Synthesis of hexa- peri -hexobenzocoronenes carrying linear or branched perfluoroalkylated side chains

PAPER

1123

Synthesis of Hexa-peri-hexobenzocoronenes Carrying Linear or Branched

Perfluoroalkylated Side Chains

P

erfluoroalkyl-Sub

l

stitute

i

v

peri-hexobe

i

nzocor

e

onenes r F. Aebischer, David T. Muñoz, Patrick Tondo, Jean-Luc Débieux, Titus A. Jenny*

Chemistry Department, University of Fribourg, 9 chemin du Musée, 1700 Fribourg, Switzerland

Fax +41(26)3009739; E-mail: titus.jenny@unifr.ch

Received 23 November 2009; revised 11 December 2009

ther linear or branched, differ by the length of perfluoro-

alkyl chain and/or length of partitioning by the CH₂

spacer. The derivatives reported herein are shown in

Figure 1.

Abstract: Substituted disc-shaped perfluoroalkylated hexa-peri-

hexabenzocoronenes (HBC), known to self-assemble into conduct-

ing ordered architectures, were synthesized and characterized. A

systematic variation of the linear or branched perfluoroalkylated

side chains was performed in order to screen the influence of the lat-

eral chain on their one-dimensional self-aggregation.

R

Key words: HBC, perfluoroalkylated substitutions, cross-

coupling, cyclodehydrogenation, tandem Sonogashira

R

Self-assembling is emerging as a widely used strategy in

supramolecular chemical synthesis, with the potential of

generating nonbiological structures with dimensions of up

to several hundred nanometers.¹As example of involved

intermolecular forces one could mention p-p interac-

tions,²hydrogen bonding,³donor–acceptor interactions,⁴

and reversible ligand–metal interactions.⁵Molecules that

are promising self-assembling candidates with application

in advanced functional materials include liquid crystal

constituents,⁶block polymers,⁷hydrogen-bonded com-

plexes,⁸and coordination polymers.⁹

R

linear (1)

branched (2)

R = Rf_3,6

1a

1b

1c

(CH₂)₃CH[CH₂(CF₂)₄F]₂

(CH₂)₃CH[(CH₂)₂(CF₂)₆F]₂2b

(CH₂)₅CH[(CH₂)₂(CF₂)₆F]₂2c

2a

R =

Rf_3,8

Rf_4,4

Rf_4,101d

Rf_5,6

Rf_6,8

Rf_8,4

Rf_8,6

Rf_8,8

Rf_5,8

1e

1f

1g

1h

1i

Among supramolecular self-organizing systems, liquid

crystals, formed of disc-shaped molecules, are of particu-

lar interest.^9a,10They have great potential for incorporat-

ing desirable chemical functionalities in their periphery

and the physical properties of the supramolecular struc-

tures they form may, therefore, be tuned at nanoscaled di-

mensions. An outstanding class of polycondensed

aromatic hydrocarbons (PAH) are hexa-peri-hexabenzo-

coronene derivatives (HBC), which excel over their coun-

terparts due to their high chemical and thermal stability

and by their high charge carrier mobility measured in

bulk.¹¹

1j

Rf_n,m= (CH₂)_n(CF₂)_mF

Figure

described in this paper

1

Hexa-peri-hexabenzocoronene

target

molecules

The most convenient way of synthesizing HBC deriva-

tives consists of cyclodehydrogenation of the correspond-

ing hexaphenylbenzene (HPB) under Kovacic

conditions.¹³Among numerous variations of the Kovacic

conditions, the mild iron(III) chloride reagent, which acts

both as Lewis acid and as the oxidant, is superior to other

alternative reagents, as, in most cases, the reaction goes to

completion without unwanted chlorination. As the elec-

tron-withdrawing effect of a perfluorinated lateral chain

prevents the final cyclodehydrogenation reaction, a mini-

mum spacer of two CH₂groups is required between the ar-

omatic core and the perfluorinated part.¹⁴

The replacement of purely alkyl chains by partially per-

fluoroalkylated chains should, in principle, not alter the

electronic properties of these molecules, but should even-

tually prevent or reduce lateral aggregation of formed

one-dimensional self-aggregated molecular wires. Prom-

ising results in this respect involving some perfluoroalkyl-

ated HBC derivatives have recently been reported.¹²In

order to investigate the influence of the nature of the lat-

eral chain, several derivatives have been systematically

synthesized and characterized. The lateral substituents, ei-

Symmetrical HPB derivatives are best prepared by cyclo-

trimerization of an alkyne species.¹⁵Although other tran-

sition metals, such as nickel and iron, or even silicon

catalyze the cyclotrimerization of alkynes to arenes, co-

SYNTHESIS 2010, No. 7, pp 1123–1140

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Advanced online publication: 05.02.2010

DOI: 10.1055/s-0029-1218667; Art ID: Z25209SS

1124

O. F. Aebischer et al.

PAPER

balt complexes such as Co₂(CO)₈and CpCo(CO)₂are more reactive iodinated compound 5b for subsequent

among the most efficient.¹⁶

Sonogashira cross-coupling.

Cyclodehydrogenation, as well as cyclotrimerization, has HBC derivatives bearing a four-CH₂spacer were prepared

been studied extensively in the past for the preparation of by a slightly different method, in which the alkyl–aryl

hexaalkyl-substituted HBC derivatives,¹⁷but, neverthe- bond was formed prior to the attachment of the perfluori-

less, needed modification for the preparation of perfluori- nated part to avoid any cross-coupling of perfluoroalkyl

nated analogues.

substituents. Heck reaction of an analogue of compound 3

bearing four nonfluorinated carbons was found inappro-

priate as many side products were formed.

The main challenge in preparing symmetrical perfluori-

nated HBC derivatives remains, therefore, in the prepara-

tion of correctly substituted tolane derivatives. These As illustrated in Scheme 2, compound 7, formed by

starting substituted tolanes, used in turn for cyclotrimer- Wurtz-type coupling,²³was reacted with the correspond-

ization, were found to be favorably made by tandem ing perfluoroalkyl iodide (Rf_mI) in the presence of a cata-

Sonogashira cross-couping¹⁸using the corresponding ha- lytic amount of 2,2¢-azobis(isobutyronitrile) to initiate the

logenated aryl species bearing the desired perfluorinated reaction and 30% aqueous sodium metabisulfite solution

lateral chain. Mostly their preparation was very similar for to reduce the formation of side products.^20aRemoval of

derivatives with the same length CH₂spacer, but varied the iodine group of the side chain in 8a,b was achieved

greatly when the number of CH₂groups changed.

with lithium aluminum hydride^20caffording the desired

aryl bromides 9a,b without cleavage of the aryl bromide.

Even milder cleavage may be achieved using lauroyl per-

oxide in the presence of cyclohexane,²⁴a procedure which

afforded comparable yields in our case. Radical-mediated

halogen exchange furnished, finally, the iodoaryl deriva-

tives 5c,d.

The preparation of compounds 5a,b and 6a bearing a three

CH₂spacer between the phenyl ring and the perfluorinat-

ed tail has been reported involving a Wittig reaction of 4-

bromobenzaldehyde and [Ph₃PCH₂CH₂Rf_n]⁺I^–(n = 6, 8,

10) and subsequent hydrogenation.¹⁹Nevertheless, we de-

cided (Scheme 1) to use a different strategy due to easier

access to the Heck starting compounds. The perfluorinat-

ed allyl derivatives 3a,b, synthesized in two steps²⁰are

reacted with 4-bromo- or 4-iodobenzenediazonium tet-

rafluoroborate affording the desired cross-coupled prod-

ucts 4a–c by palladium-catalyzed Heck reaction;²¹

Rf_mI, AIBN

Na₂S₂O₅

I

Br

8a m = 4 (71%)

8b m = 10 (98%)

Rf_m

7

1

LiAlH₄

THF

Ni, KI, I₂

DMF

exclusively E-isomers were formed, as shown by H

Rf_4,m

NMR. The yield obtained from the iodinated diazonium

salt is much lower than that from using the bromine ana-

logue, because the iodinated diazonium salt undergoes

partially a twofold Heck reaction forming a dialkylated

product (up to 30%) which has to be separated by tedious

column chromatography purification.

Br

I

9a m = 4 (80%)

9b m = 10 (40%)

5c m = 4 (77%)

5d m = 10 (75%)

Scheme 2 Three-step synthesis of the iodoaryl derivatives 5c,d

The preparation of the key aryl derivatives 5h,i is shown

in Scheme 3 with yield data in Table 1. All polyfluoro-

alkyl bromides 10a–e were obtained as colorless oils in

very good yield according to a published procedure.^20c

The two-carbon elongation of the brominated alkynes was

achieved by their treatment with lithium acetylide–ethyl-

enediamine complex in dimethyl sulfoxide.²⁵In order to

improve the homogeneity of the reaction mixture, the

starting bromides were diluted with pentane prior to the

addition yielding the perfluoroalkynes 11a–e as colorless,

very volatile liquids in modest yield. The yields of the de-

rivatives bearing an eight CH₂spacer were, interestingly,

much better than those of the corresponding shorter ones,

probably due to lower volatility. An alternative way to

produce semiperfluorinated alkynes has been reported for

11c. Dimethylpropargyl alcohol was reacted with 6-bro-

mohex-1-ene, which was subsequently transformed by

addition of perfluorobutyl iodide. Reduction of the iodo

group followed by deprotection of the alkyne yielded

11c.²⁶

N₂BF₄

X

Rf_m

X

reagents

3a m = 6

3a m = 8

4a X = I m = 6 (59%)

4b X = Br m = 8 (93%)

4c X = I m = 8 (35%)

Rf_m

Ni, KI, I₂

DMF

I

Rh/C

pentane–CH₂Cl₂

Rf_3,m

Rf_3,6

X

H₂(50 bar), r.t.

5a X = I m = 6 (98%)

6a X = Br m = 8 (98%)

5b (99%)

Scheme 1 Preparation of perfluoroalkylated iodoaryl derivatives

bearing a three-CH₂spacer

Hydrogenation without halogen hydrogenolysis is best

done by using the mild rhodium/carbon catalyst in pen-

tane–dichloromethane (1:1). The reaction requires high

hydrogen pressure (up to 60 bars) and a reaction time of

around 12 hours to afford the hydrogenated compounds

5a and 6a quantitatively. Halogen exchange²²on 6a

with potassium iodide using nickel as catalyst yields the

The subsequent unfavorable Sonogashira cross-coupling

(the alkyne bears an alkyl and not an aryl substituent) of

11a–e was found to work best with Pd(PPh₃)₄as the cata-

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1125

Br

Rh/C

pentane–CH₂Cl₂

H₂(50 bar)

H

TMS

Pd(PPh₃)₄, CuI

Et₃N, THF

Ni, KI, I₂

DMF

DMSO, pentane

Rf_m

11a–e

Rf_m

Br

Rf_n,m

Br

I

n–2

1-bromo-4-

iodobenzene

10a–e

5h,i

5e–g, 13a,b

Rf_n–2,m

12a–e

Scheme 3 Preparation of the brominated bromoaryls 5e–g and the iodoaryls 5h,i

Table 1 Yields of All Derivatives Shown in Scheme 3

Rf_n,m

n

Starting compound Derivative Yield

(%)

Derivative Yield

(%)

Derivative Yield

(%)

Derivative Yield

(%)

m

6

8

4

6

8

5

6

8

10a

10b

10c

10d

10e

11a

11b

11c

11d

11e

38

39

62

73

44

12a

12b

12c

12d

12e

38

36

78

35

5e

95

99

97

89

93

5f

5g

13a

13b

5h

5i

88

90

lyst with 1-bromo-4-iodobenzene. Even at elevated reac- rial were recovered after the reaction. The high yield of

tion temperatures (80 °C) no trace of any doubly alkylated 14d was surprising, as extremely low solubility, due to the

product was found. The cross-coupling was repeated sev- ten perfluorinated carbon tail, was expected to hamper the

eral times under various conditions in order to improve reaction resulting in a drop in the yield instead of an in-

the yield, but the simplest conditions [Pd(PPh₃)₄, CuI, crease. In the case of the brominated precursors 5e,f, the

Et₃N] excel over more elaborated ones [such as Pd(PPh₃)₄, corresponding tolane 14e was afforded in very low yield,

LDA, ZnBr₂] that involve in situ preformed zinc deriva- only requiring separation from large amounts of recov-

tives as active transmetalation species. Subsequent hydro- ered starting material, whereas 14f was isolated in accept-

genation of the alkynes 12a–e under 50 bar of hydrogen, able yield. Tandem Sonogashira reaction using

afforded the reduced perfluorinated bromoaryl key prod- brominated 5g or iodinated 5h,i yielded the tolanes 14g–i

ucts 5e–g and 13a,b in quantitative yield as colorless oils. in moderate to good yields. It appears that the influence of

Halogen exchange was only performed for two deriva- the more reactive iodo group as compared to bromine is

tives 13a,b affording 5h,i.

negligible in the presence of bulky perfluoroalkylated

chains.

The tandem Sonogashira reaction (Scheme 4, Table 2)

uses the standard PdCl₂(PPh₃)₂/CuI catalyst with trimeth- Subsequent cobalt-mediated cyclotrimerization afforded

ylsilylacetylene, tetrahydrofuran as solvent and 1,8-diaza- most of the desired HPB derivatives 15a–i in good yields.

bicyclo[5.4.0]undec-7-ene–water as base to deprotect the The very low solubility of the tolanes 14b and 14d as well

formed TMS intermediate. This procedure allowed for to- as the corresponding HPB derivatives 15b and 15d pre-

tal suppression of the homocoupled product. The only im- vented completion of the reaction on one hand, and se-

purity found was the unreacted halogenated starting verely hampered the purification of the obtained products

compound. It is noteworthy that the tandem Sonogashira on the other. To overcome these difficulties hexafluo-

reaction was also attempted with unsaturated compound robenzene (HFB) was added as co-solvent to prevent in-

4a. This reaction, however, afforded exclusively a tolane complete reaction due to co-precipitation of starting

derivative, in which HF was eliminated from the side material with the even less soluble product. Purification

chain. We also attempted direct formation of tolane 14b was performed by filtration through a short silica gel plug

by twofold Kumada cross-coupling reaction between 11- using hot benzotrifluoride (a,a,a-trifluorotoluene, BTF)

bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro- as solvent. It must be noted that HPB derivatives 15g and

undecane and 1-bromo-4-[(4-bromophenyl)ethynyl]ben- 15h bearing an eight CH₂spacer terminated by a short

zene, but this reaction gave, at best, the desired product in perfluorinated part of four or six carbon atoms are the first

19% yield. The Kumada cross-coupling reaction seems to HPBs with linear, partially fluorinated side chains that are

be severely hampered due to the electron-withdrawing ef- oily instead of solid. This behavior was, to date, only re-

fect of the perfluorinated part, despite the three CH₂spac- ported for HPB derivatives bearing purely alkyl chains or

er. In contrary, both tolanes 14a,b were formed in good branched lateral groups in their periphery.^15bHPB 15i,

yield for a tandem reaction. For tolane 14c, low yield was carrying eight perfluorinated carbon atoms, was again ob-

obtained since large quantities of unreacted starting mate- tained as a powder.

