone (4; 1 mmol) and tetra-

amine 8b (1 mmol). The reaction mixture was chromatographed

with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 10b as a violet solid:

yield 70 mg (8%, entry 9; 19%, entry 10). Further chromatography

with CH₂Cl₂/CH₃OH/NH₃30:6:1 yielded a violet solid, which was

identified as a mixture of compound 14b and compound 15b in 1:2

ratio: yield 69 mg (18%, entry 10). 10b: ¹H NMR (CDCl₃, ppm):

δ ϭ 1.68 (q, J ϭ 6.6 Hz, 2 H), 1.86 (br. s, 2 H), 2.93 (t, J ϭ 6.6 Hz,

4 H), 3.00 (t, J ϭ 5.0 Hz, 4 H), 3.28 (q, J ϭ 5.0 Hz, 4 H), 6.90 (m,

2 H), 7.42 (m, 4 H), 10.10 (t, J ϭ 5.0 Hz, 2 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 31.3 (1 C), 44.0 (2 C), 48.3 (2 C), 49.2 (2 C), 114.4 (2 Anthraquinono-1,4,7,10,13-pentaazacyclooctadecane

10e:

See

C), 115.3 (2 C), 118.0 (2 C), 133.9 (2 C), 134.4 (2 C), 150.9 (2 C), Table 3, entry 14. This compound was synthesised from dichloro-

185.2 (1 C), 188.2 (1 C). MALDI-TOF: m/z ϭ 365.01 ([M ϩ H]^ϩ).

14b: H NMR (CDCl₃, ppm): δ ϭ 1.72 (q, J ϭ 6.4 Hz, 2 H), 2.38 tion mixture was chromatographed on silica with CH₂Cl₂/CH₃OH/

(br. s, 4 H), 2.66 (m, 8 H), 2.87 (t, J ϭ 6.2 Hz, 2 H), 3.43 (br. q, NH₃30:6:1 to yield 10e (212 mg, 27%) as a violet solid. H NMR

anthraquinone (4; 2 mmol) and pentaamine 8e (2 mmol). The reac-

1

J ϭ 5.7 Hz, 2 H), 7.09 (m, 1 H), 7.54 (m, 4 H), 7.69 (dd, J ϭ 7.5, (CDCl₃, ppm): δ ϭ 1.95 (br. s, 3 H), 2.79 (m, 4 H), 2.94 (m, 4 H),

1.6 Hz, 1 H), 8.24 (dd, J ϭ 7.5, 1.6 Hz, 1 H), 9.83 (br. s, 1 H). ¹³C 3.02 (t, J ϭ 5.3 Hz, 4 H), 3.34 (dd, J ϭ 5.3, 4.0 Hz, 4 H), 6.93 (d,

NMR*** (CDCl₃, ppm): δ ϭ 29.9 (1 C), 41.2 (1 C), 42.7 (1 C),

J ϭ 8.5 Hz, 2 H), 7.41 (br. t, J ϭ 7.8 Hz, 2 H), 7.49 (d, J ϭ 7.4 Hz,

48.2 (1 C), 48.3 (1 C), 52.1 (1 C), 52.2 (1 C), 113.8 (1 C), 115.7 (1 2 H), 9.98 (t, J ϭ 4.0 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 41.5

C), 117.9 (1 C), 126.4 (1 C), 126.7 (1 C), 132.6 (1 C), 133.9 (1 C), (2 C), 47.4 (2 C), 48.9 (2 C), 49.3 (2 C), 113.8 (4 C), 116.7 (2 C),

135.3 (1 C), 151.5 (1 C), 184.1 (1 C), 184.9 (1 C). MALDI-TOF: 133.1 (2 C), 133.5 (2 C), 149.9 (2 C), 184.1 (1 C), 187.7 (1 C).

m/z ϭ 366.93 [M^ϩ]. 15b: ¹H NMR (CDCl₃, ppm): δ ϭ 1.72 (q, J ϭ

6.4 Hz, 2 H), 2.38 (br. s, 4 H), 2.66 (m, 8 H), 2.87 (t, J ϭ 6.2 Hz,

2 H), 3.44 (br. q, J ϭ 5.6 Hz, 2 H), 7.04 (m, 1 H), 7.50 (m, 2 H),

7.55 (t, J ϭ 8.0 Hz, 1 H), 7.73 (dd, J ϭ 8.0, 1.3 Hz, 1 H), 8.21 (dd,

J ϭ 8.0, 1.3 Hz, 1 H), 9.67 (t, J ϭ 4.5 Hz, 1 H). ¹³C NMR***

(CDCl₃, ppm): δ ϭ 29.8 (1 C), 41.2 (1 C), 42.9 (1 C), 48.2 (1 C),

48.4 (1 C), 52.1 (1 C), 52.2 (1 C), 115.2 (1 C), 118.3 (1 C), 126.7 (1

C), 132.9 (1 C), 134.4 (1 C), 135.0 (1 C), 138.0 (1 C), 151.5 (1 C),

183.0 (1 C), 184.1 (1 C). MALDI-TOF: m/z ϭ 400.93 [M^ϩ]. ***

Some quaternary carbon signals of the anthraquinone system were

not unambiguously determined.

MALDI-TOF: m/z ϭ 394.20 ([M ϩ H]^ϩ).

Compound 19a: See Table 4, entry 1. This compound was syn-

thesised from dichloroanthracene (1; 1 mmol) and dioxadiamine

18a (1 mmol). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH 100:1 to give brown-greenish 19a (90 mg,

28%) and the cyclic dimer 21a (27 mg, 8%) as a brown solid. 19a:

¹H NMR (CDCl₃, ppm): δ ϭ 3.53 (t, J ϭ 4.8 Hz, 4 H), 3.81 (t,

J ϭ 4.8 Hz, 4 H), 3.82 (s, 4 H), 4.92 (br. s, 2 H), 6.78 (d, J ϭ

7.0 Hz, 2 H), 7.42 (dd, J ϭ 8.5, 7.0 Hz, 2 H), 7.59 (d, J ϭ 8.5 Hz,

2 H), 8.41 (s, 1 H), 9.15 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ

47.4 (2 C), 70.3 (2 C), 71.1 (2 C), 108.2 (2 C), 114.7 (1 C), 119.5 (2

C), 124.4 (1 C), 126.1 (2 C), 126.5 (2 C), 132.8 (2 C), 144.9 (2 C).

MALDI-TOF: m/z ϭ 321.83 [M^ϩ]. C₂₀H₂₂N₂O₂(322.40): calcd. C

74.51, H 6.88; found C 75.30, H 7.06. 21a: ¹H NMR (CDCl₃, ppm):

Compound 10c: See Table 3, entry 11. This compound was syn-

thesised from 1,8-dichloroanthraquinone (4; 1 mmol) and tetra-

amine 8c (1 mmol). The reaction mixture was chromatographed

with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 10c as a violet solid: δ ϭ 3.47 (t, J ϭ 4.8 Hz, 8 H), 3.72 (s, 8 H), 3.89 (t, J ϭ 4.8 Hz, 8

1

yield 95 mg (25%). H NMR (CDCl₃, ppm): δ ϭ 1.90 (br. s, 2 H), H), 5.10 (br. s, 4 H), 6.38 (dd, J ϭ 7.1, 1.0 Hz, 4 H), 7.27 (br. t,

1.95 (br. q, J ϭ 6.0, 4 H), 2.84 (s, 4 H), 2.89 (dd, J ϭ 5.6, 5.2 Hz,

J ϭ 7.2 Hz, 4 H), 7.34 (dd, J ϭ 7.3, 1.0 Hz, 4 H), 8.26 (s, 2 H),

4 H), 3.32 (br. q, J ϭ 6.2 Hz, 4 H), 6.89 (d, J ϭ 7.8 Hz, 2 H), 7.40 8.72 (s, 2 H). MALDI-TOF: m/z ϭ 644.09 [M^ϩ].

(br. t, J ϭ 7.7 Hz, 2 H), 7.48 (d, J ϭ 7.5 Hz, 2 H), 9.94 (br. s, 2

Compound 19b: See Table 4, entry 2. This compound was syn-

H). ¹³C NMR (CDCl₃, ppm): δ ϭ 28.3 (2 C), 44.1 (2 C), 50.6 (2

C), 50.9 (2 C), 114.6 (2 C), 115.1 (2 C), 117.4 (2 C), 134.1 (2 C),

134.3 (2 C), 150.9 (2 C), 184.9 (1 C), 188.5 (1 C).

