Combinatorial organic materials research (COMR): design, synthesis and screening of a 225-membered materials library of liquid crystalline fluorinated p-quaterphenyls

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Combinatorial organic materials research (COMR):

design, synthesis and screening of a 225-membered materials

library of liquid crystalline ﬂuorinated p-quaterphenyls†

Oliver Deeg and Peter Bäuerle*

Department of Organic Chemistry II (Organic Materials and Combinatorial Chemistry),

University of Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany.

E-mail: peter.baeuerle@chemie.uni-ulm.de

Received 5th December 2002, Accepted 10th March 2003

First published as an Advance Article on the web 9th April 2003

The rapid solution phase synthesis of novel liquid crystalline materials is demonstrated by utilising combinatorial

and parallel methods for the preparation of a library of 225 diﬀerently ﬂuorinated 4,4ٞ-dipropyl-p-quaterphenyls.

Chemical diversity was introduced into the growing oligomers via a convergent synthetic sequence of iodinations

and Suzuki cross-couplings by using various ﬂuorinated phenyl building blocks. A highly eﬃcient rapid parallel

puriﬁcation method was developed that provided HPLC-pure library members in amounts suﬃcient for the

characterization of bulk properties.

2. development of an eﬀective synthetic route; 3. library gener-

Introduction

ation; 4. puriﬁcation. The ﬁnal steps of the developmental loop,

screening and data analysis, will be described in a forthcoming

paper.⁷

During the last decade, the concept of combinatorial chemistry

emerged as a key technology in pharmaceutical research:

numerous examples of lead structure identiﬁcation and opti-

misation have been published.¹A similar development was

recently seen in the area of inorganic solid state materials,²

catalysts³and polymers,⁴where combinatorial techniques have

been successfully used to discover new materials. Due to rapidly

advancing technologies in the area of organic materials, there

is a strong need to accelerate the development process. The

bottlenecks of conventional material research, namely the time

consuming “one-at-a-time” synthesis, puriﬁcation and sub-

sequent evaluation of materials, could be overcome by imple-

menting combinatorial methodologies that were developed

for high-speed synthesis and high-throughput screening of

pharmaceuticals. The ﬁrst examples of combinatorial organic

materials research (COMR) have been published only recently.⁵

Single molecule libraries of ﬂuorescence dyes as potential

candidates for laser dyes or bio-labelling,^5aand conjugated

oligomers for organic electronic devices^5b,cwere generated by

combinatorial strategies and their molecular properties investi-

gated by automated screening methods.

In the case of solid state materials, where for applications the

bulk-properties are crucial, the development of new materials is

aggravated by the fact that the appropriate structure–property

relationships are not readily predictable by current theories,

because these bulk properties strongly depend on numerous

interdependent parameters as well as on packing-eﬀects and

subtle intermolecular interactions in the solid state. In this con-

text, the preparation of a library of liquid crystals (LCs)

for display application seems to be particularly challenging,

because the aforementioned lack of predictability of solid state

materials renders LCs a prime target for a combinatorial

optimisation strategy.

Results and discussion

Library design

Despite the fact that numerous liquid crystalline compounds

are already known today, the steadily progressing technological

advancement demands the provision of continuously new and

better materials. For example, whereas most LC displays (LCD)

so far were operated at room temperature, in automotive appli-

cations operating temperature ranges from Ϫ40 to 110 ЊC are

desirable. Whereas biphenyl and terphenyl based LCs have been

extensively studied in the past⁸and are part of commercial LC

mixtures, quaterphenyl LCs are very rare and only published in

recent patents.⁹This is mainly due to the very high melting

point of the core structure and unfavourable phase behaviour

of known quaterphenyls. The increased length-to-breadth ratio

of the conjugated core of a quaterphenyl, however, should

result in increased clearing temperatures (T _clear) which would

render them suitable candidates for LC mixtures with an

extended temperature range. Therefore, we chose as the lead

structure a p-quaterphenyl which is substituted with two ter-

minal alkyl chains and lateral ﬂuoro substituents. The rigid core

should induce anisotropy and is a prerequisite for liquid crystal-

linity. The terminal alkyl side chains serve as ﬂexible elements

that should lower the melting point to an extent that liquid

crystalline mesophases occur. Lateral ﬂuoro substituents are

known to have a distinct inﬂuence on the phase behaviour by

altering the association of the molecules in the liquid crystalline

phase.¹⁰Both the terminal alkyl and the lateral ﬂuoro substi-

tuents serve as diversity elements in the combinatorial devel-

opment process (Fig. 1). In addition to the expected improved

values for T _clear, the quaterphenyl target molecules are expected

to posses an intrinsic high chemical, thermal and photo-

chemical stability that is also important for application in

LCDs.