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

1126

O. F. Aebischer et al.

PAPER

Rf_n,m

FeCl₃, MeNO₂

CH₂Cl₂, HFB

Co₂(CO)₈

dioxane

PdCl₂(PPh₃)₂, CuI

THF, DBU, H₂O

H

TMS

X

5a–i

Rf_n,m

14a–i

15a–i

1a–i

Scheme 4 Formation of HBC derivatives bearing linear perfluorinated side chains

Cyclodehydrogenation of all HPB derivatives bearing lin- silica gel filtration using hot benzotrifluoride, hot toluene,

ear perfluoralkylated chains 15a–i afforded the corre- diethyl ether, or dichloromethane was attempted, but the

sponding HBC derivatives in moderate yields. HPB HBC stuck irreversibly to the silica gel. Chromatography

carrying short perfluorinated parts or long alkyl parts, nor- on preparative TLC plates afforded an observable migra-

mally well soluble in dichloromethane, were reacted using tion, but it was impossible to recover the compound from

the standard iron(III) chloride/nitromethane protocol²⁷the solid support. The usual solublilization/precipitation

whereas hexafluorobenzene was added as co-solvent for technique was therefore applied yielding HBC 1h as a

less soluble HPB derivatives as otherwise the transforma- dark yellow solid whereas HBC 1g remained a dark pow-

tion could not be completed. After the reaction the crude der. MALDI-TOF analysis of 1g revealed a mixture of

mixtures were quenched by the addition of methanol, chlorinated products (up to five chlorine substituents) of

which induced precipitation of the desired HBC deriva- the target HBC. We assume that chlorination was pro-

tives, commonly as brown solids. Precipitation from com- voked by the high solubility of the final product, since this

mon organic solvents (Et₂O, CH₂Cl₂, MeNO₂, and EtOH) chlorination occurred even at room temperature.

and a fluorinated solvent such as benzotrifluoride or

hexafluorobenzene yielded, after several suction filtra-

tions over Millipore®, the desired HBCs as yellow solids.

HBC 1i with its eight perfluorinated carbons showed rath-

er low solubility. Purification was, therefore, attempted by

suspending 1i in common organic solvents followed by

suction filtration over Millipore®. Unfortunately the

black impurity could not be removed in this way. Only re-

peated precipitation from refluxing 1,2,4-trichloroben-

zene (TCB) afforded 1i as dark yellow solid.

Interestingly, the four CH₂spacer, independent on the

length of the perfluoro part [4 CF₂(1c), 6 CF₂,²⁷8 CF₂,¹⁴

10 CF₂(1d)], proved to be ideal for purification as precip-

itation from benzotrifluoride and hexafluorobenzene af-

forded these products as very bright yellow solids.²⁷

An alternative very short sequence to prepare symmetri-

cally substituted tolane derivatives consists of a twofold

Despite of the fact that HBCs 1g and 1h, bearing short

perfluorinated parts, were even moderately soluble in

Kumada cross-coupling reaction of a perfluorinated bro-

common organic solvents, their purification proved to be

moalkane with 1-bromo-4-[(4-bromophenyl)ethynyl]ben-

more cumbersome. Due to moderate solubility of the later,

Table 2 Yields of All Derivatives Presented in Scheme 4

Rf_n,m

n

X

Starting compound

Derivative

Yield

(%)

Derivative

Yield

(%)

Derivative

Yield

(%)

m

6

3

4

5

6

8

I

5a

5b

5c

5d

5e

5f

14a

14b

14c

14d

14e

14f

14g

14h

14i

61

66

20

80

6

15a

15b

15c

15d

15e

15f

15g

15h

15i

86

84

95

85

79

64

73

92

51

1a

1b

1c

1d

1e

1f

33

56

55

70

60

65

46

64

40

8

I

4

I

10

6

I

Br

I

8

46

50

21

4

5g

5h

5i

1g

1h

1i

6

8

I

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1127

Rf_5,8

Br

Rf_5,8

FeCl₃, MeNO₂

Rf_5,8

PdCl₂(dppf), THF

MgBr

Co₂(CO)₈

dioxane

Rf₈

CH₂Cl₂, HFB

83%

54%

Rf_5,8

Br

Rf_5,8

14j

15j

1j

16

Scheme 5 Tolane preparation via Kumada cross-coupling followed by HBC formation

zene (16) (Scheme 5). Unfortunately the yield proved to orinated end tails was synthesized by twofold Grignard

be at best moderate and, in addition, not reproducible, the reaction on ethyl formate (17)³¹followed by iodination of

reason being, most probably, incomplete Grignard forma- the obtained alcohol 18. Interestingly, all iodination at-

tion of the perfluorinated bromoalkyl hindered by micelle tempts using hydrogen iodide and aliquat 336 as phase-

formation.²⁸The very long reaction time (one week) of the transfer catalyst failed completely, most probably due to

subsequent Kumada cross-coupling, underlined these dif- solubility problems. Only the use of tetrabutylammonium

ficulties. Out of the large variety of different catalysts test- iodide in the presence of 2,3-dichloro-5,6-dicyano-1,4-

ed PdCl₂(dppf)·CH₂Cl₂²⁹proved to be the most promising, benzoquinone and triphenylphosphine afforded the de-

since with other catalysts, such as Pd₂(dba)₃or sired iodide 19b.³²

Pd(OAc)₂³⁰the reaction did not go to completion.

The subsequent Kumada reaction was found to be very

Only the use of highly pure tolane 14j allowed the prepa- tricky as the reaction was very sensitive to the applied

ration of the desired HPB derivative 15j in good yield as conditions. It appeared crucial that the allylmagnesium

a white powder, as the remaining impurities of the Kumada bromide is added slowly over several hours at 0 °C as

cross-coupling catalyst appeared to poison the cobalt cat- otherwise many side products are formed. Again

alyst, preventing, therefore, the cyclotrimerization.

PdCl₂(dppf)·CH₂Cl₂was found to be the most adapted cat-

alyst to form selectively 21a,b.

Oxidation of HPB 15j was attempted first by using

iron(III) chloride in nitromethane and dichloromethane as Heck reaction of the branched perfluorinated precursors

solvent. However, only starting material was recovered, 21a,b with reactive 4-bromobenzenediazonium tetrafluo-

presumably because the solubility was too low for the re- roborate did not work properly. Different catalytic sys-

action to occur. Only by adding hexafluorobenzene as a tems were tested, from which Pd(OAc)₂/CaCO₃and

co-solvent was the desired HBC 1j obtained as slightly Pd₂(dba)₃/NaOAc excelled over all the others. Subsequent

brown-yellow powder after several re-precipitations from hydrogenation of 22a,b afforded the desired aryl deriva-

benzotrifluoride and hexafluorobenzene solutions.

tives carrying branched perfluoroalkylated side chains

23a,b.

To further increasing the fluorine coat of the HBC colum-

nar stacks, HBC derivatives carrying branched perfluori- Reaction of iodide 19b with 5-bromopent-1-ene under

nated side chains were designed. One derivative 2a was Kumada cross-coupling conditions did not allow the di-

decorated with six branched chains each carrying two per- rect preparation of the 21b analogue. The Kumada cross-

fluorobutyl end groups. Modeling of the geometry of this coupling worked only by using very reactive allylmagne-

side chain revealed a T-shaped arrangement of the per- sium bromide. Hence 21b was oxidized³³to the alcohol 24

fluorinated end part with respect to the CH₂spacer at the which was, thereafter, converted into its brominated ana-

branching point. This geometry inherently imposes large logue 25 by using tetrabutylammonium bromide, 2,3-

steric hindrance on the p–p stacking. To reduce this steric dichloro-5,6-dicyano-1,4-benzoquinone, and triphenyl-

hindrance two other derivatives were added, one with a phosphine. Subsequent acylation using lithium acetylide–

longer CH₂spacer after the branching point 2b and a sec- ethylenediamine complex in a mixture of dimethyl sulfox-

ond derivative with an elongated CH₂spacer before and ide and pentane afforded finally compound 26

after the branching point 2c.

(Scheme 7). Sonogashira cross-coupling of 26 gave the

desired aryl derivative 27 in low yield. The low reactivity

of the starting alkyne 26 was the reason that no traces of

doubly coupled product were found. Hydrogenation of 27

using the already discussed rhodium/carbon conditions

afforded the desired aryl bromide 23c in good yield.

The addition of a second perfluorinated tail onto a per-

fluoroalkylated allyl derivative 20 proved to work

smoothly, but required, in general, longer reaction times.

Furthermore the addition of several portions of the radical

initiator (AIBN) were needed to afford the desired

branched iodide 19a after distillation (Scheme 6). The an- Conversion of the brominated aryl derivatives 23a–c with

alogue 19b with a five-carbon spacer between the perflu- their branched chains into the corresponding tolanes was

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

1128

O. F. Aebischer et al.

PAPER

Ph₃P, DDQ

TBAI

CH₂Cl₂

I

Rf₄I, AIBN

Na₂S₂O₅

OH

O

Mg, Et₂O, 81%

Rf₄

Rf_m

Rf₆

H

O

n

I

20

Rf₆

19a n = 1 m = 4 (49%)

19b n = 2 m = 6 (90%)

17

18

Rf_m

n

Rf_m

Rh/C

pentane, CH₂Cl₂

H₂(50 bar)

n

Pd₂(dba)₃, NaOAc

MeCN

PdCl₂(dppf), THF

19a

19b

Rf_m

n

MgBr

n

N₂BF₄

Br

21a n = 1 m = 4 (71%)

21b n = 2 m = 6 (84%)

Br

22a n = 1 m = 4 (31%)

22b n = 2 m = 6 (56%)

23a n = 1 m = 4 (98%)

23b n = 2 m = 6 (77%)

Scheme 6 Formation of branched polyfluoroalkyl-substituted aryl bromides 23a,b

Br

OH

AlCl_3,LiAlH₄

PhB(OH)₂

O₂, Et₂O, 47%

Ph₃P, DDQ

DMSO

TBAB

pentane, 60%

CH₂Cl₂, 84%

Rf₆

H

TMS

21b

25

24

Rf₆

Rh/C

pentane, CH₂Cl₂

H₂(50 bar), 86%

PdCl₂(PPh₃)₂, Et₃N

CuI, BTF, 30%

Rf₆

26

I

Br

27

Br

23c

Scheme 7 Preparation of derivative 23c

R

Co₂(CO)₈

dioxane

FeCl₃, MeNO₂

CH₂Cl₂, HFB

PdCl₂(PPh₃)₂, CuI

THF, DBU, H₂O

H

TMS

Br

R

23a R = (CH₂)₃CH[CH₂(CF₂)₄F]₂

23b R = (CH₂)₃CH[(CH₂)₂(CF₂)₆F]₂

23c R = (CH₂)₅CH[(CH₂)₂(CF₂)₆F]₂

R

29a (84%)

29b (46%)

29c (74%)

28a (59%)

28b (94%)

28c (76%)

2a (84%)

2b (83%)

2c (73%)

Scheme 8 Formation of HBC derivatives 2a–c bearing branched perfluoroalkylated side chains

performed by tandem Sonogashira reactions. Purification that are obtained as oils instead of solids. The highly sol-

was achieved for all three derivatives by column chroma- uble tolanes afforded after Co₂(CO)₈-mediated cyclotri-

tography over silica gel. The branched T-shaped lateral merization the desired HPB derivatives 29a–c in

chain seems to impede considerably the p-p-aggregation moderate to high yields (Scheme 8). These oily com-

of the central part as 28a–c are the first reported tolanes pounds had to be purified by column chromatography.

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1129

UV/VIS (BTF, 10^–6M): l (e) = 352, 369 (1.5 × 10⁵), 396 nm.

The oily consistence of HPB derivatives was already men-

tioned in literature for compounds that carry long linear

(>C₁₂) or branched alkyl chains in their periphery.³⁴

2,5,8,11,14,17-Hexakis(5,5,6,6,7,7,8,8,8-nonafluorooctyl)hexa-

benzo[bc,ef,hi,kl,no,qr]coronene (1c)

The oxidation of HPB 29a–c was performed under mild

iron(III) chloride conditions (Scheme 8). As a solvent

dichloromethane was largely sufficient, since all starting

materials were oils and, therefore, readily dissolved in

dichloromethane. The purification of HBC 2a was per-

formed in the usual way by precipitation of the HBC from

benzotrifluoride and hexafluorobenzene solution by the

addition of diethyl ether, pentane, and methanol, which

yielded finally the desired HBC 2a as a yellow powder,

whereas HBCs 2b,c were obtained as dark powders.

As described for 1a using HPB 15c (0.2 g, 92 mmol), FeCl₃(535 mg,

3.3 mmol, 3.0 equiv/H to be removed), CH₂Cl₂(15 mL), and

MeNO₂(5 mL) gave 1c (110 mg, 55%).

¹H NMR (500 MHz, HFB, CDCl₃): d = 9.06 (s, 12 H, Ar), 3.57 (t,

J = 7.8 Hz, 12 H, CH₂), 2.59–2.63 (m, 24 H, CH₂), 2.30 (quint,

J = 7.8 Hz, 12 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 2166.36 (100) ([M⁺], calcd

for C₉₀H₆₀F₅₄: 2166.38), 1906.34 (20), 1644.28 (10), 1384.27 (5).

UV/VIS (BTF, 10^–6M): l (e) = 343, 360 (1.2 × 10⁵), 391 nm.

2,5,8,11,14,17-

Hexakis(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-

henicosafluorotetradecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene

(1d)

As described for 1a using HPB 15d (0.1 g, 25 mmol), FeCl₃(366

mg, 2.26 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(10 mL),

MeNO₂(8 mL), and HFB (10 mL) gave 1d (70 mg, 70%).

¹H NMR (500 MHz, CDCl₃): d = 9.12 (br s, 12 H, Ar), 3.58 (br s,

12 H, CH₂), 2.52 (br s, 24 H, CH₂), 2.37 (br s, 12 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3966.22 (100) ([M⁺], calcd

for C₁₂₆H₆₀F₁₂₆: 3966.27), 3405.01 (43).

All reagents and solvents were purchased from commercial sources

and used without further purification. THF and CH₂Cl₂were dried

and deoxygenated by the Grubbs method.³⁵All reactions were per-

formed under inert atmosphere (N₂or Ar). ¹H and ¹³C NMR spectra

were recorded on a Bruker DPX 360 or a Bruker DRX 500 spec-

trometer, using CDCl₃or HFB as solvent. Mass spectra were re-

corded on a Finnigan Thermo Quest GC/MS Voyager spectrometer,

a Bruker 4.7 T BioAPEX II FT-ICR spectrometer using DCTB

(trans-2-[3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malo-

nonitrile) as matrix, or a Bruker Ultraflex II spectrometer. Analyti-

cal TLC was performed on Merck Kieselgel 60 F254 pre-coated

glass plates and visualized by spraying with a KMnO₄soln.

UV/VIS (BTF, 10^–5M): l (e) = 364 nm (4.2 × 10⁴).

2,5,8,11,14,17-Hexakis(6,6,7,7,8,8,9,9,10,10,11,11,11-trideca-

fluoroundecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene (1e)

As described for 1a using HPB 15e (0.1 g, 35 mmol), FeCl₃(340 mg,

2.1 mmol, 5.0 equiv/H to be removed), CH₂Cl₂(20 mL), and

MeNO₂(8 mL) gave 1e (60 mg, 60%).

¹H NMR (360 MHz, HFB, CDCl₃): d = 8.99 (br s, 12 H, Ar), 3.55

(br s, 12 H, CH₂), 2.50 (br s, 24 H, CH₂), 2.15 (br s, 24 H).

MS (MALDI-ICR, DCTB): m/z (%) = 2850.44 (100) ([M⁺], calcd

for C₁₀₈H₇₂F₇₈: 2850.44), 2476.40 (50), 2101.36 (15), 1725.33 (10).

UV/VIS (BTF, 10^–6M): l (e) = 346, 360 (2.8 × 10⁵), 391 nm.

2,5,8,11,14,17-Hexakis(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-

nonyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene (1a); Typical

Procedure

In a 3-necked flask, HPB 15a (0.2 g, 74 mmol) was dissolved in an-

hyd CH₂Cl₂(15 mL) under an inert atmosphere. At the same time a

soln of FeCl₃(433 mg, 2.67 mmol, 3 equiv/H to be removed) was

prepared in MeNO₂(5 mL). The FeCl₃soln was added to the soln

of 15a at 45 °C drop by drop with a syringe. Argon was bubbled

through the mixture by a Teflon capillary during the entire reaction.