C₂₂H₂₆N₄O₂·0.5H₂O (378.21·0.5H₂O): calcd. C 67.95, H 6.59;

found C 68.19, H 7.02.

thesised from dichloroanthracene (1; 1 mmol) and dioxadiamine

18b (1 mmol). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH 200:1 to yield 19b (75 mg, 20%) as a brown-

greenish solid), and further chromatography with CH₂Cl₂/CH₃OH/

NH₃30:6:1 gave 108 mg (27%) of a mixture of 19b and compound

1

Compound 10d: See Table 3, entries 12, 13. This compound was

synthesised from 1,8-dichloroanthraquinone (4; 1 mmol) and tetra-

amine 8d (1 mmol). The reaction mixture was chromatographed

with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield a mixture of compound

25 (1:2). 19b: H NMR (CDCl₃, ppm): δ ϭ 1.74 (q, J ϭ 2.8 Hz, 4

H), 2.11 (q, J ϭ 5.3 Hz, 4 H), 3.50 (m, 8 H), 3.65 (t, J ϭ 5.3 Hz,

4 H), 5.47 (br. s, 2 H), 6.51 (m, 2 H), 7.38 (m, 4 H), 8.33 (s, 1 H),

8.35 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.6 (2 C), 27.8 (2 C),

16d and Compound 17d: (1:2) as a violet solid: yield 35 mg (3%, 43.4 (2 C), 70.5 (2 C), 70.9 (2 C), 101.4 (2 C), 111.3 (1 C), 116.7 (2

Eur. J. Org. Chem. 2005, 281Ϫ305

I. P. Beletskaya, R. Guilard et al.

FULL PAPER

C), 122.8 (1 C), 126.3 (2 C), 127.2 (2 C), 132.6 (2 C), 144.0 (2 C). N 6.86; found C 70.38, H 7.01, N 6.67. 26b (x ϭ 2): ¹H NMR

MALDI-TOF: m/z ϭ 377.96 [M^ϩ]. 25: ¹H NMR (CDCl₃, ppm):

δ ϭ 1.64 (m, 8 H), 2.60 (br. s, 2 H), 2.77 (m, 2 H), 3.37 (m, 6 H),

3.46 (t, J ϭ 6.5 Hz, 2 H), 3.61 (t, J ϭ 4.7 Hz, 2 H), 5.46 (br. s, 1

(CDCl₃, ppm): δ ϭ 1.72 (br. s, 8 H), 1.98 (q, J ϭ 6.2 Hz, 8 H), 3.39

(q, J ϭ 6.2 Hz, 8 H), 3.50 (br. s, 8 H), 3.58 (t, J ϭ 6.2 Hz, 8 H),

6.98 (d, J ϭ 7.9 Hz, 4 H), 7.46 (m, 8 H), 9.64 (t, J ϭ 6.2 Hz, 4 H).

H), 6.46 (dd, J ϭ 5.9, 2.3 Hz, 1 H), 7.36 (m, 3 H), 7.50 (d, J ϭ ¹³C NMR (CDCl₃, ppm): δ ϭ 26.4 (4 C), 29.0 (4 C), 40.3 (4 C),

7.2 Hz, 1 H), 7.85 (d, J ϭ 8.5 Hz, 1 H), 8.32 (s, 1 H), 8.74 (s, 1 H). 68.2 (4 C), 70.8 (4 C), 114.5 (4 C), 115.1 (4 C), 117.8 (4 C), 134.1

¹³C NMR (CDCl₃, ppm): δ ϭ 26.9 (2 C), 29.4 (1 C), 33.2 (1 C),

39.8 (1 C), 43.7 (1 C), 69.2 (1 C), 69.3 (1 C), 71.0 (1 C), 71.1 (1 C),

(4 C),134.3 (4 C), 150.8 (4 C), 184.5 (2 C), 188.5 (2 C). MALDI-

1

TOF: m/z ϭ 816.75 [M^ϩ]. 26b (x ϭ 3): H NMR (CDCl₃, ppm):

102.5 (1 C), 116.9 (1 C), 117.3 (1 C), 125.3 (2 C), 126.9 (1 C), 127.6 δ ϭ 1.77 (q, J ϭ 2.6 Hz, 12 H), 1.95 (q, J ϭ 6.2 Hz, 12 H), 3.32

(1 C), 127.7 (1 C), 127.8 (1 C), 128.3 (1 C), 129.1 (1 C), 132.5 (1 (q, J ϭ 6.2 Hz, 12 H), 3.46 (t, J ϭ 2.6 Hz, 12 H), 3.53 (t, J ϭ

C), 133.5 (1 C), 145.0 (1 C). MALDI-TOF: m/z ϭ 413.90 [M^ϩ].

5.9 Hz, 12 H), 6.94 (dd, J ϭ 8.2, 1.4 Hz, 6 H), 7.38 (dd, J ϭ 8.2,

7.2 Hz, 6 H), 7.45 (dd, J ϭ 7.2, 1.4 Hz, 6 H), 9.58 (t, J ϭ 6.2 Hz,

6 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.5 (6 C), 29.3 (6 C), 40.1 (6

C), 68.2 (6 C), 70.8 (6 C), 114.3 (6 C), 114.8 (6 C), 117.5 (6 C),

134.0 (6 C), 134.2 (6 C), 151.0 (6 C), 184.4 (3 C), 188.7 (3 C).

MALDI-TOF: m/z ϭ 1224.83 [M^ϩ].

Compound 19c: See Table 4, entry 3. This compound was syn-

thesised from dichloroanthracene (1; 1 mmol) and trioxadiamine

18c (1 mmol). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH 100:1 to yield 19c (100 mg, 25%) as a dark

yellow-greenish solid, and further chromatography with CH₂Cl₂/

CH₃OH 50:1 gave the cyclic dimer 21c (x ϭ 2, 38 mg, 10%) as a

brown-greenish solid and 35 mg (9%) of a mixture of cyclic trimer

21c (x ϭ 3) and tetramer 21c (x ϭ 4). 19c: ¹H NMR (CDCl₃, ppm):

δ ϭ 2.05 (q, J ϭ 5.5. Hz, 4 H), 3.57 (t, J ϭ 5.5 Hz, 4 H), 3.72 (m,

12 H), 5.70 (br. s, 2 H), 6.47 (m, 2 H), 7.31 (m, 4 H), 8.26 (s, 1 H),

8.49 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 28.1 (2 C), 42.5 (2 C),

70.1 (2 C), 70.2 (2 C), 70.6 (2 C), 101.5 (2 C), 112.1 (1 C), 116.7 (2

C), 123.1 (1 C), 126.7 (2 C), 127.3 (2 C), 133.1 (2 C), 144.3 (2 C).

MALDI-TOF: m/z ϭ 394.51 [M^ϩ]. C₂₄H₃₀N₂O₃(394.51): calcd. C

73.07, H 7.66; found C 73.24, H 7.35. 21c (x ϭ 2): ¹H NMR

(CDCl₃, ppm): δ ϭ 1.98 (br. q, J ϭ 6.0 Hz, 8 H), 3.37 (t, J ϭ

6.3 Hz, 8 H), 3.51 (t, J ϭ 5.5 Hz, 8 H), 3.54 (m, 8 H), 3.69 (m, 8

H), 5.50 (br. s, 4 H), 6.42 (m, 4 H), 7.29 (m, 8 H), 8.23 (s, 2 H),

8.45 (s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 29.0 (4 C), 42.9 (4 C),

70.5 (4 C), 70.6 (8 C), 101.8 (4 C), 112.4 (2 C), 117.0 (4 C), 123.1

(2 C), 126.8 (4 C), 127.1 (4 C), 132.9 (4 C), 144.5 (4 C). MALDI-

TOF: m/z ϭ 788.06 [M^ϩ]. 21c (x ϭ 3): MALDI-TOF: m/z ϭ

1182.96 [M^ϩ]. 21c (x ϭ 4): MALDI-TOF: m/z ϭ 1576.37 [M^ϩ].

Compound 20c: See Table 4, entries 6, 7. Method (a), entry 6. The

compound was synthesised from dichloroanthraquinone (4;

0.5 mmol) and dioxadiamine 18c (0.5 mmol). The reaction mixture

was chromatographed on silica with CH₂Cl₂/CH₃OH 200:1 to yield

20c (62 mg, 29%) as a violet solid. Further chromatography with

CH₂Cl₂/CH₃OH 100:1 gave 67 mg (ca. 32%) of a mixture of higher

mass cyclic (26c, x ϭ 2Ϫ4) and linear (27c, x ϭ 1Ϫ4) oligomers.

Chromatography with CH₂Cl₂/CH₃OH 40:1 yielded 32 mg (ca.

16%) of a mixture of cyclic (26c, x ϭ 5, 6) and linear (27c, x ϭ

5Ϫ8) oligomers. 20c: ¹H NMR (CDCl₃, ppm): δ ϭ 1.95 (br. q, J ϭ

5.5 Hz, 4 H), 3.44 (br. q, J ϭ 5.4 Hz, 4 H), 3.66 (t, J ϭ 5.6 Hz, 4

H), 3.69 (m, 4 H), 3.82 (m, 4 H), 6.95 (dd, J ϭ 8.2, 1.4 Hz, 2 H),

7.41 (dd, J ϭ 8.2, 7.3 Hz, 2 H), 7.48 (dd, J ϭ 7.3, 1.4 Hz, 2 H),

9.74 (t, J ϭ 4.9 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 28.2 (2

C), 40.5 (2 C), 69.1 (2 C), 70.5 (2 C), 71.1 (2 C), 114.6 (4 C), 117.3

(2 C), 133.9 (2 C), 134.4 (2 C), 150.9 (2 C), 184.5 (1 C), 188.3 (1 C).