In a very recent publication, we already described the fabri-

cation of a ﬁrst small 16-membered library of liquid crystals by

combinatorial approaches.⁶In this publication, we describe the

ﬁrst parts of a full combinatorial development process leading

to a much bigger library of a novel class of liquid crystalline

(LC) materials which includes: 1. design of the lead structure;

Synthetic strategy

† Electronic supplementary information (ESI) available: tables of

product yield and purity, and NMR spectra and HPLC traces.. See

http://ww w .rsc.org/suppdata/ob/b2/b212107g/

The oligomer elongation sequence that is based on an iterative

synthesis that we developed recently, is outlined in Scheme 1.⁶

T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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6. After conversion of the TMS-group into the iodo moiety by

treatment with iodine chloride, the resulting iodoterphenyl 7 is

cross-coupled with boronic ester 5 to yield quaterphenyl 8.

Building block selection and synthesis

In a recent study, we evaluated the inﬂuence of the terminal

alkyl chains on the mesomorphic behaviour of quaterphenyls

by synthesis and screening of a ﬁrst 16-membered library of

novel 4,4ٞ-dialkyl-3Ј,2Љ,3Љ-triﬂuoro-p-quaterphenyls. The data

analysis clearly revealed that short linear alkyl terminal chains

are favourable for large mesophase ranges.^6bTherefore, in the

synthesis of this second, more extended material library, the

terminal alkyl chains were kept constant and the terminal build-

ing blocks 5{T } were designed to bear exclusively short propyl

chains (Scheme 1). Instead of a variation of the alkyl chains, in

this library, the number and positions of the ﬂuoro atoms at the

quaterphenyl core were varied since the properties of LCs are

strongly inﬂuenced by ﬂuoro substituents.¹⁰The selection of

building blocks was also based on the aim of maximizing the

overall eﬃciency of the combinatorial synthesis: Terminal

building blocks 5{T } are used twice in the synthesis to intro-

duce diversity and with utilizing a larger number of these build-

ing blocks, the diversity of the ﬁnal library can be enhanced

surpassingly. After careful selection of a set of suitable diversity

reagents, that bear up to two ﬂuoro substituents at various posi-

tions of the phenyl core (Scheme 1), the next step towards the

Fig. 1 p-Quaterphenyl as the lead structure for novel liquid crystalline

materials.

A convergent bi-directional stepwise addition approach seems

to be well suited for the construction of a library of p-quater-

phenyls, since the bi-directional growth-strategy minimises the

number of reactions and intermediates, compared to a stand-

ard linear oligomer synthesis. Furthermore, iterative Suzuki-

couplings can be easily translated into a combinatorial protocol

by using diﬀerent building blocks as diversity reagents.⁵

In a ﬁrst Suzuki cross-coupling, a halogen component 1

and a trimethylsilyl (TMS) protected phenylboronic ester 2

react to give biphenyl 3, which is subsequently transformed into

iodo biphenyl 4 by treatment with n-butyllithium and 1,2-

diiodoethane. Biphenyl 4 undergoes palladium-catalysed cross-

coupling with boronic ester 5 to yield TMS-protected terphenyl

Scheme 1 Combinatorial synthesis of quaterphenyls 8{T,H,B,T } and utilised building blocks 1{H}, 2{B} and 5{T }.

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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library construction was the synthesis of the building blocks,

which are the halogen components 1{H}, the TMS-protected

boronic esters 2{B} and the terminal boronic esters 5{T }. It

was envisaged to implement the boronic functionalities of

building blocks 2{B} and 5{T } as boronic esters and not as

boronic acids. Boronic acids show a tendency to form adducts

with coordinating solvents, such as THF, and are usually

obtained as waxy solids that are mixtures of free acid and the

anhydride of unknown stoichiometric composition, which ren-

ders it impossible to dose them in exact amounts.¹¹In contrast

to that, boronic esters are molecularly well deﬁned compounds,

that can be exactly dosed, which is essential for our combin-

atorial synthetic strategy. Boronic esters derived from neo-

pentyl glycol have the particular advantage of being crystalline

solids that can easily be puriﬁed in large amounts by recrystal-

lisation, whereas propanediol boronic esters and boronic acids

have to be puriﬁed by chromatography in small batches. More-

over, especially ﬂuorinated arylboronic esters are much more

stable towards deboronation than the free acids. This improved

robustness of building blocks 2{B} and 5{T } is a prerequisite

for the parallelisation of the individual reaction under standard

coupling conditions, which are not individually optimised for

each reaction. The synthesis of the terminal alkylbenzene

boronic esters 5 is shown in Scheme 2.