After 6 h the mixture was quenched by the addition of MeOH (20

mL). The black precipitate was collected by suction filtration over

Millipore^®and was suspended in various common organic solvents

(CH₂Cl₂, MeOH, Et₂O, and pentane). The suspensions formed were

each treated in an ultrasonic bath for 30 min followed by reflux for

1 h. After 2 h of cooling in the refrigerator the suspensions were fil-

tered over Millipore^®to yield 1a (62 mg, 33%) as a bright yellow

powder.

2,5,8,11,14,17-

Hexakis(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-hepta-

decafluorotetradecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene (1f)

As described for 1a using HPB 15f (0.2 g, 56 mmol), FeCl₃(820 mg,

5.0 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(15 mL), MeNO₂

(12 mL), and HFB (15 mL) gave 1f (130 mg, 65%).

¹H NMR (360 MHz, HFB, CDCl₃): d = 8.83 (br s, 12 H, Ar), 3.48

(br s, 12 H, CH₂), 2.46 (br s, 24 H, CH₂), 2.10 (br s, 36 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3534.55 (100) ([M⁺], calcd

for C₁₂₆H₈₄F₁₀₂: 3534.49), 3046.68 (24).

UV/VIS (BTF, 10^–6M): l (e) = 346, 360 (2.5 × 10⁵), 391 nm.

¹H NMR (500 MHz, HFB, CDCl₃): d = 8.69 (br s, 12 H, Ar), 3.55

(br s, 12 H), 2.74 (m, 24 H).

MS (MALDI-ICR, DCTB): m/z (%) = 2682.22 (100) ([M⁺], calcd

for C₉₆H₄₈F₇₈: 2682.25), 2336.20 (20).

UV/VIS (BTF, 10^–5M): l (e) = 344, 361 (5.6 × 10³), 386, 412 nm.

2,5,8,11,14,17-Hexakis(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-

heptadecafluoroundecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene

(1b)

As described for 1a using HPB 15b (50 mg, 15 mmol), FeCl₃(220

mg, 1.36 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(5 mL),

MeNO₂(4 mL), and HFB (5 mL) gave 1b (28 mg, 56%).

¹H NMR (500 MHz, HFB, CDCl₃): d = 8.95 (s, 12 H, Ar), 3.61 (br

s, 12 H, CH₂), 2.73 (br s, 24 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3282.21 (100) ([M⁺], calcd

for C₁₀₈H₄₈F₁₀₂: 3282.21), 2836.20 (10).

2,5,8,11,14,17-Hexakis(9,9,10,10,11,11,12,12,12-nonafluoro-

dodecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene (1g)

As described for 1a using HPB 15g (1.0 g, 0.4 mmol), FeCl₃(5.8 g,

36 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(80 mL), and MeNO₂

(20 mL) gave 1g (0.46 g, 46%).

MS (MALDI-ICR, DCTB): m/z (%) = 2502.1 (100) ([M⁺], calcd for

C

₁₁₄H₁₀₈F₅₄: 2502.76), 2536.1 (25) [M – H + Cl]⁺, 2570.0 (16) [M –

2 H + 2 Cl]⁺, 2604.0 (5) [M – 3 H + 3 Cl]⁺, 2637.9 (2) [M – 4 H +

4 Cl]⁺.

UV/VIS (BTF, 10^–6M): l (e) = 323, 372 (5.2 × 10⁵), 451 nm.

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

1130

O. F. Aebischer et al.

PAPER

2,5,8,11,14,17-Hexakis[9,9,10,10,11,11,12,12,13,13,14,14,14-

tridecafluoro-6-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tet-

radecyl]hexabenzo[bc,ef,hi,kl,no,qr]coronene (2c)

2,5,8,11,14,17-Hexakis(9,9,10,10,11,11,12,12,13,13,14,14,14-

tridecafluorotetradecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene

(1h)

As described for 1a using HPB 15h (0.1 g, 32 mmol), FeCl₃(468

mg, 2.9 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(18 mL), and

MeNO₂(4 mL) gave 1h (64 mg, 64%).

As described for 1a using HPB 29c (55 mg, 10 mmol), FeCl₃(153

mg, 0.94 mmol, 7.8 equiv/H to be removed), CH₂Cl₂(15 mL), and

MeNO₂(1.5 mL) gave 2c (40 mg, 73%).

MS (MALDI-TOF, DCTB): m/z (%) = 3103.4 (35) ([M⁺], calcd for

MS (MALDI-TOF, DCTB): m/z (%) = 5180.04 (100) ([M⁺], calcd

C₁₂₆H₁₀₈F₇₈: 3102.72), 1001.6 (100).

for C₁₇₄H₁₂₆F₁₅₆: 5178.74).

UV/VIS (BTF, 10^–6M): l (e) = 371 nm (9.2 × 10⁵).

UV/VIS (BTF, 10^–6M): l (e) = 345, 360 (1.3 × 10⁵), 390 nm.

2,5,8,11,14,17-

1-Iodo-4-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoronon-1-enyl)ben-

zene (4a); Typical Procedure

Hexakis(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-hep-

tadecafluorohexadecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene

(1i)

As described for 1a using HPB 15i (0.2 g, 54 mmol), FeCl₃(523 mg,

3.2 mmol, 5.0 equiv/H to be removed), CH₂Cl₂(30 mL), MeNO₂

(12 mL), and HFB (10 mL) gave 1i (80 mg, 40%).

¹H NMR (360 MHz, HFB, CDCl₃): d = 9.00 (br s, 12 H, Ar), 3.51

(br s, 12 H, CH₂), 2.34 (br s, 24 H, CH₂), 1.88 (br s, 60 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3702.71 (100) ([M⁺], calcd

for C₁₃₈H₁₀₈F₁₀₂: 3702.68), 3186.87 (17), 2656.42 (12), 2139.37 (8).

4-Iodobenzenediazonium tetrafluoroborate (9.7 g, 30.5 mmol),

Pd₂(dba)₃(508 mg, 0.56 mmol), and NaOAc (7.9 g, 97.0 mmol)

were added to a 2-necked round-bottomed flask equipped with a re-

flux condenser under an inert atmosphere. Degassed MeCN (100

mL) was added. Compound 3a (10 g, 27.8 mmol) was degassed in

a separate flask and was diluted with MeCN (40 mL) and syringed

into the reaction vessel. The inert gas entry was changed against a

bubble counter. The mixture was stirred at r.t. for 4 h until the for-

mation of N₂had stopped. All volatiles were removed under re-

duced pressure yielding a dark brown solid that was dissolved in

pentane (400 mL) and filtered through a plug of silica gel (pentane)

under reduced pressure. After removing all volatiles, 4a was recov-

ered as slightly yellow solid which was further purified by column

chromatography (pentane). Evaporating all volatiles from the de-

sired fractions yielded 4a (10.14 g, 59%) as a white solid; R_f= 0.66

(pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.66 (d, J = 8.2 Hz, 2 H, Ar), 7.12

(d, J = 8.2 Hz, 2 H, Ar), 6.55 (d, J = 15.4 Hz, 1 H, CH), 6.15 (dt,

J = 15.4, 7.5 Hz, 1 H, CH), 3.00 (dt, J = 17.9, 7.5 Hz, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 137.75, 136.22, 135.66, 128.17,

117.00 (t, J = 4.6 Hz), 105.70–120.02 (m, Rf₆), 93.57, 35.14 (t,

J = 22.8 Hz).

UV/VIS (BTF, 10^–6M): l (e) = 345, 360 (1.5 × 10⁵), 391 nm.

2,5,8,11,14,17-

Hexakis(6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heptadeca-

fluorotridecyl)hexabenzo[bc,ef,hi,kl,no,qr]coronene (1j)

As described for 1a using HPB 15j (0.1 g, 28 mmol), FeCl₃(423 mg,

2.6 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(10 mL), MeNO₂(8

mL), and HFB (10 mL) gave 1j (54 mg, 54%).

¹H NMR (360 MHz, CDCl₃): d = 9.06 (br s, 12 H, Ar), 3.60 (br s,

12 H, CH₂), 2.65 (br s, 24 H, CH₂), 2.20 (br s, 24 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3450.50 (100) ([M⁺], calcd

for C₁₂₀H₇₈F₁₀₂: 3450.40), 2976.34 (10).

UV/VIS (BTF, 10^–6M): l (e) = 345, 360 (1.9 × 10⁵), 391 nm.

MS (EI, 70 eV): m/z (%) = 562.8 (7) [M⁺], 116.0 (100).

1-Bromo-4-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca-

fluoroundec-1-enyl)benzene (4b)

As described for 4a using 3b (13.0 g, 28.25 mmol), 4-bromoben-

zenediazonium tetrafluoroborate (8.4 g, 31.08 mmol), Pd₂(dba)₃

(440 mg, 0.42 mmol), NaOAc (8.1 g, 9.89 mmol), and MeCN (140

mL) gave 4b (16.2 g, 93%); R_f= 0.54 (pentane).

2,5,8,11,14,17-Hexakis[6,6,7,7,8,8,9,9,9-nonafluoro-4-

(2,2,3,3,4,4,5,5,5-nonafluoropentyl)nonyl]hexa-

benzo[bc,ef,hi,kl,no,qr]coronene (2a)

As described for 1a using HPB 29a (0.2 g, 55 mmol), FeCl₃(800 mg,

4.9 mmol, 7.5 equiv/H to be removed), CH₂Cl₂(10 mL), MeNO₂(8

mL), and HFB (10 mL) gave 2a (170 mg, 84%).

¹H NMR (360 MHz, CDCl₃): d = 7.46 (d, J = 8.2 Hz, 2 H, Ar), 7.25

(d, J = 8.2 Hz, 2 H, Ar), 6.56 (d, J = 15.4 Hz, 1 H, CH), 6.13 (dt,

J = 15.4, 7.5 Hz, 1 H, CH), 3.00 (dt, J = 17.7, 7.5 Hz, 2 H, CH₂).

¹H NMR (360 MHz, CDCl₃): d = 9.29 (br s, 12 H, Ar), 3.67 (br s,

12 H, CH₂), 2.99 (br s, 6 H, CH), 2.44–2.71 (m, 36 H, CH₂), 2.54

(m, 12 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 136.09, 135.09, 131.78, 127.96,

122.02, 116.89 (t, J = 4.3 Hz), 105.70–120.02 (m, Rf₈), 35.14 (t,

J = 22.8 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 3642.43 (100) ([M⁺], calcd

for C₁₂₆H₇₈F₁₀₈: 3642.44).

UV/VIS (BTF, 10^–6M): l (e) = 346, 361 (2.4 × 10⁵), 391 nm.

MS (EI, 70 eV): m/z (%) = 615.0 (7) [M⁺], 535.8 (1), 168.9 (100).

2,5,8,11,14,17-Hexakis[7,7,8,8,9,9,10,10,11,11,12,12,12-tri-

decafluoro-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)do-

decyl]hexabenzo[bc,ef,hi,kl,no,qr]coronene (2b)

As described for 1a using HPB 29b (142 mg, 30 mmol), FeCl₃(413

mg, 2.54 mmol, 7.0 equiv/H to be removed), CH₂Cl₂(15 mL), and

MeNO₂(6 mL) gave 2b (118 mg, 83%).

MS (MALDI-TOF, DCTB): m/z (%) = 5011.66 (100) ([M⁺], calcd

for C₁₆₂H₁₀₂F₁₅₆: 5010.55).

UV/VIS (BTF, 10^–6M): l (e) = 345, 361 (3.5 × 10⁵), 390 nm.

1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoroundec-

1-enyl)-4-iodobenzene (4c)

As described for 4a using 3b (6.0 g, 13.04 mmol), 4-iodobenzene-

diazonium tetrafluoroborate (4.14 g, 13.04 mmol), Pd(OAc)₂(58

mg, 0.26 mmol), MeOH (20 mL), and THF (5 mL), NaOAc (8.1 g,

9.89 mmol), and MeCN (140 mL) at 40 °C for 18 h gave 4c (3.0 g,

35%); R_f= 0.54 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.66 (d, J = 8.4 Hz, 2 H, Ar), 7.12

(d, J = 8.4 Hz, 2 H, Ar), 6.55 (d, J = 15.4 Hz, 1 H, CH), 6.15 (dt,

J = 15.4, 7.5 Hz, 1 H, CH), 3.00 (dt, J = 17.7, 7.5 Hz, 2 H, CH).

¹³C NMR (90.55 MHz, CDCl₃): d = 137.76, 136.22, 135.67, 128.17,

117.03 (t, J = 4.3 Hz), 105.70–120.02 (m, Rf₈), 93.56, 35.16 (t,

J = 22.8 Hz).

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1131

MS (EI, 70 eV): m/z (%) = 663.1 (7) [M⁺], 535.8 (1), 115.7 (100).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.26, 137.50, 130.44,

107.79–121.91 (m, Rf₁₀), 90.98, 35.05, 30.67, 30.67 (t, J = 21.8

Hz), 19.77 (t, J = 3.5 Hz).

1-Iodo-4-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)benzene

(5a); Typical Procedure

MS (EI, 70 eV): m/z (%) = 777.9 (95) [M⁺], 216.9 (100).

Iodoaryl 4a (6.4 g, 11.4 mmol) was dissolved in CH₂Cl₂(15 mL)

and added to a 200-mL autoclave. After the addition of pentane (50

mL), argon was bubbled through the mixture for 10 min before

Rh/C (5% Rh, 929 mg, 0.456 mmol) was added. The autoclave was

then tightly closed and purged with H₂(3 × 50 bar). The mixture

was then stirred at r.t. under H₂(60 bar) for 28 h. The suspension

was filtered through a plug of silica gel (pentane); removal of all

volatiles gave 5a (6.3 g, 98%) as a white solid; R_f= 0.66 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.64 (d, J = 8.2 Hz, 2 H, Ar), 6.96

(d, J = 8.2 Hz, 2 H, Ar), 2.67 (t, J = 7.5 Hz, 2 H, CH₂), 2.00–2.18

(m, 2 H, CH₂), 1.93 (quint, J = 7.5 Hz, 2 H, CH₂).

1-Bromo-4-(6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoro-

undecyl)benzene (5e)

As described for 5a using alkyne 12a (4.8 g, 8.9 mmol), Rh/C (300

mg), pentane (45 mL), and CH₂Cl₂(15 mL) gave 5e (4.61 g, 95%);

R_f= 0.85 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.40 (d, J = 8.2 Hz, 2 H, Ar), 7.04

(d, J = 8.2 Hz, 2 H, Ar), 2.58 (t, J = 7.7 Hz, 2 H, CH₂), 1.97–2.11

(m, 2 H, CH₂), 1.60–1.68 (m, 4 H, CH₂), 1.36–1.43 (m, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.06, 131.39, 130.12, 119.53,

105.33–118.80 (m, Rf₆), 35.01, 30.86, 30.79 (t, J = 22.5 Hz), 28.54,

19.99 (t, J = 3.3 Hz).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.20, 137.65, 130.40,

107.69–121.51 (m, Rf₆), 91.41, 34.49, 30.20 (t, J = 22.5 Hz), 21.66

(t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 544.9 (8) [M⁺], 168.9 (100), 91.0 (27).

MS (EI, 70 eV): m/z (%) = 564.8 (42) [M⁺], 437.5 (1), 217.0 (100).