MALDI-TOF: m/z ϭ 424.77 [M^ϩ]. C₂₄H₂₈N₂O₅(424.49): calcd. C

67.91, H 6.65, N 6.60; found C 67.40, H 6.84, N 6.04.

Compound 20a: See Table 4, entry 4. This compound was syn-

thesised from dichloroanthraquinone (4; 1 mmol) and dioxadi-

amine 18a (1 mmol). The reaction mixture was chromatographed

on silica with CH₂Cl₂/CH₃OH 100:1 to yield 20a (127 mg, 36%) as

a violet solid, and 7 mg (2%) of a mixture of cyclic tetramer and

Method (b), entry 7. The compound was synthesised from di-

chloroanthraquinone (4; 1 mmol) and dioxadiamine 18c (1 mmol).

The reaction mixture was chromatographed on silica with CH₂Cl₂/

CH₃OH 200:1 to yield 20c (159 mg, 37%) as a violet solid. Further

chromatography with CH₂Cl₂/CH₃OH 100:1 gave the cyclic dimer

26c (x ϭ 2, 79 mg, 18%) as a violet solid, then with CH₂Cl₂/

CH₃OH 50:1 a mixture of 26c (x ϭ 3Ϫ6), 27c (x ϭ 2Ϫ7) and 28c

(x ϭ 1Ϫ6) was collected (64 mg, ca. 14%), and finally with CH₂Cl₂/

CH₃OH 20:1 a mixture of 26c (x ϭ 6Ϫ8), 27c (x ϭ 6Ϫ8) and 28c

1

pentamer 26a (x ϭ 4, 5). 20a: H NMR (CDCl₃, ppm): δ ϭ 3.46

(m, 4 H), 3.50 (m, 4 H), 3.54 (s, 4 H), 7.03 (m, 2 H), 7.41 (m, 4

H), 9.25 (t, J ϭ 4.9 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 45.4

(2 C), 69.1 (2 C), 70.6 (2 C), 115.5 (2 C), 119.0 (2 C), 120.4 (2 C),

133.7 (2 C), 134.8 (2 C), 151.3 (2 C), 176.3 (1 C), 179.0 (1 C).

MALDI-TOF: m/z ϭ 353.18 ([M ϩ H]^ϩ).

1

(x ϭ 5Ϫ7) was collected (48 mg, ca. 11%). 26c (x ϭ 2): H NMR

(CDCl₃, ppm): δ ϭ 1.98 (br. q, J ϭ 6.1 Hz, 8 H), 3.30 (br. q, J ϭ

6.0 Hz, 8 H), 3.62 (t, J ϭ 6.2 Hz, 8 H), 3.63 (m, 8 H), 3.70 (m, 8

H), 6.88 (dd, J ϭ 8.5 Hz, 4 H), 7.34 (dd, J ϭ 8.5, 7.0 Hz, 4 H),

7.39 (d, J ϭ 7.0 Hz, 4 H), 9.54 (br. t, J ϭ 4.8 Hz, 4 H). ¹³C NMR

(CDCl₃, ppm): δ ϭ 29.7 (4 C), 40.5 (4 C), 69.2 (4 C), 70.8 (4 C),

71.1 (4 C), 114.7 (4 C), 115.2 (4 C), 117.8 (4 C), 134.3 (4 C), 134.6

(4 C), 151.4 (4 C), 184.8 (2 C), 188.9 (2 C). MALDI-TOF: m/z ϭ

848.11 [M^ϩ].

Compound 20b: See Table 4, entry 5. This compound was syn-

thesised from dichloroanthraquinone (4; 1 mmol) and dioxadi-

amine 18b (1 mmol). The reaction mixture was chromatographed

on silica with CH₂Cl₂/CH₃OH 200:1 to yield 20b (134 mg, 33%) as

a violet solid. Further chromatography with CH₂Cl₂/CH₃OH 100:1

gave cyclic dimer 26b (x ϭ 2, 48 mg, 12%) and cyclic trimer 26b

(x ϭ 3, 35 mg, 8%). Chromatography with CH₂Cl₂/CH₃OH 50:1

produced 82 mg (ca. 20%) of a complex mixture of higher mass

cyclic (26b, x ϭ 4Ϫ8) and linear (27b, x ϭ 2Ϫ8, 28b, x ϭ 2Ϫ7) Compound 31a (x ϭ 2): See Table 5, entry 1. This compound was

oligomers. 20b: ¹H NMR (CDCl₃, ppm): δ ϭ 1.75 (br. s, 4 H), 1.90 synthesised from 1,5-dichloroanthracene (29; 1 mmol) and tetra-

(br. q, J ϭ 5.0 Hz, 4 H), 3.34 (br. q, J ϭ 4.8 Hz, 4 H), 3.48 (br. s,

4 H), 3.53 (t, J ϭ 5.4 Hz, 4 H), 6.87 (d, J ϭ 8.2 Hz, 2 H), 7.34 (br. silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield cyclic dimer 31a

amine 8a (1 mmol). The reaction mixture was chromatographed on

(x ϭ 2, 58 mg, 18%) as a brown solid. ¹H NMR*^,** (CDCl₃, ppm):

t, J ϭ 7.9 Hz, 2 H), 7.44 (d, J ϭ 7.5 Hz, 2 H), 9.77 (t, J ϭ 4.6 Hz,

2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.3 (2 C), 28.2 (2 C), 40.9 (2 δ ϭ 2.88 (br. s, 8 H), 3.02 (br. s, 8 H), 3.34 (br. s, 8 H), 6.48 (br. s,

C), 68.8 (2 C), 71.3 (2 C), 114.4 (4 C), 117.2 (2 C), 133.8 (2 C), 4 H), 7.39 (m, 8 H), 8.37 (br. s, 4 H). MALDI-TOF: m/z ϭ 640.36

134.3 (2 C), 150.9 (2 C), 184.7 (1 C), 188.3 (1 C). MALDI-TOF: [M^ϩ]. * NH signals are not indicated. ** Broad signals, multiplets

m/z ϭ 408.13 [M^ϩ]. C₂₄H₂₈N₂O₄(408.49): calcd. C 70.57, H 6.91,

were not resolved.

300

www.eurjoc.org

Eur. J. Org. Chem. 2005, 281Ϫ305

Palladium-Catalysed Amination of Anthracenes

FULL PAPER

Anthraceno-1,4,8,11-tetraazacyclononadecane 30b: See Table 5, en-

s, 4 H), 6.23 (d, J ϭ 7.0 Hz, 4 H), 6.71 (d, J ϭ 8.3 Hz, 4 H), 6.88

try 2. This compound was synthesised from 1,5-dichloroanthracene (dd, J ϭ 8.3, 7.0 Hz, 4 H), 7.50 (s, 4 H). ¹³C NMR (CDCl₃, ppm):

(29; 1 mmol) and tetraamine 8b (1 mmol). The reaction mixture

δ ϭ 43.8 (4 C), 69.8 (4 C), 70.4 (4 C), 102.5 (4 C), 118.3 (4 C),

was chromatographed on silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 118.6 (4 C), 125.5 (4 C), 129.1 (4 C), 132.6 (4 C), 142.8 (4 C).

to yield first 49 mg (15%) of a complex mixture of 30b with 31b

(x ϭ 2Ϫ4) and 32b (x ϭ 1Ϫ3), and then free 30b (67 mg, 20%) and

the cyclic dimer 31b (x ϭ 2, 35 mg, 10%) as yellow-brown solids.

MALDI-TOF: m/z ϭ 644.75 [M^ϩ].

Anthraceno-1,14-diaza-5,10-dioxacyclodocosane 33b: See Table 5,

entry 6. This compound was synthesised from 1,5-dichloroanthra-

cene (29; 1 mmol) and dioxadiamine 18b (1 mmol). The reaction

mixture was chromatographed on silica with CH₂Cl₂/CH₃OH 500:1

to yield 32 mg (ca. 10%) of a mixture of 35b, 36b and 37b (x ϭ 0)

in 1:4:2 mol ratio (brown solid), and then with CH₂Cl₂/CH₃OH

250:1 to yield 33b (92 mg, 24%) as a brown-green solid. 33b: ¹H

NMR (CDCl₃, ppm): δ ϭ Ϫ0.22 (m, 2 H), 0.55 (m, 2 H), 1.47 (m,

2 H), 1.82 (td, J ϭ 9.0, 6.0 Hz, 2 H), 2.14 (m, 2 H), 2.59 (td, J ϭ

9.0, 6.0 Hz, 2 H), 3.22 (ddd, J ϭ 8.5, 6.0, 2.5 Hz, 2 H), 3.55 (ddd,

J ϭ 8.5, 6.0, 2.5 Hz, 2 H), 3.60 (ddd, J ϭ 14.5, 6.0, 3.0 Hz, 2 H),

3.73 (ddd, J ϭ 14.5, 6.0, 3.0 Hz, 2 H), 4.60 (br. s, 2 H), 6.67 (d,

J ϭ 7.0 Hz, 2 H), 7.24 (dd, J ϭ 8.5, 7.0 Hz, 2 H), 7.38 (d, J ϭ

8.5 Hz, 2 H), 8.38 (s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 25.9 (2

C), 26.9 (2 C), 44.5 (2 C), 70.2 (2 C), 70.9 (2 C), 105.4 (2 C), 118.4

(2 C), 120.1 (2 C), 124.7 (2 C), 125.4 (2 C), 131.8 (2 C), 144.3 (2

C). MALDI-TOF: m/z ϭ 378.66 [M^ϩ].