1-Bromo-4-(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-hepta-

decafluorotetradecyl)benzene (5f)

As described for 5a using alkyne 12b (2.0 g, 3.1 mmol), Rh/C (100

mg), pentane (18 mL), and CH₂Cl₂(6 mL) gave 5f (2.0 g, 99%);

R_f= 0.65 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.39 (d, J = 8.2 Hz, 2 H, Ar), 7.04

(d, J = 8.2 Hz, 2 H, Ar), 2.56 (t, J = 7.7 Hz, 2 H, CH₂), 1.96–2.11

(m, 2 H, CH₂), 1.56–1.65 (m, 4 H, CH₂), 1.34–1.42 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.39, 131.32, 130.12, 119.40,

107.69–118.71 (m, Rf₈), 35.19, 30.99, 30.83 (t, J = 22.5 Hz), 28.92,

28.72, 20.03 (t, J = 3.3 Hz).

1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoro-

undecyl)-4-iodobenzene (5b); Typical Procedure

Ni (6.2 g, 10.6 mmol), KI (7.0 g, 42.2 mmol), and I₂(268 mg, 1.1

mmol) were charged into a Schlenk reaction vessel and suspended

in DMF (30 mL) under an inert atmosphere. Compound 6a (13.0 g,

21.0 mmol) was degassed in a separate flask, diluted with DMF (30

mL) and added to the mixture which was then heated to 150 °C for

27 h. The dark brown mixture was, after cooling to r.t., decanted off

from the nickel residue. The crude product was extracted with pen-

tane (3 × 100 mL) and the combined organic fractions were washed

with H₂O (100 mL), 3% HCl (50 mL), and H₂O (100 mL), and dried

(Na₂SO₄). Removal of all volatiles gave 5b as a yellow crystalline

solid. Purification was completed by filtration through a plug of sil-

ica gel (pentane) under reduced pressure to give 5b (13.7 g, 99%) as

a white crystalline solid; R_f= 0.54 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.63 (d, J = 8.2 Hz, 2 H, Ar), 6.94

(d, J = 8.2 Hz, 2 H, Ar), 2.65 (t, J = 7.5 Hz, 2 H, CH₂), 1.95–2.14

(m, 2 H, CH₂), 1.91 (quint, J = 7.5 Hz, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.22, 137.66, 130.40,

107.74–120.13 (m, Rf₈), 91.41, 34.51, 30.21 (t, J = 22.5 Hz), 21.68

(t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 659.3 (6) [M⁺], 168.9 (100), 91.0 (24).

1-Bromo-4-(9,9,10,10,11,11,12,12,12-nonafluorododecyl)ben-

zene (5g)

As described for 5a using alkyne 12c (2.4 g, 4.96 mmol), Rh/C (150

mg), pentane (18 mL), and CH₂Cl₂(6 mL) gave 5g (2.34 g, 97%);

R_f= 0.91 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.39 (d, J = 8.2 Hz, 2 H, Ar), 7.05

(d, J = 8.2 Hz, 2 H, Ar), 2.56 (t, J = 7.7 Hz, 2 H, CH₂), 1.97–2.12

(m, 2 H, CH₂), 1.54–1.60 (m, 4 H, CH₂), 1.28–1.39 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.67, 131.26, 130.15, 119.29,

105.35–120.77 (m, Rf₄), 35.29, 31.26, 30.75 (t, J = 22.5 Hz), 29.02,

29.98, 29.15, 29.17, 20.03 (t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 665.1 (15) [M⁺], 537.8 (1), 217.0 (100).

1-Iodo-4-(5,5,6,6,7,7,8,8,8-nonafluorooctyl)benzene (5c)

As described for 5b using 9a (5.5 g, 12.75 mmol), Ni (3.74 g, 63.78

mmol), KI (4.23 g, 25.51 mmol), I₂(160 mg, 0.63 mmol), and DMF

(35 mL) gave 5c (4.71 g, 77%); R_f= 0.85 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.60 (d, J = 8.2 Hz, 2 H, Ar), 7.04

(d, J = 8.2 Hz, 2 H, Ar), 2.59 (t, J = 7.3 Hz, 2 H, CH₂), 1.99–2.16

(m, 2 H, CH₂), 1.62–1.67 (m, 4 H, CH₂).

MS (EI, 70 eV): m/z (%) = 488.7 (13) [M⁺], 168.9 (100), 91.0 (41).

1-Iodo-4-(9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-

tetradecyl)benzene (5h)

As described for 5b using 13a (2.1 g, 3.6 mmol), Ni (1.05 g, 17.9

mmol), KI (1.2 g, 7.15 mmol), I₂(45 mg, 0.18 mmol), and DMF (15

mL) gave 5h (2.0 g, 88%); R_f= 0.90 (pentane).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.24, 137.47, 130.44,

108.55–122.20 (m, Rf₄), 90.98, 35.03, 30.58 (t, J = 22.5 Hz), 30.06,

19.72 (t, J = 3.3 Hz).

¹H NMR (360 MHz, CDCl₃): d = 7.58 (d, J = 8.2 Hz, 2 H, Ar), 6.92

(d, J = 8.2 Hz, 2 H, Ar), 2.54 (t, J = 7.3 Hz, 2 H, CH₂), 1.96–2.11

(m, 2 H, CH₂), 1.54–1.60 (m, 4 H, CH₂), 1.28–1.39 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 142.78, 137.67, 130.94, 90.94,

105.79–119.70 (m, Rf₆), 35.79, 31.60, 31.26 (t, J = 22.5 Hz), 29.45,

29.47, 29.50, 29.52, 20.47 (t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 478.6 (45) [M⁺], 217.0 (100).

1-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-Heni-

cosafluorotetradecyl)-4-iodobenzene (5d)

As described for 5b using 9b (6.0 g, 8.2 mmol), Ni (2.4 g, 41.0

mmol), KI (2.7 g, 16.4 mmol), I₂(104 mg, 0.4 mmol), and DMF (25

mL) gave 5d (4.8 g, 75%); R_f= 0.90 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.60 (d, J = 8.2 Hz, 2 H, Ar), 6.92

(d, J = 8.2 Hz, 2 H, Ar), 2.59 (t, J = 6.8 Hz, 2 H, CH₂), 2.01–2.16

(m, 2 H, CH₂), 1.64–1.75 (m, 4 H, CH₂).

MS (EI, 70 eV): m/z (%) = 635.2 (16) [M⁺], 217.0 (100), 90.9 (29).

1-(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-Heptadeca-

fluorohexadecyl)-4-iodobenzene (5i)

As described for 5b using 13b (4.1 g, 5.9 mmol), Ni (1.75 g, 29.8

mmol), KI (2.0 g, 11.9 mmol), I₂(76 mg, 0.30 mmol), and DMF (20

mL) gave 5i (3.96 g, 90%); R_f= 0.85 (pentane).

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

1132

O. F. Aebischer et al.

PAPER

¹H NMR (360 MHz, CDCl₃): d = 7.58 (d, J = 8.2 Hz, 2 H, Ar), 6.92

(d, J = 8.2 Hz, 2 H, Ar), 2.54 (t, J = 7.3 Hz, 2 H, CH₂), 1.96–2.09

(m, 2 H, CH₂), 1.54–1.59 (m, 4 H, CH₂), 1.28–1.39 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 142.78, 137.67, 130.94,

105.79–119.70 (m, Rf₈), 90.94, 35.79, 31.61, 31.26 (t, J = 22.5 Hz),

29.45–29.52 (4C), 20.47 (t, J = 3.3 Hz).

was quenched by the addition of H₂O (5 mL), 15% NaOH (5 mL),

and H₂O (15 mL). The crude reaction product was extracted with

Et₂O (3 × 200 mL). The combined organic phases were filtered

through a Büchner and the filtrate was washed with H₂O (50 mL)

and dried (Na₂SO₄) and all volatiles were removed under reduced

pressure yielding 9a (13.6 g, 80%) as a colorless oil; R_f= 0.85 (pen-

tane).

¹H NMR (360 MHz, CDCl₃): d = 7.37 (d, J = 8.6 Hz, 2 H, Ar), 7.04

(d, J = 8.6 Hz, 2 H, Ar), 2.58 (t, J = 6.8 Hz, 2 H, CH₂), 2.00–2.13

(m, 2 H, CH₂), 1.58–1.69 (m, 4 H, CH₂).

MS (EI, 70 eV): m/z (%) = 735.4 (8) [M⁺], 217.0 (100), 91.0 (24).

1-Bromo-4-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca-

fluoroundecyl)benzene (6a)

As described for 5a using alkene 4b (14.0 g, 23.0 mmol), Rh/C (702

mg), pentane (60 mL), and CH₂Cl₂(20 mL) gave (13.9 g, 98%);

R_f= 0.54 (pentane).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.53, 131.46, 130.05, 119.7,

107.19–121.07 (m, Rf₄), 35.11, 30.64, 30.54 (t, J = 22.5 Hz), 19.69

(t, J = 3.3 Hz).

¹H NMR (360 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 2 H, Ar), 7.06

(d, J = 8.2 Hz, 2 H, Ar), 2.67 (t, J = 7.5 Hz, 2 H, CH₂), 2.0–2.14 (m,

2 H, CH₂), 1.92 (quint, J = 7.5 Hz, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 139.55, 131.68, 130.06, 120.13,

107.78–122.29 (m, Rf₈), 34.41, 30.21 (t, J = 22.5 Hz), 21.71 (t,

J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 430.5 (12) [M⁺], 168.9 (100).

1-Bromo-4-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-

henicosafluorotetradecyl)benzene (9b)

As described for 9a using aryl 8b (18.0 g, 21.0 mmol), LiAlH₄(797

mg, 21 mmol), and THF (50 mL) gave 9b (6.2 g, 40%); R_f= 0.80

(pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.41 (d, J = 8.2 Hz, 2 H, Ar), 7.04

(d, J = 8.2 Hz, 2 H, Ar), 2.61 (t, J = 6.8 Hz, 2 H, CH₂), 2.00–2.17

(m, 2 H, CH₂), 1.63–1.76 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.54, 131.48, 130.08, 119.72,

107.77–121.88 (m, Rf₁₀), 34.94, 30.69, 30.69 (t, J = 21.1 Hz), 19.75

(t, J = 4.0 Hz).

MS (EI, 70 eV): m/z (%) = 617.0 (15) [M⁺], 537.8 (1), 170.8 (100).

1-Bromo-4-(5,5,6,6,7,7,8,8,8-nonafluoro-3-iodooctyl)benzene

(8a)

1-Bromo-4-but-3-enylbenzene (7, 17 g, 80.53 mmol) was added to

a round-bottomed flask and heated to 50 °C; 30% aq Na₂S₂O₅soln

(7.6 mL) and perfluorobutyl iodide (27 g, 78.45 mmol) were added.

Under a positive stream of argon AIBN (230 mg, 1.39 mmol) was

added and the mixture was heated to 80 °C for 2 h. The mixture was

allowed to reach r.t. and then H₂O (50 mL) was added. The obtained

suspension was extracted with Et₂O (3 × 100 mL). The combined

organic phases were washed with H₂O (50 mL) and dried (Na₂SO₄)

and all volatiles were removed under reduced pressure to give 8a

(31.1 g, 71%) as a colorless oil; R_f= 0.85 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.38 (d, J = 8.6 Hz, 2 H, Ar), 7.09

(d, J = 8.6 Hz, 2 H, Ar), 4.23 (tt, J = 8.2, 5.0 Hz, 1 H, CH), 2.67–

3.02 (m, 2 H, CH₂), 2.66 (t, J = 8.2 Hz, 2 H, CH₂), 2.02–2.16 (m, 2

H, CH₂).

MS (EI, 70 eV): m/z (%) = 731.8 (80) [M⁺], 170.9 (100).

6,6,7,7,8,8,9,9,10,10,11,11,11-Tridecafluoroundec-1-yne (11a);

Typical Procedure

Lithium acetylide–ethylenediamine complex (18.2 g, 0.20 mol) was

suspended in DMSO (90 mL) in a round-bottomed flask under an

inert atmosphere. To the brown-colored suspension 9-bromo-

1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorononane (10a, 29 g, 65.7

mmol) dissolved in pentane (10 mL) was added at 8 °C. The black

suspension was stirred at r.t. for 17 h and the mixture was quenched

by the addition of H₂O (30 mL). The resulting suspension was dilut-

ed with CH₂Cl₂(100 mL), Büchner filtered, and extracted with

CH₂Cl₂(3 × 100 mL). The combined organic phases were dried

(Na₂SO₄) and all volatiles were removed under reduced pressure.

The resulting black oily liquid was filtered over a plug of silica gel

under reduced pressure (pentane). After removal of pentane the title

compound (9.64 g, 38%) was obtained as colorless oil; R_f= 0.95

(pentane).

¹H NMR (360 MHz, CDCl₃): d = 2.33 (td, J = 6.8, 2.7 Hz, 2 H,

CH₂), 2.16–2.28 (m, 2 H, CH₂), 2.02 (t, J = 2.7 Hz, 1 H, CH), 1.78–

1.89 (m, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 108.10–121.18 (m, Rf₆), 82.27,

79.72, 29.83 (t, J = 22.5 Hz), 19.34 (t, J = 3.3 Hz), 17.91.

¹³C NMR (90.55 MHz, CDCl₃): d = 138.76, 131.68, 130.22, 120.21,

108.40–122.40 (m, Rf₄), 41.57 (t, J = 22.5 Hz), 41.38, 35.12, 19.65

(t, J = 2.5 Hz).

MS (EI, 70 eV): m/z (%) = 556.7 (8) [M⁺], 429.5 (12), 168.9 (100).

1-Bromo-4-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-

henicosafluoro-3-iodo-tetradecyl)benzene (8b)

As described for 8a using 7 (4.45 g, 21.1 mmol), perfluorodecyl io-

dide (15.0 g, 23.2 mmol), AIBN (70 mg, 0.42 mmol), and 30%

Na₂S₂O₅(5 mL) gave 8b (17.7 g, 98%); R_f= 0.91 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 2 H, Ar), 7.09

(d, J = 8.2 Hz, 2 H, Ar), 4.23 (tt, J = 8.6, 5.0 Hz, 1 H, CH), 2.65–

3.04 (m, 2 H, CH₂), 2.65–2.73 (m, 2 H, CH₂), 2.05–2.12 (m, 2 H,

CH₂).

MS (EI, 70 eV): m/z (%) = 117.0 (15), 66.9 (100).

7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-Heptadecafluoro-

tetradec-1-yne (11b)

¹³C NMR (90.55 MHz, CDCl₃): d = 138.78, 131.70, 130.24, 120.21,

108.37–121.10 (m, Rf₁₀), 41.71 (t, J = 21.1 Hz), 41.42, 35.14,

19.74.

As

described

for

11a

using

12-bromo-

1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorododecane

(10b,

MS (EI, 70 eV): m/z (%) = 857.5 (1) [M⁺], 730.3 (4), 168.9 (100).

15.0 g, 25.2 mmol), lithium acetylide–ethylenediamine complex

(7.0 g, 75.6 mmol), DMSO (30 mL), and pentane (15 mL) gave 11b

(4.94 g, 39%); R_f= 0.90 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 2.25 (td, J = 6.8, 2.7 Hz, 2 H,

CH₂), 2.02–2.17 (m, 2 H, CH₂), 1.98 (t, J = 2.7 Hz, 1 H, CH), 1.71–

1.80 (m, 2 H, CH₂), 1.59–1.67 (m, 2 H, CH₂).

1-Bromo-4-(5,5,6,6,7,7,8,8,8-nonafluorooctyl)benzene (9a);

Typical Procedure

LiAlH₄(1.8 g, 47.4 mmol) was placed in a 500-mL 3-necked flask

under inert atmosphere and THF (60 mL) was added by syringe.

Compound 8a (22 g, 39.5 mmol) was dissolved in THF (40 mL) and

was carefully added to the LiAlH₄slurry in such a rate to maintain

the reaction medium at a gentle reflux. After 6 h at r.t. the mixture

¹³C NMR (90.55 MHz, CDCl₃): d = 107.43–121.94 (m, Rf₈), 83.27,

68.94, 30.44 (t, J = 22.5 Hz), 27.76, 19.34 (t, J = 3.3 Hz), 18.13.