1

30b: H NMR (CDCl₃, ppm): δ ϭ 0.29 (q, J ϭ 7.5 Hz, 2 H), 0.90

(m, 4 H), 1.32 (m, 4 H), 1.73 (br. s, 2 H), 3.70 (m, 4 H), 5.35 (br.

s, 2 H), 6.82 (dd, J ϭ 7.0, 0.6 Hz, 2 H), 7.28 (dd, J ϭ 8.6, 7.0 Hz,

2 H), 7.59 (dd, J ϭ 8.6, 0.6 Hz, 2 H), 8.65 (s, 2 H). ¹³C NMR

(CDCl₃, ppm): δ ϭ 29.7 (1 C), 45.7 (2 C), 47.1 (2 C), 49.1 (2 C),

112.8 (2 C), 121.1 (2 C), 121.7 (2 C), 125.2 (2 C), 125.9 (2 C), 131.9

(2 C), 144.3 (2 C). MALDI-TOF: m/z ϭ 334.90 [M^ϩ]. 31b (x ϭ 2):

¹H NMR (CDCl₃, ppm): δ ϭ 1.70 (q, J ϭ 5.6 Hz, 4 H), 2.00 (br.

s, 4 H), 2.69 (t, J ϭ 5.6 Hz, 8 H), 2.77 (t, J ϭ 5.5 Hz, 8 H), 2.84

(t, J ϭ 5.5 Hz, 8 H), 4.27 (br. s, 4 H), 5.97 (d, J ϭ 7.0 Hz, 4 H),

7.17 (dd, J ϭ 8.3, 7.0 Hz, 4 H), 7.32 (d, J ϭ 8.3 Hz, 4 H), 8.02 (s,

4 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 29.5 (2 C), 42.6 (4 C), 47.2 (4

C), 48.4 (4 C), 102.1 (4 C), 117.5 (4 C), 118.9 (4 C), 123.5 (4 C),

125.7 (4 C), 131.4 (4 C), 142.8 (4 C). MALDI-TOF: m/z ϭ

668.66 [M^ϩ].

Anthraceno-1,5,8,12-tetraazacycloeicosane 30c: See Table 5, entry 3.

This compound was synthesised from 1,5-dichloroanthracene (29;

1 mmol) and tetraamine 8c (1 mmol). The reaction mixture was

chromatographed on silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to

yield 30c (120 mg, 34%) as a yellow-brown solid together with

traces of cyclic dimer and trimer 31c (x ϭ 2, 3). 30c: ¹H NMR*

(CDCl₃, ppm): δ ϭ 0.81 (m, 2 H), 1.38 (m, 2 H), 1.72 (m, 4 H),

2.26 (ddd, J ϭ 12.1, 7.3, 4.8 Hz, 2 H), 2.48 (m, 2 H), 3.44 (dt, J ϭ

14.9, 4.7 Hz, 2 H), 3.66 (ddd, J ϭ 14.9, 9.2, 3.5 Hz, 2 H), 6.79 (d,

J ϭ 7.0 Hz, 2 H), 7.26 (dd, J ϭ 8.3, 7.0 Hz, 2 H), 7.51 (d, J ϭ

8.3 Hz, 2 H), 8.53 (s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 28.7 (2

C), 44.4 (2 C), 47.7 (2 C), 49.0 (2 C), 110.9 (2 C), 120.2 (2 C), 121.3

(2 C), 124.9 (2 C), 125.7 (2 C), 131.7 (2 C), 144.8 (2 C). MALDI-

TOF: m/z ϭ 347.98 [M^ϩ]. 31c: MALDI-TOF: m/z ϭ 696.65 (x ϭ

2, M^ϩ), 1043.94 (x ϭ 3, M^ϩ). * NH signals are not indicated.

Anthraceno-1,15-diaza-5,8,11-dioxacyclotricosane 33c: See Table 5,

entry 7. This compound was synthesised from 1,5-dichloroanthra-

cene (29; 1 mmol) and dioxadiamine 18c (1 mmol). The reaction

mixture was chromatographed on silica with CH₂Cl₂/CH₃OH 500:1

to yield 23 mg (ca. 7%) of a mixture of 35c, 36c and 37c (x ϭ 0)

in 1:4:2 mol ratio (brown solid), and then with CH₂Cl₂/CH₃OH

200:1 to yield 33c (78 mg, 20%) as a brown-green solid. Further

chromatography with CH₂Cl₂/CH₃OH 100:1 gave the cyclic dimer

34c (x ϭ 2, 15 mg, 4%). 33c: ¹H NMR (CDCl₃, ppm): δ ϭ 1.68

(dtt, J ϭ 14.0, 7.5, 3.5 Hz, 2 H), 2.06 (dtt, J ϭ 14.0, 7.5, 3.5 Hz, 2

H), 2.19 (ddd, J ϭ 10.0, 7.5, 6.0 Hz, 2 H), 2.42 (ddd, J ϭ 10.0, 7.5,

5.5 Hz, 2 H), 2.65 (ddd, J ϭ 9.5, 7.5, 6.0 Hz, 2 H), 2.75 (ddd, J ϭ

9.5, 7.5, 5.5 Hz, 2 H), 3.25 (ddd, J ϭ 10.0, 7.0, 3.0 Hz, 2 H), 3.50

(ddd, J ϭ 10.0, 7.0, 3.0 Hz, 2 H), 3.56 (ddd, J ϭ 11.0, 7.5, 3.5 Hz,

2 H), 3.64 (ddd, J ϭ 11.0, 7.5, 3.5 Hz, 2 H), 4.50 (br. s, 2 H), 6.65

(d, J ϭ 7.0 Hz, 2 H), 7.32 (dd, J ϭ 8.3, 7.0 Hz, 2 H), 7.42 (d, J ϭ

8.3 Hz, 2 H), 8.36 (s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 27.2 (2

C), 44.1 (2 C), 68.2 (2 C), 68.6 (2 C), 70.3 (2 C), 104.4 (2 C), 117.4

(2 C), 119.0 (2 C), 124.0 (2 C), 125.2 (2 C), 131.2 (2 C), 143.8 (2 C).

MALDI-TOF: m/z ϭ 394.09 [M^ϩ]. C₂₄H₃₀N₂O₃(394.51): calcd. C

73.07, H 7.66, N 7.10; found C 73.49, H 7.55, N 6.56. 34c (x ϭ 2):

¹H NMR (CDCl₃, ppm): δ ϭ 1.88 (br. q, J ϭ 5.9 Hz, 8 H), 3.20

(t, J ϭ 6.2 Hz, 8 H), 3.53 (t, J ϭ 5.1 Hz, 8 H), 3.68 (m, 16 H), 5.10

(br. s, 4 H), 6.31 (d, J ϭ 6.7 Hz, 4 H), 7.31 (m, 8 H), 8.13 (s, 4 H).

MALDI-TOF: m/z ϭ 788.50 [M^ϩ].

Anthraceno-1,5,9,13-tetraazacycloheneicosane 30d: See Table 5, en-

try 4. This compound was synthesised from 1,5-dichloroanthracene

(29; 1 mmol) and tetraamine 8d (1 mmol). The reaction mixture

was chromatographed on silica with CH₂Cl₂/CH₃OH/NH₃30:6:1

to yield 30d (78 mg, 22%) as a yellow-brown solid together with

5% of cyclic dimer and trimer 31d (x ϭ 2, 3). 30d: ¹H NMR*

(CDCl₃, ppm): δ ϭ 0.19 (q, J ϭ 7.8 Hz, 2 H), 1.33 (m, 2 H), 1.54

(m, 2 H), 1.78 (m, 2 H), 1.93 (m, 2 H), 2.13 (ddd, J ϭ 11.8, 7.0,

4.4 Hz, 2 H), 2.28 (ddd, J ϭ 11.8, 7.0, 4.4 Hz, 2 H), 3.45 (ddd, J ϭ

15.0, 9.2, 3.5 Hz, 2 H), 3.63 (dt, J ϭ 15.0, 4.3 Hz, 2 H), 6.68 (d,

J ϭ 7.3 Hz, 2 H), 7.28 (dd, J ϭ 8.6, 7.3 Hz, 2 H), 7.43 (d, J ϭ

8.6 Hz, 2 H), 8.45 (s, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.5 (2

C), 28.9 (1 C), 44.7 (2 C), 46.6 (2 C), 47.2 (2 C), 107.9 (2 C), 119.0

(2 C), 120.2 (2 C), 124.6 (2 C), 125.9 (2 C), 131.9 (2 C), 143.4 (2

C). MALDI-TOF: m/z ϭ 362.01 [M^ϩ]. 31d (x ϭ 2, 3): MALDI-

TOF: m/z ϭ 724.65 (x ϭ 2, M^ϩ), 1086.34 (x ϭ 3, M^ϩ). * NH

signals are not indicated.

Compound 40a (x ϭ 2): See Table 6, entry 1. This compound was

synthesised from 1,5-dichloroanthraquinone (38; 1 mmol) and di-

oxadiamine 18a (1 mmol). The reaction mixture was chromato-

graphed on silica with CH₂Cl₂/CH₃OH 100:1 to yield 40a (x ϭ 2,

64 mg, 18%) as a red solid (containing admixed 41, 42a (x ϭ 1,

1

2)). 40a: H NMR (CDCl₃, ppm): δ ϭ 3.43 (br. q, J ϭ 4.7 Hz, 8

H), 3.82 (s, 8 H), 3.91 (t, J ϭ 5.3 Hz, 8 H), 6.85 (d, J ϭ 8.0 Hz, 4

H), 7.35 (m, 8 H), 9.59 (t, J ϭ 3.4 Hz, 4 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 43.1 (4 C), 69.9 (4 C), 71.3 (4 C), 113.4 (4 C), 115.0 (4

C), 116.0 (4 C), 134.9 (4 C), 135.0 (4 C), 151.2 (4 C), 184.8 (4 C).

MALDI-TOF: m/z ϭ 704.16 [M^ϩ]. 41a: MALDI-TOF: m/z ϭ

946.37 (x ϭ 1, M^ϩ), 1298.85 (x ϭ 2, M^ϩ). 42a: MALDI-TOF:

m/z ϭ 980.17 (x ϭ 1, M^ϩ), 1332.65 (x ϭ 2, M^ϩ).

Compound 34a (x ϭ 2): See Table 5, entry 5. This compound was

synthesised from 1,5-dichloroanthracene (29; 1 mmol) and dioxadi-

amine 18a (1 mmol). The reaction mixture was chromatographed

on silica with CH₂Cl₂to yield 53 mg (ca. 18%) of a mixture of 35a,

36a and 37a (x ϭ 0, 1) (brown solid), and then with CH₂Cl₂/

CH₃OH 100:1 to yield cyclic dimer 34a (x ϭ 2, 25 mg, 8%) as a

brown-greenish solid. 34a: ¹H NMR (CDCl₃, ppm): δ ϭ 3.44 (t, Anthraquinono-1,14-diaza-5,10-dioxacyclodocosane

J ϭ 4.8 Hz, 8 H), 3.86 (s, 8 H), 3.96 (t, J ϭ 4.8 Hz, 8 H), 4.90 (br. Table 6, entry 2. This compound was synthesised from 1,5-di-

39b:

See

Eur. J. Org. Chem. 2005, 281Ϫ305

www.eurjoc.org

301

I. P. Beletskaya, R. Guilard et al.

FULL PAPER

chloroanthraquinone (38; 1 mmol) and dioxadiamine 18b

(1 mmol). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH 200:1 to yield 39b (123 mg, 30%) as a violet

solid. Further chromatography with CH₂Cl₂/CH₃OH 100:1 yielded

(1 C), 49.2 (1 C), 52.5 (1 C), 112.3 (1 C), 115.9 (1 C), 117.3 (1 C),

126.2 (1 C), 129.2 (1 C), 133.4 (1 C), 134.4 (1 C), 135.6 (2 C), 136.3

(1 C), 137.5 (1 C), 151.2 (1 C), 183.2 (2 C). MALDI-TOF: m/z ϭ

1

387.08 ([M ϩ H]^ϩ). 46a: H NMR (CDCl₃, ppm): δ ϭ 2.39 (br. s,

the cyclic dimer 40b (x ϭ 2, 44 mg, 10%), and the cyclic trimer 40b

(x ϭ 3, 27 mg, 6%) as violet solids. 39b: H NMR (CDCl₃, ppm): 5.8 Hz, 4 H), 6.74 (dd, J ϭ 7.3, 2.2 Hz, 2 H), 7.42 (m, 4 H), 7.56

2 H), 2.94 (s, 4 H), 2.92 (t, J ϭ 6.7 Hz, 4 H), 3.32 (br. q, J ϭ

1

δ ϭ 0.60 (br. s, 4 H), 1.55 (m, 2 H), 1.96 (m, 2 H), 2.42 (m, 2 H),

2.62 (m, 2 H), 3.29 (m, 6 H), 3.76 (m, 2 H), 7.06 (dd, J ϭ 8.3, H). ¹³C NMR (CDCl₃, ppm): δ ϭ 40.1 (2 C), 42.6 (2 C), 45.7 (2

1.0 Hz, 2 H), 7.41 (dd, J ϭ 8.3, 7.3 Hz, 2 H), 7.51 (dd, J ϭ 7.3, C), 112.3 (2 C), 115.8 (2 C), 117.2 (2 C), 126.2 (2 C), 129.0 (2 C),

(m, 4 H), 8.14 (dd, J ϭ 7.3, 1.3 Hz, 2 H), 9.61 (t, J ϭ 4.1 Hz, 2

1.0 Hz, 2 H), 9.51 (dd, J ϭ 9.2, 4.4 Hz, 2 H). ¹³C NMR (CDCl₃, 133.1 (2 C), 133.3 (2 C), 135.6 (4 C), 136.3 (2 C), 137.4 (2 C), 151.0

ppm): δ ϭ 26.5 (2 C), 28.2 (2 C), 42.2 (2 C), 69.7 (2 C), 70.8 (2 C), (2 C), 182.4 (2 C), 182.5 (2 C). MALDI-TOF: m/z ϭ 626.81 [M^ϩ].

115.0 (2 C), 115.3 (2 C), 118.6 (2 C), 134.3 (2 C), 136.2 (2 C), 152.8 45a: MALDI-TOF: m/z ϭ 592.93 [M^ϩ].

(2 C), 185.2 (2 C). MALDI-TOF: m/z ϭ 408.54 [M^ϩ]. C₂₄H₂₈N₂O₄

Compound 44b: See Table 6, entry 5. This compound was syn-

thesised from 1,5-dichloroanthraquinone (38; 1 mmol) and tetra-

(408.49): calcd. C 70.57, H 6.91, N 6.86; found C 70.23, H 6.85, N

6.48. 40b (x ϭ 2): H NMR (CDCl₃, ppm): δ ϭ 1.72 (br. s, 8 H),

1

amine 8b (1 mmol). The reaction mixture was chromatographed on

1.91 (br. q, J ϭ 5.6 Hz, 8 H), 3.32 (br. q, J ϭ 5.7 Hz, 8 H), 3.51

silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 44b (102 mg, 25%)

(br. s, 8 H), 3.54 (t, J ϭ 5.4 Hz, 8 H), 6.81 (m, 4 H), 7.31 (m, 8 H),

as a deep-red solid and compound 46b (15 mg, 5%), also as a deep-

9.58 (t, J ϭ 4.8 Hz, 4 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.4 (4

red solid, together with traces of compound 45b. 44b: ¹H NMR

C), 29.3 (4 C), 39.9 (4 C), 67.9 (4 C), 70.9 (4 C), 112.7 (4 C), 114.5

(4 C), 116.0 (4 C), 134.8 (4 C), 135.9 (4 C), 151.2 (4 C), 185.2 (4

(CDCl₃, ppm): δ ϭ 1.68 (q, J ϭ 6.8 Hz, 2 H), 1.98 (br. s, 4 H), 2.68

(m, 8 H), 2.93 (t, J ϭ 6.0 Hz, 2 H), 3.38 (br. q, J ϭ 5.7 Hz, 2 H),

C). MALDI-TOF: m/z ϭ 816.09 [M^ϩ]. 40b (x ϭ 3): ¹H NMR

6.95 (m, 1 H), 7.45 (m, 2 H), 7.55 (dd, J ϭ 8.9, 7.9 Hz, 1 H), 7.62

(CDCl₃, ppm): δ ϭ 1.67 (m, 12 H), 1.92 (br. q, J ϭ 6.0 Hz, 12 H),

(dd, J ϭ 7.9, 1.6 Hz, 1 H), 8.18 (dd, J ϭ 8.9, 1.6 Hz, 1 H), 9.62 (t,

3.35 (br. q, J ϭ 6.1 Hz, 12 H), 3.44 (t, J ϭ 5.5 Hz, 12 H), 3.52 (t,

J ϭ 4.8 Hz, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 30.1 (1 C), 41.5