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1133

MS (EI, 70 eV): m/z (%) = 500.8 (2) [M⁺], 131.0 (42), 81.0 (100).

¹H NMR (360 MHz, CDCl₃): d = 7.42 (d, J = 8.2 Hz, 2 H, Ar), 7.25

(d, J = 8.2 Hz, 2 H, Ar), 2.53 (t, J = 6.8 Hz, 2 H, CH₂), 2.20–2.34

(m, 2 H, CH₂), 1.88–1.96 (m, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 133.01, 131.51, 122.35, 122.06,

107.70–118.79 (m, Rf₆), 89.06, 81.00, 30.06 (t, J = 22.5 Hz), 19.58

(t, J = 3.3 Hz), 18.94.

9,9,10,10,11,11,12,12,12-Nonafluorododec-1-yne (11c)

As described for 11a using 10-bromo-1,1,1,2,2,3,3,4,4-nonafluoro-

decane (10c, 24.0 g, 62.6 mmol), lithium acetylide–ethylenedi-

amine complex (17.3 g, 0.19 mol), DMSO (100 mL), and pentane

(10 mL) gave 11c (12.8 g, 62%); R_f= 0.99 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 2.21 (td, J = 7.0, 2.7 Hz, 2 H,

CH₂), 2.01–2.15 (m, 2 H, CH₂), 1.95 (t, J = 2.7 Hz, 1 H, CH), 1.59–

1.67 (m, 2 H, CH₂), 1.52–1.59 (m, 2 H, Hz, CH₂), 1.39–1.52 (m, 4

H, CH₂).

MS (EI, 70 eV): m/z (%) = 540.9 (32) [M⁺], 461.7 (8), 223.1 (17),

192.9 (100), 172.0 (45), 142 (63), 128.0 (63).

1-Bromo-4-(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-hepta-

decafluorotetradec-1-ynyl)benzene (12b)

As described for 12a using alkyne 11b (4.8 g, 9.6 mmol), Pd(PPh₃)₄

(670 mg, 0.57 mmol), CuI (183 mg, 0.96 mmol), 1-bromo-4-iodo-

benzene (2.7 g, 9.6 mmol), Et₃N (8.0 mL, 57.6 mmol), and THF (50

mL) gave 12b (2.27 g, 36%); R_f= 0.62 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.41 (d, J = 8.2 Hz, 2 H, Ar), 7.24

(d, J = 8.2 Hz, 2 H, Ar), 2.46 (t, J = 6.8 Hz, 2 H, CH₂), 2.06–2.20

(m, 2 H, CH₂), 1.75–1.84 (m, 2 H, CH₂), 1.66–1.74 (m, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 106.03–123.20 (m, Rf₄), 84.27,

68.32, 30.71 (t, J = 22.5 Hz), 28.56, 28.24, 28.11, 19.97 (t, J = 3.3

Hz), 18.27.

MS (EI, 70 eV): m/z (%) = 95.0 (25), 81.4 (100), 67.0 (76).

9,9,10,10,11,11,12,12,13,13,14,14,14-Tridecafluorotetradec-1-

yne (11d)

As described for 11a using 12-bromo-1,1,1,2,2,3,3,4,4,5,5,6,6-

tridecafluorododecane (10d, 12.0 g, 24.8 mmol), lithium acetylide–

ethylenediamine complex (16.9 g, 0.18 mol), DMSO (30 mL), and

pentane (20 mL) gave 11d (7.72 g, 73%); R_f= 0.84 (silica gel, pen-

tane, KMnO₄).

¹H NMR (360 MHz, CDCl₃): d = 2.21 (td, J = 7.0, 2.7 Hz, 2 H,

CH₂), 2.00–2.15 (m, 2 H, CH₂), 1.96 (t, J = 2.7 Hz, 1 H, CH), 1.59–

1.67 (m, 2 H, CH₂), 1.52–1.59 (m, 2 H, CH₂), 1.39–1.52 (m, 4 H,

CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 132.99, 131.46, 122.65, 121.82,

107.74–119.07 (m, Rf₈), 90.16, 80.36, 30.45 (t, J = 22.5 Hz), 27.89,

19.50 (t, J = 3.3 Hz), 19.13.

MS (EI, 70 eV): m/z (%) = 655.2 (12) [M⁺], 576.1 (16), 221.0 (27),

192.9 (90), 142 (100), 128.0 (83).

1-Bromo-4-(9,9,10,10,11,11,12,12,12-nonafluorododec-1-

ynyl)benzene (12c)

As described for 12a using alkyne 11c (10.1 g, 30.7 mmol),

Pd(PPh₃)₄(1.4 g, 1.2 mmol), CuI (470 mg, 2.5 mmol), 1-bromo-4-

iodobenzene (8.7 g, 30.7 mmol), Et₃N (25.6 mL, 0.18 mol), and

THF (120 mL) gave 12c (11.6 g, 78%); R_f= 0.81 (pentane).

¹³C NMR (90.55 MHz, CDCl₃): d = 103.61–121.66 (m, Rf₆), 84.30,

68.34, 30.81 (t, J = 22.5 Hz), 28.56, 28.24, 28.11, 20.00 (t, J = 3.3

Hz), 18.28.

MS (EI, 70 eV): m/z (%) = 95.1 (33), 81.1 (100), 67.1 (36).

¹H NMR (360 MHz, CDCl₃): d = 7.42 (d, J = 8.2 Hz, 2 H, Ar), 7.26

(d, J = 8.2 Hz, 2 H, Ar), 2.42 (t, J = 6.8 Hz, 2 H, CH₂), 2.01–2.16

(m, 2 H, CH₂), 1.59–1.69 (m, 4 H, CH₂), 1.45–1.53 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 132.99, 131.42, 122.90, 121.64,

108.54–121.07 (m, Rf₄), 91.23, 79.82, 30.72 (t, J = 22.5 Hz), 28.61,

28.45, 28.27, 20.00 (t, J = 3.3 Hz), 19.31.

9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-Heptadeca-

fluorohexadec-1-yne (11e)

As

described

for

11a

using

14-bromo-

1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorotetradecane (10e,

14.1 g, 24.2 mmol), lithium acetylide ethylenediamine complex (6.7

g, 72.6 mmol), DMSO (40 mL), and pentane (30 mL) gave (5.6 g,

44%); R_f= 0.80 (pentane).

MS (EI, 70 eV): m/z (%) = 484.7 (9) [M⁺], 237.1 (8), 223.1 (22),

209.0 (6), 194.9 (65), 181.8 (12), 168.9 (8), 142 (100).

¹H NMR (360 MHz, CDCl₃): d = 2.21 (td, J = 7.0, 2.7 Hz, 2 H,

CH₂), 2.00–2.15 (m, 2 H, CH₂), 1.95 (t, J = 2.7 Hz, 1 H, CH), 1.59–

1.67 (m, 2 H, CH₂), 1.52–1.59 (m, 2 H, CH₂), 1.40–1.52 (m, 4 H,

CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 107.80–118.72 (m, Rf₈), 84.30,

68.34, 30.82 (t, J = 22.5 Hz), 28.56, 28.24, 28.11, 20.00 (t, J = 3.3

Hz), 18.28.

1-Bromo-4-(9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluo-

rotetradec-1-ynyl)benzene (12d)

As described for 12a using alkyne 11d (5.5 g, 12.8 mmol),

Pd(PPh₃)₄(890 mg, 0.77 mmol), CuI (245 mg, 1.28 mmol), 1-bro-

mo-4-iodobenzene (3.6 g, 12.8 mmol), Et₃N (10.75 mL, 77.0

mmol), and THF (65 mL) gave 12d (2.63 g, 35%); R_f= 0.86 (pen-

tane).

MS (EI, 70 eV): m/z (%) = 131.0 (43), 81.0 (100), 67.0 (30).

¹H NMR (360 MHz, CDCl₃): d = 7.42 (d, J = 8.2 Hz, 2 H, Ar), 7.26

(d, J = 8.2 Hz, 2 H, Ar), 2.42 (t, J = 6.8 Hz, 2 H, CH₂), 2.01–2.16

(m, 2 H, CH₂), 1.59–1.70 (m, 4 H, CH₂), 1.45–1.55 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 132.99, 131.42, 122.90, 121.64,

107.22–119.17 (m, Rf₆), 91.23, 79.83, 30.83 (t, J = 22.5 Hz), 28.62,

28.45, 28.29, 20.03 (t, J = 3.3 Hz), 19.32.

1-Bromo-4-(6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoroundec-

1-ynyl)benzene (12a); Typical Procedure

Pd(PPh₃)₄(1.65 g, 1.43 mmol), CuI (453 mg, 2.38 mmol), and 1-

bromo-4-iodobenzene (6.74 g, 23.8 mmol) were dissolved in THF

(110 mL) in a Schlenk reaction vessel under an inert atmosphere.

Compound 11a (9.2 g, 23.8 mmol) was degassed in a separate flask,

diluted with THF (20 mL), and added into the Schlenk flask, and

then Et₃N (20.0 mL, 143 mmol) was added by syringe. The Schlenk

tube was sealed and heated to 80 °C for 6 d. The cold mixture was

then quenched by the addition of H₂O (100 mL) and extracted with

Et₂O (3 × 100 mL). The combined organic fractions were washed

with 10% HCl (150 mL) and H₂O (100 mL) and dried (Na₂SO₄) and

all volatiles were removed yielding a brown oil. Several filtrations

through silica gel (pentane–Et₂O, 9:1 then pentane for successive

filtrations) yielded 12a (4.91 g, 38%) as a colorless oil; R_f= 0.78

(pentane).

MS (EI, 70 eV): m/z (%) = 584.9 (7) [M⁺], 237.1 (8), 223.1 (35),

209.0 (6), 194.9 (84), 181.8 (12), 168.9 (18), 142 (100).

1-Bromo-4-(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-

heptadecafluorohexadec-1-ynyl)benzene (12e)

As described for 12a using alkyne 11e (5.5 g, 10.4 mmol),

Pd(PPh₃)₄(720 mg, 0.62 mmol), CuI (198 mg, 1.04 mmol), 1-bro-

mo-4-iodobenzene (2.9 g, 10.4 mmol), Et₃N (8.7 mL, 62.5 mmol),

and THF (70 mL) gave 12e (2.46 g, 35%); R_f= 0.79 (pentane).

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

1134

O. F. Aebischer et al.

PAPER

1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoro-

undecyl)-4-{[4-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca-

fluoroundecyl)phenyl]ethynyl}benzene (14b)

¹H NMR (360 MHz, CDCl₃): d = 7.42 (d, J = 8.2 Hz, 2 H, Ar), 7.25

(d, J = 8.2 Hz, 2 H, Ar), 2.41 (t, J = 6.8 Hz, 2 H, CH₂), 2.00–2.15

(m, 2 H, CH₂), 1.59–1.69 (m, 4 H, CH₂), 1.45–1.55 (m, 4 H, CH₂).

As described for 14a using iodoaryl 5b (5.0 g, 7.7 mmol),

PdCl₂(PPh₃)₂(530 mg, 0.46 mmol), CuI (146 mg, 0.77 mmol), DBU

(6.9 mL, 45.2 mmol), THF (40 mL), H₂O (55 mL, 3.1 mmol), and

trimethylsilylacetylene (0.56 mL, 3.8 mmol) gave 14b (2.71 g,

66%); R_f= 0.90 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 7.47 (d, J = 8.2 Hz, 4 H, Ar), 7.17

(d, J = 8.2 Hz, 4 H, Ar), 2.73 (t, J = 7.5 Hz, 4 H, CH₂), 1.95–2.14

(m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 132.99, 131.42, 122.89, 121.64,

108.17–118.36 (m, Rf₈), 91.23, 79.82, 30.82 (t, J = 22.5 Hz), 28.62,

28.45, 28.27, 20.03 (t, J = 3.3 Hz), 19.31.

MS (EI, 70 eV): m/z (%) = 685.2 (7) [M⁺], 237.1 (8), 223.1 (34),

209.0 (9), 194.9 (82), 181.8 (15), 168.9 (18), 142 (100).

1-Bromo-4-(9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluo-

rotetradecyl)benzene (13a)

As described for 5a using alkyne 12d (2.5 g, 4.3 mmol), Rh/C (130

mg), pentane (24 mL), and CH₂Cl₂(7 mL) gave 13a (2.24 g, 89%);

R_f= 0.90 (pentane).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.87, 131.80, 128.39, 121.30,

107.74–120.13 (m, Rf₈), 89.01, 34.89, 30.23 (t, J = 22.5 Hz), 21.63

(t, J = 3.3 Hz).

¹H NMR (360 MHz, CDCl₃): d = 7.39 (d, J = 8.2 Hz, 2 H, Ar), 7.05

(d, J = 8.2 Hz, 2 H, Ar), 2.56 (t, J = 7.7 Hz, 2 H, CH₂), 1.98–2.13

(m, 2 H, CH₂), 1.56–1.60 (m, 4 H, CH₂), 1.27–1.38 (m, 8 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 1349.27 (80) [M + DCTB]⁺,

1098.10 (100) [M⁺].

1-(5,5,6,6,7,7,8,8,8-Nonafluorooctyl)-4-{[4-(5,5,6,6,7,7,8,8,8-

nonafluorooctyl)phenyl]ethynyl}benzene (14c)

As described for 14a using iodoaryl 5c (11.2 g, 26.0 mmol),

PdCl₂(PPh₃)₂(1.09 g, 1.56 mmol), CuI (496 mg, 2.6 mmol), DBU

(23.3 mL, 156.2 mmol), THF (125 mL), H₂O (190 mL, 10.4 mmol),

and trimethylsilylacetylene (1.9 mL, 13.0 mmol) gave 14c (1.9 g,

20%); R_f= 0.82 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 7.45 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.67 (t, J = 7.3 Hz, 4 H, CH₂), 2.01–2.17

(m, 4 H, CH₂), 1.62–1.76 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.89, 131.64, 128.38,

110.50–125.52 (m, Rf₄), 120.94, 88.96, 35.44, 30.62, 30.62 (t,

J = 22.5 Hz), 19.75 (t, J = 3.3 Hz).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.67, 131.27, 130.15, 119.29,

105.35–120.77 (m, Rf₆), 35.30, 31.23, 30.85 (t, J = 22.5 Hz, 29.05,

29.08, 29.10, 29.11, 20.07 (t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 589.7 (9) [M⁺], 170.9 (100), 90.9 (33).

1-Bromo-4-(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-

heptadecafluorohexadecyl)benzene (13b)

As described for 5a using alkyne 12e (4.5 g, 6.6 mmol), Rh/C (200

mg), pentane (21 mL), and CH₂Cl₂(7 mL) gave 13b (4.21 g, 93%);

R_f= 0.85 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.39 (d, J = 8.2 Hz, 2 H, Ar), 7.05

(d, J = 8.2 Hz, 2 H, Ar), 2.56 (t, J = 7.7 Hz, 2 H, CH₂), 1.98–2.13

(m, 2 H, CH₂), 1.56–1.60 (m, 4 H, CH₂), 1.27–1.39 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 142.08, 131.67, 130.55, 119.70,

106.40–118.86 (m, Rf₈), 35.70, 31.64, 31.26 (t, J = 22.5 Hz), 29.45,

29.49, 29.53, 29.58, 20.47 (t, J = 3.3 Hz).

MS (EI, 70 eV): m/z (%) = 727.5 (20) [M⁺], 465.7 (100).

1-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-Heni-

cosafluorotetradecyl)-4-{[4-

MS (EI, 70 eV): m/z (%) = 689.3 (9) [M⁺], 170.8 (100), 90.9 (33).

(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heni-

cosafluorotetradecyl)phenyl]ethynyl}benzene (14d)

As described for 14a using iodoaryl 5d (3.25 g, 4.8 mmol),

PdCl₂(PPh₃)₂(203 mg, 0.29 mmol), CuI (92 mg, 0.48 mmol), DBU

(4.3 mL, 29.0 mmol), THF (40 mL), H₂O (35 mL, 1.9 mmol), and

trimethylsilylacetylene (0.35 mL, 2.4 mmol) gave 14d (2.15 g,

80%); R_f= 0.60 (pentane–Et₂O, 1:1).

¹H NMR (360 MHz, CDCl₃): d = 7.45 (d, J = 7.7 Hz, 4 H, Ar), 7.15

(d, J = 7.7 Hz, 4 H, Ar), 2.67 (t, J = 6.8 Hz, 4 H, CH₂), 2.01–2.16

(m, 4 H, CH₂), 1.64–1.75 (m, 8 H, CH₂).

1-(4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluorononyl)-4-{[4-

(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)phenyl]eth-

ynyl}benzene (14a); Typical Procedure

CuI (209 mg, 1.1 mmol) and PdCl₂(PPh₃)₂(463 mg, 0.66 mmol)

were suspended in THF (10 mL) in an oven dried Schlenk reaction

vessel under an inert atmosphere. Iodoaryl 5a (6.2 g, 11.0 mmol)

was dissolved in THF (10 mL) and degassed separately then added

into the reaction vessel. Degassed DBU (9.9 mL, 65.9 mmol) was

added via syringe into the Schlenk and the reaction medium was

purged with argon. H₂O (79 mL, 4.4 mmol) and cooled (4 °C) tri-

methylsilylacetylene (0.8 mL, 5.5 mmol) were added simultaneous-

ly with two syringes. The Schlenk was then covered with aluminum

foil and heated to 75 °C. After 29 h, the black mixture was washed

with H₂O (2 × 100 mL), 10% HCl (50 mL), brine (50 mL), and H₂O

(50 mL). The combined organic fractions were purified by several

precipitations (Et₂O–pentane–EtOH) to yield 14a (3.0 g, 61%) as a

white solid; R_f= 0.42 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.47 (d, J = 8.2 Hz, 4 H, Ar), 7.17

(d, J = 8.2 Hz, 4 H, Ar), 2.73 (t, J = 7.3 Hz, 4 H, CH₂), 1.91–2.17

(m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.88, 131.81, 128.39, 121.32,

105.69–120.49 (m, Rf₆), 89.01, 34.90, 30.23 (t, J = 22.5 Hz), 21.63

(t, J = 3.3 Hz).

¹³C NMR (125.77 MHz, CDCl₃): d = 141.89, 131.73, 128.37,

121.28, 107.79–121.91 (m, Rf₁₀), 89.08, 35.47, 30.97 (t, J = 22.1

Hz), 30.59, 19.93.

MS (MALDI-ICR, DCTB): m/z (%) = 1577.27 (85) [M + DCTB]⁺,

1326.12 (100) [M⁺].

1-(6,6,7,7,8,8,9,9,10,10,11,11,11-Tridecafluoroundecyl)-4-{[4-

(6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoroundecyl)phe-

nyl]ethynyl}benzene (14e)

As described for 14a using bromoaryl 5e (4.6 g, 8.4 mmol),

PdCl₂(PPh₃)₂(585 mg, 0.5 mmol), CuI (161 mg, 0.84 mmol), DBU

(7.6 mL, 50.6 mmol), THF (50 mL), H₂O (60 mL, 3.38 mmol), and

trimethylsilylacetylene (0.74 mL, 5.1 mmol) gave 14e (225 mg,

6%); R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 7.37 (d, J = 8.2 Hz, 4 H, Ar), 7.08

(d, J = 8.2 Hz, 4 H, Ar), 2.57 (t, J = 7.3 Hz, 4 H, CH₂), 1.90–2.09

(m, 4 H, CH₂), 1.56–1.64 (m, 8 H, CH₂), 1.30–1.38 (m, 4 H, CH₂).

MS (EI, 70 eV): m/z (%) = 900.0 (11) [M⁺], 551.9 (100).

Synthesis 2010, No. 7, 1123–1140 © Thieme Stuttgart · New York

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1135

¹³C NMR (90.55 MHz, CDCl₃): d = 142.45, 131.56, 128.40, 120.83,

108.10–118.79 (m, Rf₆), 88.93, 35.55, 30.79, 30.79 (t, J = 22.5 Hz),

28.59, 20.00 (t, J = 3.3 Hz).

1-(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-Heptadeca-

fluorohexadecyl)-4-{[4-

(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-heptadeca-

fluorohexadecyl)phenyl]ethynyl}benzene (14i)

As described for 14a using iodoaryl 5i (3.8 g, 5.2 mmol), Pd(PPh₃)₄

(360 mg, 0.31 mmol), CuI (98.5 mg, 0.52 mmol), DBU (4.6 mL,

31.05 mmol), THF (30 mL), H₂O (30 mL, 2.07 mmol), and trimeth-

ylsilylacetylene (0.38 mL, 2.6 mmol) gave 14i (680 mg, 21%);

R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.61 (t, J = 7.7 Hz, 4 H, CH₂), 1.99–2.14

(m, 4 H, CH₂), 1.56–1.61 (m, 8 H, CH₂), 1.28–1.39 (m, 16 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 1205.34 (90) [M + DCTB]⁺,

954.18 (100) [M⁺].

1-(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-Heptadecafluo-

rotetradecyl)-4-{[4-

(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluo-

rotetradecyl)phenyl]ethynyl}benzene (14f)

As described for 14a using bromoaryl 5f (3.0 g, 4.6 mmol),

Pd(PPh₃)₄(316 mg, 0.27 mmol), CuI (87 mg, 0.46 mmol), DBU

(4.08 mL, 27.3 mmol), THF (25 mL), H₂O (32 mL, 27.3 mmol), and

trimethylsilylacetylene (0.33 mL, 2.27 mmol) gave 14f (1.2 g,

46%); R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (500 MHz, CDCl₃): d = 7.42 (d, J = 8.2 Hz, 4 H, Ar), 7.13

(d, J = 8.2 Hz, 4 H, Ar), 2.62 (t, J = 7.7 Hz, 4 H, CH₂), 1.99–2.10

(m, 4 H, CH₂), 1.57–1.67 (m, 8 H, CH₂), 1.36–1.40 (m, 8 H, CH₂).

¹³C NMR (90.55 MHz, CDCl3): d = 143.05, 131.46, 128.43,

120.64, 105.02–118.85 (m, Rf₈), 89.90, 35.84, 31.17, 30.86 (t,

J = 22.5 Hz), 29.03, 29.05, 29.06, 29.08, 20.07 (t, J = 3.3 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 1489.41 (22) [M + DCTB]⁺,

1238.26 (100) [M]⁺.

¹³C NMR (125.77 MHz, CDCl₃): d = 142.76, 131.57, 128.40,

120.92, 109.13–121.02 (m, Rf₈), 89.00, 35.75, 31.00 (t, J = 22.5

Hz), 30.88, 28.99, 28.78, 20.13 (t, J = 3.3 Hz).

1-(6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Heptadecafluoro-

tridecyl)-4-{[4-(6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-hepta-

decafluorotridecyl)phenyl]ethynyl}benzene (14j)

An oven dried Schlenk reaction vessel was charged with freshly ac-

tivated Mg turning (87.5 mg, 3.6 mmol) under an inert atmosphere.

The Mg was stirred under vacuum for 1 h and heated with a heat

gun (3 ×). As soon as the reaction vessel reached r.t. THF (2 mL)

MS (MALDI-ICR, DCTB): m/z (%) = 1433.35 (45) [M + DCTB]⁺,

1182.20 (100) [M⁺].

1-(9,9,10,10,11,11,12,12,12-Nonafluorododecyl)-4-{[4-

(9,9,10,10,11,11,12,12,12-nonafluorododecyl)phenyl]eth-

ynyl}benzene (14g)

As described for 14a using bromoaryl 5g (11.4 g, 23.4 mmol),

Pd(PPh₃)₄(1.62 g, 1.4 mmol), CuI (446 mg, 2.3 mmol), DBU (20.9

mL, 0.14 mol), THF (120 mL), H₂O (150 mL, 9.4 mmol), and tri-

methylsilylacetylene (1.29 mL, 13.0 mmol) gave 14g (4.8 g, 50%);

R_f= 0.52 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.61 (t, J = 7.3 Hz, 4 H, CH₂), 1.97–2.12

(m, 4 H, CH₂), 1.55–1.63 (m, 8 H, CH₂), 1.28–1.39 (m, 16 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 143.06, 131.48, 128.44, 120.65,

105.25–119.03 (m, Rf₄), 88.92, 35.85, 31.19, 30.77 (t, J = 22.5 Hz),

29.06, 29.11, 29.13, 29.22, 20.06 (t, J = 3.3 Hz).

was

syringed

in

under

argon.

13-Bromo-

1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorotridecane (1.71 g,

3.0 mmol), dissolved in THF (2 mL) was syringed into the Mg sus-

pension. The sealed Schlenk tube was heated to 75 °C for 12 h. In a

second oven-dried Schlenk tube PdCl₂(dppf)·CH₂Cl₂(61.5 mg, 75

mmol) and 1-bromo-4-[(4-bromophenyl)ethynyl]benzene (252 mg,

0.74 mmol) were suspended under an inert atmosphere in THF (6

mL). The previously freshly prepared brownish Grignard soln was

diluted with THF (3 mL) and added by syringe. The Schlenk tube

was sealed and heated to 75 °C for 7 d and then the mixture was

quenched by the addition of MeOH (20 mL). The formed precipitate

was Büchner filtered and washed with MeOH and pentane. The ob-

tained solid was dissolved in CH₂Cl₂(50 mL) and was washed with

H₂O (3 × 50 mL). Removal of all volatiles of the organic fraction

and precipitation (Et₂O–pentane) gave 14j (720 mg, 83%);

R_f= 0.77 (CH₂Cl₂–cyclohexane, 3:7).

¹H NMR (360 MHz, CDCl₃): d = 7.45 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.64 (t, J = 7.7 Hz, 4 H, CH₂), 1.97–2.13

(m, 4 H, CH₂), 1.61–1.71 (m, 8 H, CH₂), 1.37–1.46 (m, 4 H, CH₂).

¹³C NMR (125.77 MHz, CDCl₃): d = 142.44, 131.54, 128.40,

120.80, 107.21–121.24 (m, Rf₈), 88.91, 35.53, 30.78 (t, J = 22.1

Hz), 30.78, 28.58, 19.99.

MS (MALDI-ICR, DCTB): m/z (%) = 1089.44 (100) [M + DCTB]⁺,

838.29 (63) [M⁺].

1-(9,9,10,10,11,11,12,12,13,13,14,14,14-Tridecafluorotetra-

decyl)-4-{[4-(9,9,10,10,11,11,12,12,13,13,14,14,14-trideca-

fluorotetradecyl)phenyl]ethynyl}benzene (14h)

As described for 14a using iodoaryl 5h (2.0 g, 3.15 mmol),

Pd(PPh₃)₄(219 mg, 0.19 mmol), CuI (60 mg, 0.32 mmol), DBU (2.8

mL, 18.9 mmol), THF (20 mL), H₂O (23 mL, 1.26 mmol), and tri-

methylsilylacetylene (0.23 mL, 1.57 mmol) gave 14h (346 mg,

21%); R_f= 0.95 (pentane–Et₂O, 9:1).

MS (EI, 70 eV): m/z (%) = 1154.14 (10) [M⁺], 679.08 (100), 204.07

(70).

¹H NMR (360 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.61 (t, J = 7.7 Hz, 4 H, CH₂), 1.97–2.12

(m, 4 H, CH₂), 1.55–1.61 (m, 8 H, CH₂), 1.28–1.39 (m, 16 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 143.45, 131.87, 128.83, 121.05,

104.64–122.38 (m, Rf₆), 89.31, 36.25, 31.57, 31.26 (t, J = 22.5 Hz),

29.46, 29.48, 29.51, 29.54, 20.47 (t, J = 3.3 Hz).

Hexakis[4-(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)phe-

nyl]benzene (15a); Typical Procedure

A two necked round bottomed flask was charged with tolane 14a

(2.8 g, 3.1 mmol) under an inert atmosphere. Addition of deoxygen-

ated dioxane (180 mL) followed by Co₂(CO)₈(64 mg, 0.19 mmol)

under a positive pressure of argon, afforded a dark brown soln

which was refluxed for 60 h. Removal of the solvent under reduced

pressure yielded the crude target compound as a grey solid, which

was dissolved in pentane and agitated in an ultrasonic bath for 2 h.

Collection of the solid by suction filtration over Millipore^®afforded

15a (2.4 g, 86%); R_f= 0.95 (pentane–Et₂O, 9:1).

MS (MALDI-ICR, DCTB): m/z (%) = 1289.43 (100) [M + DCTB]⁺,

1038.27 (91) [M⁺].

¹H NMR (360 MHz, CDCl₃): d = 6.70 (d, J = 7.7 Hz, 12 H, Ar), 6.63

(d, J = 7.7 Hz, 12 H, Ar), 2.43 (t, J = 6.8 Hz, 12 H, CH₂), 1.71–1.83

(m, 24 H, CH₂).

1136

O. F. Aebischer et al.

PAPER

¹³C NMR (90.55 MHz, CDCl₃): d = 140.10, 138.75, 137.11, 131.65,

126.53, 104.19–120.29 (m, Rf₆), 34.13, 29.71 (t, J = 22.5 Hz),

21.45.

Hexakis[4-(7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-hepta-

decafluorotetradecyl)phenyl]benzene (15f)

As described for 15a using tolane 14f (1.0 g, 0.85 mmol), Co₂(CO)₈

(17.4 mg, 51.0 mmol), and dioxane (75 mL) gave 15f (0.64 g, 64%);

R_f= 0.98 (pentane–Et₂O, 9:1).

MS (MALDI-ICR, DCTB): m/z (%) = 2695.34 (100) [M⁺].

Hexakis[4-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluo-

roundecyl)phenyl]benzene (15b)

As described for 15a using tolane 14b (0.5 g, 0.45 mmol), Co₂(CO)₈

(12.4 mg, 36.4 mmol), dioxane (50 mL), and HFB (10mL) gave 15b

(0.42 g, 84%); R_f= 0.43 (pentane–Et₂O, 1:1).

¹H NMR (500 MHz, CDCl₃): d = 6.74 (d, J = 8.2 Hz, 12 H, Ar), 6.66

(d, J = 8.2 Hz, 12 H, Ar), 2.45 (t, J = 7.3 Hz, 12 H, CH₂), 1.81–1.91

(m, 12 H, CH₂), 1.70–1.77 (m, 12 H, CH₂).

¹³C NMR (125.77 MHz, CDCl₃): d = 140.30, 138.99, 137.32,

131.83, 126.65, 105.32–120.11 (m, Rf₈), 34.32, 30.14 (t, J = 22.1

Hz), 21.63.

¹H NMR (500 MHz, CDCl₃): d = 6.67 (d, J = 8.2 Hz, 12 H, Ar), 6.60

(d, J = 8.2 Hz, 12 H, Ar), 2.34 (t, J = 7.3 Hz, 12 H, CH₂), 1.95–2.06

(m, 12 H, CH₂), 1.49–1.56 (m, 12 H, CH₂), 1.38–1.45 (m, 12 H,

CH₂), 1.27–1.33 (m, 12 H, CH₂), 1.11–1.17 (m, 12 H, CH₂).

¹³C NMR (125.77 MHz, CDCl₃): d = 140.31, 138.67, 138.48,

131.50, 126.43, 108.71–120.53 (m, Rf₈), 35.12, 30.98 (t, J = 22.5

Hz), 30.85, 29.01, 28.34, 20.14 (t, J = 3.3 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 3546.64 (100) [M⁺].