J ϭ 5.8 Hz, 12 H), 6.88 (m, 6 H), 7.42 (m, 12 H), 9.67 (t, J ϭ

(1 C), 42.7 (1 C), 48.1 (2 C), 48.3 (1 C), 52.4 (1 C), 112.3 (1 C),

5.2 Hz, 6 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 26.4 (6 C), 29.4 (6 C),

115.9 (1 C), 117.3 (1 C), 126.2 (1 C), 129.2 (1 C), 133.4 (1 C), 134.3

39.9 (6 C), 68.0 (6 C), 70.9 (6 C), 112.8 (6 C), 114.6 (6 C), 116.2 (6

(1 C), 135.6 (2 C), 136.3 (1 C), 137.5 (1 C), 151.3 (1 C), 183.1 (2

C), 135.0 (6 C), 136.1 (6 C), 151.4 (6 C), 185.1 (6 C). MALDI-

C). MALDI-TOF: m/z ϭ 400.77 [M^ϩ]. 46b: ¹H NMR* (CDCl₃,

TOF: m/z ϭ 1224.26 [M^ϩ].

ppm): δ ϭ 1.73 (q, J ϭ 6.2 Hz, 2 H), 2.89 (t, J ϭ 6.2 Hz, 4 H),

2.98 (t, J ϭ 6.0 Hz, 4 H), 3.32 (q, J ϭ 6.0 Hz, 4 H), 6.77 (dd, J ϭ

Anthraquinono-1,15-diaza-5,8,11-dioxacyclotricosane

39c:

See

7.9, 1.9 Hz, 2 H), 7.45 (m, 4 H), 7.56 (m, 4 H), 8.10 (dd, J ϭ 7.6,

1.6 Hz, 2 H), 9.56 (t, J ϭ 4.9 Hz, 2 H). MALDI-TOF: m/z ϭ

640.49 [M^ϩ]. 45b: MALDI-TOF: m/z ϭ 606.70 [M^ϩ]. * NH signals

are not indicated.

Table 6, entry 3. This compound was synthesised from 1,5-di-

chloroanthraquinone (38; 1 mmol) and trioxadiamine 18c

(1 mmol). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH 100:1 to yield 39c (119 mg, 28%) as a violet

solid. Further chromatography with CH₂Cl₂/CH₃OH 50:1 and 20:1

yielded fractions containing mixtures of cyclic and linear oligo-

mers: 40c (x ϭ 2Ϫ9), 41c (x ϭ 1Ϫ8), 43c (x ϭ 1Ϫ7) (194 mg, 44%).

39c: ¹H NMR (CDCl₃, ppm): δ ϭ 1.61 (m, 2 H), 1.97 (m, 2 H),

2.68 (m, 4 H), 2.92 (m, 4 H), 3.34 (m, 6 H), 3.71 (m, 2 H), 7.04

(dd, J ϭ 8.5, 1.0 Hz, 2 H), 7.43 (dd, J ϭ 8.5, 7.2 Hz, 2 H), 7.52

(dd, J ϭ 7.2, 1.0 Hz, 2 H), 9.50 (dd, J ϭ 9.2, 3.6 Hz, 2 H). ¹³C

NMR (CDCl₃, ppm): δ ϭ 28.3 (2 C), 41.8 (2 C), 68.8 (2 C), 69.5

(2 C), 69.8 (2 C), 114.8 (2 C), 115.0 (2 C), 118.6 (2 C), 134.5 (2 C),

136.1 (2 C), 152.8 (2 C), 185.1 (2 C). MALDI-TOF: m/z ϭ 424.15

[M^ϩ]. C₂₄H₂₈N₂O₅(424.49): calcd. C 67.91, H 6.65, N 6.60; found

C 67.99, H 6.53, N 6.14. 40c (x ϭ 2): ¹H NMR (CDCl₃, ppm): δ ϭ

1.92 (q, J ϭ 5.3 Hz, 8 H), 3.29 (q, J ϭ 6.2 Hz, 8 H), 3.62 (m, 24

H), 6.82 (m, 4 H), 7.27 (m, 8 H), 9.40 (t, J ϭ 5.1 Hz, 4 H). ¹³C

NMR (CDCl₃, ppm): δ ϭ 29.8 (4 C), 39.7 (4 C), 68.3 (4 C), 70.4

(4 C), 70.8 (4 C), 112.3 (4 C), 114.6 (4 C), 115.8 (4 C), 134.6 (4

C), 135.7 (4 C), 151.1 (4 C), 184.6 (4 C). MALDI-TOF: m/z ϭ

848.68 [M^ϩ].

Compound 44c: See Table 6, entry 6. This compound was syn-

thesised from 1,5-dichloroanthraquinone (38; 1 mmol) and tetra-

amine 8c (1 mmol). The reaction mixture was chromatographed on

silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 44c (96 mg, 23%)

as a deep-red solid and compound 46c (32 mg, 10%), also as a deep-

red solid, together with traces of compound 45c. 44c: ¹H NMR

(CDCl₃, ppm): δ ϭ 1.58 (br. q, J ϭ 6.9 Hz, 2 H), 1.86 (br. q, J ϭ

6.7 Hz, 2 H), 2.07 (br. s, 4 H), 2.62 (t, J ϭ 7.0 Hz, 2 H), 2.70 (s, 4

H), 2.71 (t, J ϭ 7.0 Hz, 2 H), 2.74 (t, J ϭ 7.3 Hz, 2 H), 3.32 (br.

q, J ϭ 6.3 Hz, 2 H), 6.93 (m, 1 H), 7.41 (m, 2 H), 7.53 (dd, J ϭ

7.9, 7.3 Hz, 1 H), 7.6 (dd, J ϭ 7.9, 1.9 Hz, 1 H), 8.16 (dd, J ϭ 7.3,

1.9 Hz, 1 H), 9.52 (t, J ϭ 4.9 Hz, 1 H). ¹³C NMR (CDCl₃, ppm):

δ ϭ 29.4 (1 C), 33.4 (1 C), 40.4 (1 C), 41.0 (1 C), 47.4 (1 C), 47.7

(1 C), 49.4 (2 C), 112.0 (1 C), 115.8 (1 C), 117.2 (1 C), 126.1 (1 C),

129.2 (1 C), 133.3 (1 C), 134.3 (1 C), 135.6 (2 C), 136.3 (1 C), 137.4

(1 C), 151.2 (1 C), 183.0 (2 C). MALDI-TOF: m/z ϭ 414.84 [M^ϩ].

1

46c: H NMR* (CDCl₃, ppm): δ ϭ 1.92 (br. q, J ϭ 6.7 Hz, 4 H),

2.68 (t, J ϭ 7.1 Hz, 4 H), 2.85 (s, 4 H), 3.37 (br. q, J ϭ 5.9 Hz, 4

H), 6.98 (m, 2 H), 7.45 (m, 4 H), 7.55 (t, J ϭ 7.9, 7.3 Hz, 2 H),

7.63 (dd, J ϭ 7.9, 1.6 Hz, 2 H), 8.19 (dd, J ϭ 7.3, 1.6 Hz, 2 H),

9.59 (t, J ϭ 4.6 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 28.9 (2

C), 40.9 (2 C), 52.4 (2 C), 52.7 (2 C), 112.1 (2 C), 115.8 (2 C), 117.3

(2 C), 126.1 (2 C), 129.1 (2 C), 133.3 (2 C), 134.3 (2 C), 135.6 (4

C), 136.3 (2 C), 137.5 (2 C), 151.3 (2 C), 182.3 (4 C). MALDI-TOF:

m/z ϭ 654.08 [M^ϩ]. 45c: MALDI-TOF: m/z ϭ 620.18 [M^ϩ]. * NH

signals are not indicated.

Compound 44a: See Table 6, entry 4. This compound was syn-

thesised from 1,5-dichloroanthraquinone (38; 1 mmol) and tetra-

amine 8a (1 mmol). The reaction mixture was chromatographed on

silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 44a (110 mg, 28%)

as a deep-red solid and compound 46a (32 mg, 10%), also as a deep-

red solid, together with traces of compound 45a. 44a: ¹H NMR

(CDCl₃, ppm): δ ϭ 1.86 (br. s, 4 H), 2.74 (m, 8 H), 2.97 (t, J ϭ

6.0 Hz, 2 H), 3.38 (br. q, J ϭ 5.5 Hz, 2 H), 6.96 (m, 1 H), 7.47 (m,

2 H), 7.57 (dd, J ϭ 8.3, 7.3 Hz, 1 H), 7.65 (dd, J ϭ 8.3, 1.9 Hz, 1

Compound 44d (Table 6, entries 7Ϫ9): Method (a), entry 7. The

H), 8.21 (dd, J ϭ 7.3, 1.9 Hz, 1 H), 9.70 (t, J ϭ 4.4 Hz, 1 H). ¹³C compound was synthesised from 1,5-dichloroanthraquinone (38;

NMR (CDCl₃, ppm): δ ϭ 41.2 (1 C), 42.6 (1 C), 48.1 (1 C), 48.9 1 mmol) and tetraamine 8d (1 mmol) by treatment with Pd(dba)₂/

302

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Eur. J. Org. Chem. 2005, 281Ϫ305