Hexakis[4-(9,9,10,10,11,11,12,12,12-nonafluorododecyl)phe-

nyl]benzene (15g)

As described for 15a using tolane 14g (2.5 g, 2.98 mmol), Co₂(CO)₈

(61 mg, 0.18 mmol), and dioxane (120 mL) gave 15g (1.82 g, 73%);

R_f= 0.97 (pentane–Et₂O, 9:1).

MS (MALDI-ICR, DCTB): m/z (%) = 3294.22 (100) [M⁺], 2858.20

(10).

Hexakis[4-(5,5,6,6,7,7,8,8,8-nonafluorooctyl)phenyl]benzene

(15c)

As described for 15a using tolane 14c (1.8 g, 2.48 mmol), Co₂(CO)₈

(51.0 mg, 0.15 mmol), and dioxane (150 mL) gave 15c (1.7 g, 95%);

R_f= 0.92 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 6.68 (d, J = 8.2 Hz, 12 H, Ar), 6.62

(d, J = 8.2 Hz, 12 H, Ar), 2.39 (t, J = 6.8 Hz, 12 H, CH₂), 1.90–2.03

(m, 12 H, CH₂), 1.35–1.55 (m, 24 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.19, 138.52, 137.85, 131.58,

126.44, 105.63–121.06 (m, Rf₄), 34.61, 30.45 (t, J = 22.5 Hz),

30.35, 18.94.

¹H NMR (360 MHz, CDCl₃): d = 6.67 (d, J = 8.2 Hz, 12 H, Ar), 6.61

(d, J = 8.2 Hz, 12 H, Ar), 2.34 (t, J = 7.3 Hz, 12 H, CH₂), 1.95–2.10

(m, 12 H, CH₂), 1.50–1.61 (m, 24 H, CH₂), 1.25–1.39 (m, 48 H,

CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.27, 138.85, 138.33, 131.42,

126.43, 107.63–122.18 (m, Rf₄), 35.29, 31.13, 30.77 (t, J = 22.5 Hz,

CH₂), 28.70. 28.93, 29.13, 29.24, 20.07 (t, J = 3.3 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 2514.85 (100) [M⁺].

Hexakis[4-(9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-

tetradecyl)phenyl]benzene (15h)

As described for 15a using tolane 14h (0.3 g, 0.29 mmol), Co₂(CO)₈

(5.9 mg, 17.0 mmol), and dioxane (25 mL) gave 15h (275 mg, 92%);

R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 6.67 (d, J = 8.2 Hz, 12 H, Ar), 6.61

(d, J = 8.2 Hz, 12 H, Ar), 2.34 (t, J = 7.3 Hz, 12 H, CH₂), 1.95–2.10

(m, 12 H, CH₂), 1.50–1.61 (m, 24 H, CH₂), 1.21–1.41 (m, 48 H,

CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 2179.48 (100) [M⁺].

Hexakis[4-(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,14-

henicosafluorotetradecyl)phenyl]benzene (15d)

As described for 15a using tolane 14d (0.2 g, 0.15 mmol), Co₂(CO)₈

(4.1 mg, 12.0 mmol), dioxane (10 mL), and HFB (10mL) gave 15d

(164 mg, 85%); R_f= 0.85 (BTF).

¹H NMR (500 MHz, CDCl₃): d = 6.66 (br d, J = 8.2 Hz, 12 H, Ar),

6.60 (br d, J = 8.2 Hz, 12 H, Ar), 2.33 (t, J = 6.8 Hz, 12 H, CH₂),

1.97–2.08 (m, 12 H, CH₂), 1.54–1.60 (m, 12 H, CH₂), 1.36–1.42 (m,

12 H, CH₂).

¹³C NMR (125.77 MHz, CDCl₃): d = 140.33, 138.89, 138.44,

131.48, 126.43, 108.68–120.94 (m, Rf₁₀), 35.32, 31.12, 30.83 (t,

J = 22.0 Hz), 20.17.

¹³C NMR (90.55 MHz, CDCl₃): d = 140.27, 138.86, 138.33, 131.42,

126.44, 105.03–119.65 (m, Rf₆), 35.31, 31.15, 30.77 (t, J = 22.5

Hz), 28.70, 28.95, 29.15, 29.27, 20.10 (t, J = 3.3 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 3114.82 (100) [M⁺].

Hexakis[4-(9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-

heptadecafluorohexadecyl)phenyl]benzene (15i)

As described for 15a using tolane 14i (659 mg, 0.53 mmol),

Co₂(CO)₈(10.8 mg, 31.6 mmol), and dioxane (50 mL) gave 15i (329

mg, 51%); R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (500 MHz, CDCl₃): d = 6.66 (d, J = 8.2 Hz, 12 H, Ar), 6.60

(d, J = 8.2 Hz, 12 H, Ar), 2.33 (t, J = 7.3 Hz, 12 H, CH₂), 1.97–2.08

(m, 12 H, CH₂), 1.54–1.60 (m, 12 H, CH₂), 1.35–1.42 (m, 12 H,

CH₂), 1.30–1.35 (m, 12 H, CH₂), 1.09–1.28 (m, 36 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3978.41 (100) [M⁺].

Hexakis[4-(6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoro-

undecyl)phenyl]benzene (15e)

As described for 15a using tolane 14e (0.3 g, 0.31 mmol), Co₂(CO)₈

(8.6 mg, 25.0 mmol), and dioxane (20 mL) gave 15e (238 mg, 79%);

R_f= 0.95 (pentane–Et₂O, 9:1).

¹H NMR (360 MHz, CDCl₃): d = 6.68 (d, J = 8.2 Hz, 12 H, Ar), 6.61

(d, J = 8.2 Hz, 12 H, Ar), 2.36 (t, J = 7.3 Hz, 12 H, CH₂), 1.90–2.04

(m, 12 H, CH₂), 1.47–1.55 (m, 12 H, CH₂), 1.41–1.45 (m, 12 H,

CH₂), 1.17–1.21 (m, 12 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.20, 138.43, 138.39, 131.45,

126.42, 110.39–118.72 (m, Rf₆), 34.94, 30.79, 30.79 (t, J = 22.5

Hz), 28.07, 19.87 (t, J = 3.3 Hz).

¹³C NMR (125.77 MHz, CDCl₃): d = 140.33, 138.89, 138.44,

131.48, 126.43, 108.68–120.94 (m, Rf₈), 35.32, 31.12, 31.01 (t,

J = 22.5 Hz), 28.72, 28.96, 29.17, 29.24, 20.17 (t, J = 3.3 Hz).

MS (MALDI-ICR, DCTB): m/z (%) = 3714.72 (100) [M⁺].

Hexakis[4-(6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-hepta-

decafluorotridecyl)phenyl]benzene (15j)

As described for 15a using tolane 14j (231 mg, 0.20 mmol),

Co₂(CO)₈(10.7 mg, 31.2 mmol), and dioxane (75 mL) gave 15j (191

g, 83%); R_f= 0.95 (pentane–Et₂O, 5:1).

MS (MALDI-ICR, DCTB): m/z (%) = 2862.51 (100) [M⁺].

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1137

¹H NMR (360 MHz, CDCl₃): d = 6.69 (d, J = 8.2 Hz, 12 H, Ar), 6.61

(d, J = 8.2 Hz, 12 H, Ar), 2.36 (t, J = 7.3 Hz, 12 H, CH₂), 1.88–2.04

(m, 12 H, CH₂), 1.47–1.55 (m, 12 H, CH₂), 1.36–1.45 (m, 12 H,

CH₂), 1.14–1.21 (m, 12 H, CH₂).

¹³C NMR (125.77 MHz, CDCl₃): d = 140.29, 138.55, 138.45,

131.54, 126.43, 108.67–120.49 (m, Rf₈), 34.97, 30.92 (t, J = 22.1

Hz), 30.78, 28.13, 19.96.

(16 mL), and added by syringe to the Schlenk tube. The mixture was

then cooled to 0 °C in an ice/NaCl bath. Allylmagnesium bromide

(1 M in Et₂O; 14.6 mL, 14.6 mmol) was added slowly by syringe (2

h), yielding a yellow soln. The ice bath was removed after the addi-

tion was completed and the mixture (green) was stirred at r.t. for 16

h and quenched with MeOH (8 mL). All volatiles were removed un-

der reduced pressure yielding a brown suspension that was filtered

through a silica gel plug (pentane) under reduced pressure to give

21a (3.86 g, 71%); R_f= 0.95 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 5.72 (ddt, J = 17.0, 10.0, 6.8 Hz,

1 H, CH), 5.19 (d, J = 17.0 Hz, 1 H, CH₂), 5.14 (d, J = 10.0 Hz, 1

H, CH₂), 2.54 (sept, J = 6.8 Hz, 1 H, CH), 2.33 (t, J = 6.8 Hz, 2 H,

CH₂), 2.12–2.27 (m, 4 H, CH₂).

MS (MALDI-ICR, DCTB): m/z (%) = 3462.41 (100) [M⁺], 2973.41

(10).

1,1,1,2,2,3,3,4,4,5,5,6,6,12,12,13,13,14,14,15,15,16,16,17,17,17-

Hexacosafluoroheptadecan-9-ol (18)

To a stirred soln of the Grignard reagent prepared from

1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane (50 g, 102

mmol) and Mg (3.7 g, 152 mmol) in anhyd Et₂O (150 mL) under ar-

gon at 25 °C was added dropwise a soln of ethyl formate (3.1 g, 42

mmol) in anhyd Et₂O (6 mL). The mixture was stirred at r.t. over-

night. It was then quenched by a slow addition of H₂O (100 mL), ex-

tracted with Et₂O (3 × 50 mL), washed with sat. NaCl (50 mL),

dried (Na₂SO₄), and evaporated. The product was purified by filtra-

tion (silica gel, pentane). Elution with Et₂O and evaporation of the

solvent afforded the title compound (30.6 g, 81%); R_f= 0.65 (pen-

tane).

¹H NMR (360 MHz, CDCl₃): d = 3.75 (m, 1 H, CH), 2.04–2.45 (m,

4 H, CH₂), 1.68–1.90 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 108–122 (m, Rf₆), 69.62, 28.02,

27.22 (t, J = 22 Hz).

¹³C NMR (90.55 MHz, CDCl₃): d = 133.5, 119.40, 108.86–118.89

(m, Rf₄), 38.78, 33.53 (t, J = 21.1 Hz), 24.91.

MS (EI, 70 eV): m/z (%) = 520.5 (7) [M⁺], 287.3 (100).

7,7,8,8,9,9,10,10,11,11,12,12,12-Tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodec-1-ene (21b)

As described for 21a using allyl 19b (9.5 g, 11.4 mmol),

Pd(dppf)Cl₂·CH₂Cl₂(372 mg, 0.5 mmol), allylmagnesium bromide

(1 M in Et₂O; 17.1 mL, 17.1 mmol), and THF (30 mL) gave 21b

(7.1 g, 84%); R_f= 0.93 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 5.73 (ddt, J = 16.8, 10.0, 6.8 Hz,

1 H, CH), 5.11 (dd, J = 10.0, 1.4 Hz, 1 H, CH), 5.09 (dd, J = 16.8,

1.4 Hz, 1 H, CH), 2.10 (m, 6 H, CH₂), 1.61 (m, 5 H, CH₂, CH).

¹³C NMR (90.55 MHz, CDCl₃): d = 134.94, 108–122 (m, Rf₆),

117.79, 37.23, 36.29, 28.27 (t, J = 22 Hz), 23.33.

MS (EI, 70 eV): m/z (%) = 707.7 (1), 377.3 (100), 357.3 (82).

MS (EI, 70 eV): m/z (%) = 748.7 (2) [M⁺], 720.7 (6), 706.6 (12),

401.4 (72), 387.3 (100).

1,1,1,2,2,3,3,4,4,8,8,9,9,10,10,11,11,11-Octadecafluoro-6-iodo-

undecane (19a)

As described for 8a using 4,4,5,5,6,6,7,7,7-nonafluorohept-1-ene

(20, 5.5 g, 21.14 mmol), perfluorobutyl iodide (7.67 g, 22.18

mmol), AIBN (170 mg, 1.05 mmol), and 30% aq Na₂S₂O₅soln (3.5

mL) gave 19a (6.36 mg, 49%); R_f= 0.95 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 4.52 (quint, J = 6.8 Hz, 1 H, CH),

2.89–3.02 (m, 4 H, CH₂).

1-Bromo-4-[6,6,7,7,8,8,9,9,9-nonafluoro-4-(2,2,3,3,4,4,5,5,5-

nonafluoropentyl)non-1-enyl]benzene (22a); Typical Procedure

As described for 4a using 21a (0.52 g, 1.0 mmol), 4-bromobenzene-

diazonium tetrafluoroborate (0.3 g, 1.1 mmol), Pd₂(dba)₃(15.5 mg,

15 mmol), NaOAc (287 mg, 3.5 mmol), and MeCN (5 mL) gave 22a

(200 mg, 31%); R_f= 0.71 (pentane).

¹³C NMR (90.55 MHz, CDCl₃): d = 106.21–119.36 (m, Rf₄), 41.97

(t, J = 21.1 Hz), 0.00.

MS (EI, 70 eV): m/z (%) = 606.4 (5) [M⁺], 479.4 (30), 459.4 (41),

¹H NMR (360 MHz, CDCl₃): d = 7.44 (d, J = 8.2 Hz, 2 H, Ar), 7.22

(d, J = 8.2 Hz, 2 H, Ar), 6.42 (d, J = 15.8 Hz, 1 H, CH), 6.06 (dt,

J = 15.8, 7.3 Hz, 1 H, CH), 2.63 (sept, J = 6.4 Hz, 1 H, CH), 2.48 (t,

J = 7.3 Hz, 2 H, CH₂), 2.18–2.30 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 135.63, 133.31, 131.75, 127.70,

125.65, 121.45, 109.82–120.05 (m, Rf₄), 37.95, 33.69 (t, J = 21.1

Hz), 25.46.

245.2 (69), 195.1 (95), 69.0 (100).

1,1,1,2,2,3,3,4,4,5,5,6,6,12,12,13,13,14,14,15,15,16,16,17,17,17-

Hexacosafluoro-9-iodoheptadecane (19b)

To a flask containing a stirring mixture of DDQ (3.76 g, 16.6

mmol), Ph₃P (4.35 g, 16.6 mmol), and TBAI (6.1 g, 16.6 mmol) in

CH₂Cl₂(140 mL), 18 (10.0 g, 13.8 mmol) was added at r.t. and the

mixture was stirred for 2 h. The yellow color of the mixture changed

to red. The concentrated residue was filtered (silica gel, pentane)

and evaporated to afford 19b (10.6 g, 90%); R_f= 0.92 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 4.04 (m, 1 H, CH), 2.06–2.6 (m,

4 H, CH₂), 2.06–2.3 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 108–122 (m, Rf₆), 32.61, 31.58,

31.58 (t, J = 22 Hz).

MS (EI, 70 eV): m/z (%) = 674.6 (2) [M⁺], 197.1 (30), 116.0 (100).

1-Bromo-4-[7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodec-1-enyl]ben-

zene (22b)

As described for 22a using 21b (5.0 g, 6.7 mmol), 4-bromoben-

zenediazonium tetrafluoroborate (2.0 g, 7.4 mmol), Pd₂(dba)₃(104

mg, 0.1 mmol), NaOAc (1.92 g, 23.5 mmol), and MeCN (40 mL)

gave 22b (3.8 g, 63%); R_f= 0.78 (pentane).

¹H NMR (500 MHz, CDCl₃): d = 7.43 (d, J = 8.5 Hz, 2 H, Ar), 7.20

(d, J = 8.5 Hz, 2 H, Ar), 6.38 (d, J = 15.8 Hz, 1 H, CH), 6.11 (dt,

J = 15.8, 7.4 Hz, 1 H, CH), 2.25 (m, 2 H, CH₂), 2.10 (m, 4 H, CH₂),

1.66 (m, 5 H, CH₂, CH).

MS (EI, 70 eV): m/z (%) = 707.7 (46), 687.7 (20), 437.4 (24), 327.3

(100).

6,6,7,7,8,8,9,9,9-Nonafluoro-4-(2,2,3,3,4,4,5,5,5-nonafluoropen-

tyl)non-1-ene (21a); Typical Procedure

An oven-dried Schlenk tube was charged with Pd(dppf)Cl₂·CH₂Cl₂

(250 mg, 0.30 mmol) under an inert atmosphere. Compound 19a

(6.3 g, 10.4 mmol) was separately deoxygenated, diluted with THF

¹³C NMR (125 MHz, CDCl₃): d = 136.00, 131.76, 131.69, 127.58,

127.30, 121.26, 108–122 (m, Rf₆), 36.65, 36.37, 28.16 (t, J = 20.8

Hz), 23.35.

MS (EI, 70 eV): m/z (%) = 903.7 (74) [M⁺], 805.0 (30), 475.5 (100).

1138

O. F. Aebischer et al.

PAPER

1-Bromo-4-[6,6,7,7,8,8,9,9,9-nonafluoro-4-(2,2,3,3,4,4,5,5,6,6,6-

nonafluoropentyl)nonyl]benzene (23a)

As described for 5a using alkene 22a (1.75 g, 2.6 mmol), Rh/C (100

mg), pentane (20 mL), and CH₂Cl₂(10 mL) gave 23a (1.75 g, 98%);

R_f= 0.81 (pentane).

¹H NMR (500 MHz, CDCl₃): d = 7.41 (d, J = 8.2 Hz, 2 H, Ar), 7.04

(d, J = 8.2 Hz, 2 H, Ar), 2.59 (t, J = 7.0 Hz, 2 H, CH₂), 2.44 (sept,

J = 5.9 Hz, 1 H, CH), 2.09–2.24 (m, 4 H, CH₂), 1.58–1.66 (m, 4 H,

CH₂).

9-(3-Bromopropyl)-

1,1,1,2,2,3,3,4,4,5,5,6,6,12,12,13,13,14,14,15,15,16,16,17,17,17-

hexacosafluoroheptadecane (25)

As described for 19b using alcohol 24 (3.43 g, 4.48 mmol), DDQ

(1.22 g, 5.38 mmol), Ph₃P (1.41 g, 5.38 mmol), TBAB (1.74 g, 5.38

mmol), and CH₂Cl₂(50 mL) gave 25 (3.13 g, 84%); R_f= 0.87 (pen-

tane).

¹H NMR (360 MHz, CDCl₃): d = 3.42 (m, 2 H, CH₂), 2.08 (m, 4 H,

CH₂), 1.87 (m, 2 H, CH₂), 1.4–1.8 (m, 7 H, CH₂, CH).

¹³C NMR (125 MHz, CDCl₃): d = 140.48, 131.50, 130.05, 119.78,

108.52–121.21 (m, Rf₄), 35.01, 34.24, 34.13 (t, J = 21.1 Hz), 27.76,

25.34.

¹³C NMR (90.55 MHz, CDCl₃): d = 108–122 (m, Rf₆), 35.88, 33.57,

31.16, 29.38, 28.12 (t, J = 22 Hz), 23.30.

MS (EI, 70 eV): m/z (%) = 749.9 (2), 481.4 (12), 401.5 (100).

MS (EI, 70 eV): m/z (%) = 676.6 (6) [M⁺], 171.0 (100).

9,9,10,10,11,11,12,12,13,13,14,14,14-Tridecafluoro-6-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradec-1-yne (26)

As described for 11a using bromide 25 (3.0 g, 3.62 mmol), lithium

acetylide–ethylenediamine complex (1.11 g, 10.85 mmol), DMSO

(10 mL), and pentane (4 mL) gave 26 (1.67 g, 60%); R_f= 0.84 (pen-

tane).

¹H NMR (360 MHz, CDCl₃): d = 2.22 (dt, J = 6.8, 2.3 Hz, 2 H,

CH₂), 2.0–2.14 (m, 4 H, CH₂), 1.96 (t, J = 2.3 Hz, 1 H, CH), 1.77

(dt, J = 6.3, 2.3 Hz, 2 H, CH₂), 1.4–1.67 (m, 7 H, CH₂, CH).

1-Bromo-4-[7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodecyl]benzene

(23b)

As described for 5a using alkene 22b (2.26 g, 2.5 mmol), Rh/C (250

mg), pentane (25 mL), and CH₂Cl₂(25 mL) gave 23b (1.75 g, 77%);

R_f= 0.87 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.41 (d, J = 8.5 Hz, 2 H, Ar), 7.05

(d, J = 8.5 Hz, 2 H, Ar), 2.58 (t, J = 7.5 Hz, 2 H, CH₂), 2.01 (m, 4

H, CH₂), 1.60 (m, 7 H, CH₂, CH), 1.32 (m, 2 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 140.95, 131.62, 130.21, 119.84,

108–122, 36.29, 35.45, 32.08, 28.12 (t, J = 21.1 Hz), 27.90, 23.24.

¹³C NMR (90.55 MHz, CDCl₃): d = 108–122 (m, Rf₆), 83.89, 68.97,

36.02, 31.51, 28.15 (t, J = 22 Hz), 24.99, 23.31, 18.61.

MS (EI, 70 eV): m/z (%) = 441.5 (8), 427.5 (100).

MS (EI, 70 eV): m/z (%) = 906.0 (100) [M⁺], 826 (4), 373.3 (32).

1-Bromo-4-[9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-

6-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradec-1-

ynyl]benzene (27)

As described for 12a using alkyne 26 (1.34 g, 1.74 mmol),

PdCl₂(PPh₃)₂(66 mg, 0.09 mmol), CuI (31 mg, 0.16 mmol), 1-bro-

mo-4-iodobenzene (442 mg, 1.56 mmol), Et₃N (12.0 mL, 86.4

mmol), and BTF (12 mL) gave 27 (463 mg, 30%); R_f= 0.56 (pen-

tane).

¹H NMR (360 MHz, CDCl₃): d = 7.41 (d, J = 8.6 Hz, 2 H, Ar), 7.25

(d, J = 8.6 Hz, 2 H, Ar), 2.42 (t, J = 6.8 Hz, 2 H, CH₂), 2.08 (m, 4

H, CH₂), 1.48–1.64 (m, 9 H, CH₂, CH).

¹³C NMR (90.55 MHz, CDCl₃): d = 133.08, 131.61, 122.75, 121.98,

108–122 (m, Rf₆), 90.71, 80.41, 36.09, 31.79, 28.18 (t, J = 20.8 Hz),

25.27, 23.33, 19.66.

1-Bromo-4-[9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-

6-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradecyl]ben-

zene (23c)

As described for 5a using alkyne 27 (463 mg, 0.5 mmol), Rh/C (42

mg), pentane (5 mL), and CH₂Cl₂(5 mL) gave 23c (400 mg, 86%);

R_f= 0.79 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.39 (d, J = 8.6 Hz, 2 H, Ar), 7.04

(d, J = 8.6 Hz, 2 H, Ar), 2.56 (t, J = 7.3 Hz, 2 H, CH₂), 2.04 (m, 4

H, CH₂), 1.53–1.66 (m, 7 H, CH₂, CH), 1.30 (m, 6 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 141.61, 131.84, 130.29, 118.96,

108–122, 36.44, 35.41, 32.76, 31.34, 29.47, 28.18 (t, J = 21.1 Hz),

26.27, 23.30.

MS (EI, 70 eV): m/z (%) = 854.7 (12), 687.4 (10), 327.4 (100).

MS (EI, 70 eV): m/z (%) = 760.0 (4), 581.6 (100), 516.6 (20).

7,7,8,8,9,9,10,10,11,11,12,12,12-Tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodecan-1-ol (24)

To a 2-necked flask under argon with a stirred suspension of AlCl₃

(4.17 g, 31.2 mmol) in Et₂O (12 mL) was added LiAlH₄(0.4 g, 10.4

mmol) at 0 °C. After 15 min, PhB(OH)₂(63 mg, 0.52 mmol), and

21b (7.8 g, 10.4 mmol) were added. The resulting mixture was al-

lowed to warm to r.t. and stirred at this temperature and then the in-

ert gas protection was removed. Stirring was continued overnight

under air. The mixture was quenched with 1 M HCl (10 mL), ex-

tracted with Et₂O (3 × 25 mL), dried (Na₂SO₄), and concentrated.

The product was purified by filtration (silica gel, pentane then

Et₂O). Evaporation afforded 24 (3.73 g, 47%); R_f= 0.72 (pentane).

1-[6,6,7,7,8,8,9,9,9-Nonafluoro-4-(2,2,3,3,4,4,5,5,5-nonafluoro-

pentyl) nonyl]-4-({4-[6,6,7,7,8,8,9,9,9-nonafluoro-4-

(2,2,3,3,4,4,5,5,5-nonafluoropentyl)nonyl]phenyl}ethynyl)ben-

zene (28a)

As described for 14a using bromoaryl 23a (1.0 g, 1.48 mmol),

Pd(PPh₃)₄(103 mg, 89 mmol), CuI (28 mg, 0.15 mmol), DBU (1.32

mL, 8.9 mmol), THF (10 mL), H₂O (10 mL, 0.59 mmol), and tri-

methylsilylacetylene (0.11 mL, 0.74 mmol) gave 28a (530 mg,

59%); R_f= 0.15 (pentane).

¹H NMR (360 MHz, CDCl₃): d = 7.45 (d, J = 8.2 Hz, 4 H, Ar), 7.15

(d, J = 8.2 Hz, 4 H, Ar), 2.65 (t, J = 7.1 Hz, 4 H, CH₂), 2.45 (sept,

J = 6.0 Hz, 2 H, CH), 2.05–2.26 (m, 8 H, CH₂), 1.61–1.69 (m, 8 H,

CH₂).

¹H NMR (360 MHz, CDCl₃): d = 3.67 (t, J = 6.1 Hz, 2 H, CH₂), 2.06

(m, 6 H, CH₂), 1.3–1.7 (m, 7 H, CH₂, CH).

¹³C NMR (90.55 MHz, CDCl₃): d = 108–122 (m, Rf₆), 69.89, 36.30,

29.39, 28.91, 28.15 (t, J = 22 Hz), 23.33.

¹³C NMR (90.55 MHz, CDCl₃): d = 141.83, 131.66, 128.34, 121.06,

108.10–120.69 (m, Rf₆), 88.95, 35.52, 34.31, 34.16 (t, J = 21.1 Hz),

27.66, 25.37.

MS (EI, 70 eV): m/z (%) = 720.9 (10), 401.4 (100), 357.3 (82).

MS (MALDI-ICR, DCTB): m/z (%) = 1469.33 (99) [M + DCTB]⁺,

1218.18 (100) [M⁺].

PAPER

Perfluoroalkyl-Substituted Hexa-peri-hexobenzocoronene

1139

1-[7,7,8,8,9,9,10,10,11,11,12,12,12-Tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodecyl]-4-({4-

[7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-4-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)dodecyl]phe-

nyl}ethynyl)benzene (28b)

As described for 14a using bromoaryl 23b (0.5 g, 0.52 mmol),

Pd(PPh₃)₄(36.4 mg, 30 mmol), CuI 9.9 mg, 50 mmol), DBU (0.48

mL, 3.12 mmol), THF (5 mL), H₂O (3.7 mL, 0.21 mmol), and tri-

methylsilylacetylene (37.7 mL, 0.26 mmol) gave 28b (410 mg,

94%); R_f= 0.12 (pentane).

MS (MALDI-TOF, DCTB): m/z (%) = 5023.98 (5) [M⁺], 975.25

(100).

Hexakis{4-[9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-

6-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradecyl]phe-

nyl}benzene (29c)

As described for 15a using tolane 28c (190 mg, 0.11 mmol),

Co₂(CO)₈(10 mg, 30.0 mmol), and dioxane (25 mL) gave 29c (140

mg, 74%).

¹H NMR (360 MHz, CDCl₃): d = 6.66 (d, J = 8.2 Hz, 12 H, Ar), 6.59

(d, J = 8.2 Hz, 12 H, Ar), 2.34 (t, J = 7.3 Hz, 12 H, CH₂), 2.02 (m,

24 H, CH₂), 1.56 (m, 24 H, CH₂), 1.42 (m, 18 H, CH₂, CH), 1.10–

1.32 (m, 36 H, CH₂).

¹H NMR (360 MHz, CDCl₃): d = 7.44 (d, J = 8.5 Hz, 4 H, Ar), 7.14

(d, J = 8.5 Hz, 4 H, Ar), 2.63 (t, J = 7.5 Hz, 4 H, CH₂), 2.01 (m, 8

H, CH₂), 1.60 (m, 14 H, CH₂, CH), 1.32 (m, 4 H, CH₂).

¹³C NMR (90.55 MHz, CDCl₃): d = 142.27, 131.76, 128.49,

108.13–122.98 (m, Rf₆), 121.15, 89.03, 36.29, 35.94, 32.06, 28.13

(t, J = 22.1 Hz), 27.76, 23.27.

¹³C NMR (90.55 MHz, CDCl₃): d = 140.35, 138.73, 138.53, 131.58,

126.52, 108.34–22.67 (m, Rf₆), 36.43, 35.33, 32.84, 31.16, 28.99,

28.08 (t, J = 21.1 Hz), 26.16, 23.22.

MS (MALDI-TOF, DCTB): m/z (%) = 1673.81 (100) [M⁺].

MS (MALDI-TOF, DCTB): m/z (%) = 5192.29 (100) [M⁺], 3492.82

(8), 1731.95 (17).

1-[9,9,10,10,11,11,12,12,13,13,14,14,14-Tridecafluoro-6-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradecyl]-4-({4-

[9,9,10,10,11,11,12,12,13,13,14,14,14-tridecafluoro-6-

(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tetradecyl]phe-

nyl}ethynyl)benzene (28c)

As described for 14a using bromoaryl 23c (289 mg, 0.31 mmol),

Pd(PPh₃)₄(22 mg, 20 mmol), CuI 6.0 mg, 30 mmol), DBU (0.28 mL,

1.86 mmol), THF (5 mL), H₂O (3.0 mL, 0.12 mmol), and trimethyl-

silylacetylene (21.7 mL, 0.15 mmol) gave 28c (203 mg, 76%);

R_f= 0.12 (pentane).

¹H NMR (500 MHz, CDCl₃): d = 7.43 (d, J = 8.2 Hz, 4 H, Ar), 7.14

(d, J = 8.2 Hz, 4 H, Ar), 2.62 (t, J = 7.6 Hz, 4 H, CH₂), 2.04 (m, 8

H, CH₂), 1.58 (m, 14 H, CH₂, CH), 1.31 (m, 12 H, CH₂).

¹³C NMR (125 MHz, CDCl₃): d = 142.65, 131.65, 128.57, 120.90,

108.05–120.83 (m, Rf₆), 89.06, 36.44, 35.93, 32.78, 31.23, 29.47,

28.22 (t, J = 21.1 Hz), 26.28, 23.35.

Acknowledgment

We thank Freddy Nydegger for the MALDI-ICR measurements,

Felix Fehr for the professional NMR support and Olivier Scheideg-

ger for recording the MALDI-TOF spectra.

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Article Doi

Synthesis of hexa- peri -hexobenzocoronenes carrying linear or branched perfluoroalkylated side chains

DOI: 10.1055/s-0029-1218667

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Full text of DOI:10.1055/s-0029-1218667

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