Palladium-Catalysed Amination of Anthracenes

FULL PAPER

BINAP (8/9 mol %). The reaction mixture was chromatographed

on silica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 44d (22 mg, 5%)

as a deep-red solid and compound 46d (58 mg, 17%), also as a deep-

red solid, together with traces of compound 45d. 44d: ¹H NMR*

127.2 (1 C), 129.0 (1 C), 130.7 (1 C), 132.3 (1 C), 132.7 (1 C), 133.4

(1 C), 149.4 (1 C). 52: ¹H NMR (CDCl₃, ppm): δ ϭ 2.63 (m, 11

H), 2.75 (m, 4 H), 3.21 (m, 4 H), 7.24 (d, J ϭ 8.4 Hz, 1 H), 7.30

(m, 3 H), 7.74 (d, J ϭ 8.3 Hz, 1 H), 7.90 (m, 1 H), 8.01 (m, 1 H),

(CDCl₃, ppm): δ ϭ 1.68 (br. q, J ϭ 6.7 Hz, 2 H), 1.89 (q, J ϭ 8.35 (s, 1 H), 9.22 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 46.5 (2

7.3 Hz, 4 H), 2.45 (m, 6 H), 2.78 (br. t, J ϭ 6.4 Hz, 4 H), 3.37 (br. C), 47.6 (2 C), 48.0 (2 C), 52.1 (2 C), 119.0 (1 C), 122.6 (1 C), 125.1

q, J ϭ 6.0 Hz, 2 H), 7.02 (m, 1 H), 7.49 (m, 2 H), 7.59 (dd, J ϭ

(1 C), 125.3 (1 C), 125.5 (1 C), 126.5 (1 C), 127.7 (1 C), 129.1 (1

8.0, 7.3 Hz, 1 H), 7.67 (dd, J ϭ 8.0, 1.6 Hz, 1 H), 8.24 (dd, J ϭ C), 129.3 (1 C), 130.0 (1 C), 131.4 (1 C), 131.6 (1 C), 133.2 (1 C),

7.3, 1.6 Hz, 1 H), 9.59 (t, J ϭ 5.3 Hz, 1 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 24.0 (1 C), 27.0 (1 C), 27.2 (1 C), 41.4 (2 C), 53.0 (3 C),

148.4 (1 C). MALDI-TOF: m/z ϭ 348.84 [M^ϩ].

Method (b). 1,8-Dichloroanthracene (1; 738 mg, 3.0 mmol), cyclen

53.8 (1 C), 112.5 (1 C), 116.2 (1 C), 117.8 (1 C), 126.6 (1 C), 129.6 (50; 550 mg, 3.2 mmol), NaOtBu (600 mg, 6.25 mmol), Pd(dba)₂

(1 C), 133.7 (1 C), 134.7 (1 C), 136.0 (2 C), 136.6 (1 C), 137.9 (1 (103 mg, 0.18 mmol) and BINAP (165 mg, 0.265 mmol) were dis-

C), 151.7 (1 C), 182.7 (1 C), 183.4 (1 C). MALDI-TOF: m/z ϭ

solved under argon in dioxane (80 mL) in a two-necked flask. The

428.70 [M^ϩ]. 46d: H NMR* (CDCl₃, ppm): δ ϭ 1.74 (br. q, J ϭ reaction mixture was heated at reflux for 50 h, cooled down to

7.2 Hz, 2 H), 1.90 (br. q, J ϭ 6.5 Hz, 4 H), 2.76 (t, J ϭ 6.4 Hz, 4 room temperature, and concentrated in vacuo. The residue was

1

H), 2.79 (t, J ϭ 6.0 Hz, 4 H), 3.32 (br. q, J ϭ 4.5 Hz, 4 H), 6.96 taken up with dichloromethane (30 mL), washed with water (15

(m, 2 H), 7.45 (m, 4 H), 7.60 (m, 4 H), 8.16 (dd, J ϭ 7.6, 1.6 Hz, mL) and dried over anhydrous sodium sulfate, and the solvents

2 H), 9.55 (t, J ϭ 4.9 Hz, 2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 29.1 were evaporated in vacuo. The crude product was chromatographed

(2 C), 32.0 (1 C), 43.4 (2 C), 47.4 (2 C), 48.2 (2 C), 112.5 (2 C),

on silica successively with CH₂Cl₂and CH₂Cl₂/CH₃OH/NH₃10:3:1

116.2 (2 C), 117.7 (2 C), 126.6 (2 C), 129.7 (2 C), 133.7 (2 C), 134.8 to yield 52 (565 mg, 54%).

(2 C), 136.0 (4 C), 136.7 (2 C), 137.9 (2 C), 151.8 (2 C), 182.8 (2

C), 183.5 (2 C). MALDI-TOF: m/z ϭ 668.84 [M^ϩ]. 45d: MALDI-

TOF: m/z ϭ 634.81 [M^ϩ]. * NH signals are not indicated.

Method (b), entry 8. The compound was synthesised from 1,5-di-

chloroanthraquinone (38; 1 mmol) and tetraamine 8d (1 mmol) by

treatment with Pd(dba)₂/BINAP (16/18 mol %). The reaction mix-

ture was chromatographed on silica with CH₂Cl₂/CH₃OH/NH₃

30:6:1 to yield 44d (110 mg, 25%) and 46d (89 mg, 26%), together

with traces of 45d and 47d: ¹H NMR**** (CDCl₃, ppm): δ ϭ 0.65

(q, J ϭ 8.2 Hz, 2 H), 3.76 (ddd, J ϭ 14.6, 10.2, 4.5 Hz, 2 H), 7.18

(dd, J ϭ 8.3, 1.6 Hz, 2 H), 7.58 (m, 4 H), 9.11 (dd, J ϭ 9.8, 4.5 Hz,

2 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 23.6 (1 C), 29.7 (2 C), 41.2 (2

C), 47.7 (2 C), 49.3 (2 C), 116.5 (2 C), 117.5 (2 C), 120.8 (2 C),

134.8 (2 C), 136.4 (2 C), 152.9 (2 C), 185.5 (2 C). MALDI-TOF:

m/z ϭ 393.14 ([M ϩ H]^ϩ). **** Signals of other aliphatic protons

of 47d were not determined due to their overlapping with the sig-

nals of corresponding aliphatic protons of the major compound

46d.

1-(1-Anthracenyl)-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetra-

decane (54): A two-necked flask filled with argon was charged with

1,8-dichloroanthracene (1; 247 mg, 1 mmol), N,NЈ,NЈЈ-trimethylcy-

clam (53; 484 mg, 2 mmol), Pd(dba)₂(92 mg, 0.16 mmol), PtBu₃

(26 mg, 0.14 mmol), NaOtBu (400 mg, 4.2 mmol) and dioxane (10

mL). The reaction mixture was heated at reflux for ca. 100 h and

then cooled down to room temperature, dioxane was evaporated in

vacuo, the reaction mixture was taken up with dichloromethane (30

mL) and washed with water (15 mL), the water layer was washed

twice with dichloromethane (20 mL), the organic layers were com-

bined and dried over anhydrous sodium sulfate, and the solvent

was evaporated in vacuo. The residue was chromatographed on sil-

ica with CH₂Cl₂/CH₃OH/NH₃30:6:1 to afford 54 (190 mg, 45%)

as a brown solid. ¹H NMR (CDCl₃, ppm): δ ϭ 1.67 (br. q, J ϭ

6.5 Hz, 2 H), 1.78 (br. q, J ϭ 6.2 Hz, 2 H), 2.14 (s, 3 H), 2.17 (s, 3

H), 2.30 (s, 3 H), 2.52 (m, 12 H), 3.21 (t, J ϭ 6.4 Hz, 2 H), 3.36 (t,

J ϭ 6.7 Hz, 2 H), 7.12 (d, J ϭ 7.3 Hz, 1 H), 7.28 (dd, J ϭ 8.3,

7.3 Hz, 1 H), 7.39 (m, 2 H), 7.68 (d, J ϭ 8.3 Hz, 1 H), 7.95 (dd,

J ϭ 6.2, 3.7 Hz, 1 H), 8.03 (dd, J ϭ 6.5, 3.4 Hz, 1 H), 8.34 (s, 1

H), 9.21 (s, 1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 24.3 (1 C), 24.7 (1

C), 43.1 (2 C), 43.4 (1 C), 49.5 (1 C), 51.0 (1 C), 53.0 (1 C), 53.7

(1 C), 53.9 (1 C), 54.8 (1 C), 55.0 (1 C), 55.3 (1 C), 117.6 (1 C),

123.5 (1 C), 123.7 (1 C), 124.8 (1 C), 125.3 (1 C), 126.9 (1 C), 127.2

(1 C), 127.8 (1 C), 129.7 (1 C), 130.4 (1 C), 131.3 (1 C), 131.5 (1

C), 133.2 (1 C), 149.1 (1 C). MALDI-TOF: m/z ϭ 418.65 [M^ϩ].

Method (c), entry 9. The compound was synthesised from 1,5-di-

chloroanthraquinone (38; 1 mmol) and tetraamine 8d (1 mmol) by

treatment with Pd(dba)₂/2-(di-tert-butylphosphanyl)biphenyl (10/

10 mol %). The reaction mixture was chromatographed on silica

with CH₂Cl₂/CH₃OH/NH₃30:6:1 to yield 46d (37 mg, 11%) and

44d (68 mg, 16%).

1-(8-Chloro-1-anthracenyl)-1,4,7,10-tetraazacyclododecane (51) and

1-(1-Anthracenyl)-1,4,7,10-tetraazacyclododecane (52): Method (a).

1,8-Dichloroanthracene (1; 247 mg, 1 mmol), cyclen (50; 172 mg, 1-(8-Chloro-1-anthracenyl)-4,8,11-trimethyl-1,4,8,11-tetraazacyclo-

1 mmol), NaOtBu (200 mg, 2.1 mmol), Pd(dba)₂(23 mg, tetradecane (55): The procedure used was analogous to that de-

0.05 mmol) and BINAP (62 mg, 0.1 mmol) were dissolved under

argon in dioxane (40 mL) in a two-necked flask. The reaction mix-

scribed for the synthesis of 54, except that Pd(dba)₂(46 mg,

0.08 mmol) and BINAP (55 mg, 0.088 mmol) were employed in-

ture was heated at reflux for 24 h, and then cooled down to room stead of PtBu₃. Chromatography of the crude material on silica

temperature and concentrated in vacuo. The residue was taken up

with dichloromethane (30 mL), washed with water (15 mL), and

dried over anhydrous sodium sulfate, and the solvents were evapo-

rated in vacuo. The crude product was chromatographed on silica

with CH₂Cl₂/CH₃OH/NH₃30:6:1 gave an equimolar mixture of 54

and 55 (172 mg, 39%). 55: H NMR (CDCl₃, ppm): δ ϭ 1.68 (br.

q, J ϭ 6.5 Hz, 2 H), 1.73 (br. q, J ϭ 6.2 Hz, 2 H), 2.15 (s, 3 H),

2.19 (s, 3 H), 2.27 (s, 3 H), 2.51 (m, 12 H), 3.23 (t, J ϭ 6.7 Hz, 2

1

successively with CH₂Cl₂and with CH₂Cl₂/CH₃OH/NH₃10:3:1 to H), 3.33 (t, J ϭ 6.6 Hz, 2 H), 7.17 (dd, J ϭ 7.3, 1.0 Hz, 1 H), 7.38

yield a mixture of 51 and 52 in 2:1 ratio (172 mg, yields 26 and (m, 2 H), 7.50 (dd, J ϭ 7.3, 1.0 Hz, 1 H), 7.82 (d, J ϭ 8.6 Hz, 1

13% respectively). 51: ¹H NMR (CDCl₃, ppm): δ ϭ 2.63 (m, 11 H), H), 8.01 (d, J ϭ 7.3 Hz, 1 H), 8.33 (s, 1 H), 9.41 (s, 1 H). ¹³C NMR

2.75 (m, 4 H), 3.21 (m, 4 H), 7.26 (d, J ϭ 7.8 Hz, 1 H), 7.38 (m, 2

H), 7.51 (d, J ϭ 7.7 Hz, 1 H), 7.74 (dd, J ϭ 8.5, 7.7 Hz, 1 H), 7.83

(CDCl₃, ppm): δ ϭ 22.7 (1 C), 23.7 (1 C), 41.3 (1 C), 41.5 (1 C),

42.0 (1 C), 51.8 (1 C), 53.5 (1 C), 53.7 (1 C), 54.0 (4 C), 54.5 (1 C),

(d, J ϭ 8.5 Hz, 1 H), 8.35 (s, 1 H), 9.56 (s, 1 H). ¹³C NMR (CDCl₃, 119.0 (1 C), 119.2 (1 C), 125.1 (2 C), 125.6 (1 C), 126.1 (1 C), 127.6

ppm): δ ϭ 46.2 (2 C), 46.7 (2 C), 47.5 (2 C), 52.5 (2 C), 119.7 (1

(2 C), 128.7 (1 C), 130.5 (1 C), 132.0 (1 C), 132.3 (1 C), 133.4 (1

C), 119.9 (1 C), 124.9 (2 C), 125.3 (1 C), 125.9 (1 C), 127.1 (1 C), C), 148.0 (1 C). MALDI-TOF: m/z ϭ 452.91 [M^ϩ].

Eur. J. Org. Chem. 2005, 281Ϫ305

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303

I. P. Beletskaya, R. Guilard et al.

FULL PAPER

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Maverick, Inorg. Chem. 1997, 36, 5826Ϫ5831.

R. W.

1,1Ј-(1,8-Anthracenediyl)bis(4,8,11-trimethyl-1,4,8,11-tetraazacyclo-

tetradecane) (56): The procedure used was analogous to that de-

scribed for the synthesis of 55, except that double quantities of

Pd(dba)₂(92 mg, 0.16 mmol) and BINAP (110 mg, 0.176 mmol)

were employed. Chromatography of the reaction mixture on silica

with CH₂Cl₂/CH₃OH/NH₃30:6:1 gave 54 (145 mg, 35%) and 56

Wagner, T. E. Johnson, J. S. Lindsey, Tetrahedron 1997, 53,

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H. Bouas-Laurent, P. Marsau, S. W. Riley, J.-P. Desvergne,

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[3f]

(67 mg, 10%) as a brown solid. H NMR (CDCl₃, ppm): δ ϭ 1.71

Soc. 1989, 111, 2440Ϫ2443.

Z. H. Chen, O. F. Shall, M.

(q, J ϭ 6.4 Hz, 4 H), 1.75 (q, J ϭ 6.4 Hz, 4 H), 2.17 (s, 6 H), 2.20

(s, 6 H), 2.30 (s, 6 H), 2.51 (m, 24 H), 3.38 (t, J ϭ 6.4 Hz, 4 H),

3.48 (t, J ϭ 6.4 Hz, 4 H), 7.11 (d, J ϭ 7.0 Hz, 2 H), 7.35 (dd, J ϭ

8.3, 7.0 Hz, 2 H), 7.65 (d, J ϭ 8.3 Hz, 2 H), 8.33 (s, 1 H), 9.26 (s,

1 H). ¹³C NMR (CDCl₃, ppm): δ ϭ 24.0 (4 C), 43.6 (4 C), 43.8 (2

C), 50.5 (2 C), 51.9 (2 C), 53.3 (2 C), 53.4 (2 C), 53.7 (2 C), 54.8

(2 C), 55.0 (2 C), 55.5 (2 C), 116.5 (2 C), 119.4 (1 C), 123.1 (2 C),

125.2 (2 C), 126.6 (1 C), 128.1 (2 C), 133.0 (2 C), 149.6 (2 C).

MALDI-TOF: m/z ϭ 658.71 [M^ϩ].

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13,13Ј-(1,8-Anthracenediyl)bis(1,4,7,10-tetraoxo-13-azacyclopenta-

decane) (58): 1,8-Dichloroanthracene (1; 123 mg, 0.5 mmol), 1-aza-

15-crown-5 (57; 264 mg, 1.0 mmol), NaOtBu (200 mg, 2.1 mmol),

Pd(dba)₂(23 mg, 0.04 mmol) and BINAP (62 mg, 0.1 mmol) were

dissolved under argon in dioxane (40 mL) in a two-necked flask.

The reaction mixture was heated at reflux for 48 h. After cooling

down to room temperature it was concentrated in vacuo. The resi-

due was taken up with CH₂Cl₂(30 mL), washed with water (15

mL) and dried over anhydrous sodium sulfate, and the solvents

were evaporated in vacuo. The residue was chromatographed on

silica with CH₂Cl₂/MeOH 100:3 to give 58 (36 mg, 11%) as a brown

solid and 13-(1-anthracenyl)-1,4,7,10-tetraoxa-13-azacyclopentade-

cane (59; 97 mg, 44%) as a brown solid. 58: ¹H NMR (CDCl₃,

ppm): δ ϭ 3.68 (m, 40 H), 7.23 (d, J ϭ 7.2 Hz, 2 H), 7.35 (dd, J ϭ

8.6, 7.2 Hz, 2 H), 7.67 (d, J ϭ 8.6 Hz, 2 H). ¹³C NMR (CDCl₃,

ppm): δ ϭ 54.3 (4 C), 70.3 (4 C), 70.6 (4 C), 70.8 (4 C), 71.0 (4 C),

117.0 (2 C), 119.6 (1 C), 123.4 (2 C), 125.4 (2 C), 126.9 (1 C), 128.4

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`

chard, C. Lecomte, S. Brandes, J. E. Hutchison, J. P. Collman,

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69.0 (2 C), 70.6 (2 C), 70.8 (2 C), 71.1 (2 C), 117.0 (1 C), 123.5 (1

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Article Doi

Palladium-catalysed amination of 1,8- and 1,5-dichloroanthracenes and 1,8- and 1,5-dichloroanthraquinones

DOI: 10.1002/ejoc.200400455

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