ent routes. In the ﬁrst synthetic approach, commercially avail-

able 1-bromo-3-ﬂuoro-4-iodobenzene 1{2} was metallated with

n-BuLi and then reacted with allyl bromide under copper

catalysis to form allylbenzene 10 which without isolation was

subsequently hydrogenated with PtO₂/H₂to yield alkylbenzene

11. The latter was converted into boronic ester 5{3} by the

standard reaction sequence mentioned above. In a second

approach, commercially available 5-bromo-1,3-diﬂuorobenzene

1{4} was converted into benzylic alcohol 12 by metallation with

n-BuLi and quenching with propanal. By treatment with phos-

phorus pentaoxide, benzylic alcohol 12 was dehydrated to the

corresponding styrene derivative, which was directly hydrogen-

ated to propylbenzene 13. The latter was converted to boronic

ester 5{4} by the standard reaction sequence. Analogously,

boronic ester 5{5} was prepared from 1,2-diﬂuorobenzene 14

via benzylic alcohol 15 and 1,2-diﬂuoro-3-propylbenzene 16.

Attempts to synthesize boronic ester 5{2} from commercially

available 3-bromo-2-ﬂuoroiodobenzene 1{3} failed, as both

aforementioned routes resulted in a mixture of isomeric prod-

ucts, probably due to lithium migration in lithiated 1{3}. There-

fore, another synthesis was developed, using again 1-bromo-3-

ﬂuoro-4-iodobenzene 1{2}, which was converted into silyl

benzene 17 by lithiation with n-BuLi and subsequent quenching

with trimethylsilyl chloride (TMSCl) in the presence of catalytic

amounts of N,N-dimethylaminopyridine (DMAP), which

activates the electrophile to be suﬃciently reactive at Ϫ78 ЊC.

Without the addition of DMAP, no reaction takes place at

Ϫ78 ЊC and upon warming on room temperature, decom-

position occurs, giving only a very poor yield of silyl benzene

17. Compound 17 was then converted to propylsilylbenzene 19

Commercially available p-bromopropylbenzene 9 was reacted

with butyllithium (n-BuLi) and triisopropyl borate [B(OiPr)₃],

to yield the corresponding boronic acid, which was not isolated,

but esteriﬁed in situ with neopentyl glycol to give boronic ester

5{1}. The ﬂuorinated propylbenzenes that were needed for the

other building blocks 5{2–5} were synthesized by three diﬀer-

Scheme 2 Synthesis of building blocks 5{T }: a) 1. n-BuLi, THF; 2. B(OiPr)₃; 3. neopentyl glycol. b) 1. n-BuLi, THF; 2. CuCN (5 mol%); 3. allyl

bromide. c) PtO₂, H₂, methanol. d) 1. n-BuLi, THF; 2. propanal. e) 1. P₂O₅, pentane; 2. PtO₂, H₂. f ) 1. n-BuLi, diethyl ether; 2. DMAP (5 mol%),

TMSCl. g) BBr₃, CH₂Cl₂. h) neopentyl glycol.

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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via alcohol 18, by the established synthetic protocol. Silyl-

benzene 19 was borodesilylated with BBr₃to yield dibromo-

phenylborane 20, which was directly converted to boronic ester

5{2} by reaction with neopentyl glycol.

The synthesis of the TMS-protected boronic ester building

blocks 2{1}, 2{2} and 2{5} was straightforwardly eﬀected from

silylbenzenes 21, 17 and 22 by the standard reaction sequence

lithiation, quenching with B(OiPr)₃and esteriﬁcation with neo-

pentyl glycol (Scheme 3).

synthesis by an additional step, which is the conversion of

bromo biphenyl 3 into the more reactive iodo biphenyl 4. The

Suzuki-coupling reaction of iodo compounds 4 and 7 with

boronic esters 5 had also to be further optimised, because the

crude Suzuki-coupling products were contaminated with

Pd-black, when [Pd(PPh₃)₄] was used as catalyst. This could be

completely avoided by the use of Pd(OAc)₂as catalyst pre-

cursor without the addition of additional ligands. However,

the optimisation studies also revealed some restrictions with

respect to the compatibility of the building blocks. It was found

that the Suzuki-coupling did not tolerate more than two ﬂuoro

atoms ortho to the Ar–Ar bond formed in the cross-coupling

reaction. For example, Suzuki-couplings of biphenyl 4{4,5}

and ortho-ﬂuoro boronic esters 5{2} and 5{5} proceeded in

only 16 and 0% yield, respectively, indicating that the formation

of o,o,oЈ-triﬂuoro-substituted biaryl moieties is not tolerated

under the chosen reaction conditions. This implies, that in the

synthesis of the library, combinations of ortho-ﬂuoro boronic

esters 5{2} and 5{5} with biphenyls 4{4,1}, 4{4,2} and 4{4,5},

which bear two ﬂuorine atoms ortho to the iodo moiety, have to

be omitted. Another issue that had to be addressed was the side

chain chlorination that was observed when carrying out the

iodo-desilylation of compounds 6 under standard conditions,

i.e. using iodine chloride and chlorinated solvents. Treatment of

TMS-protected terphenyl 6{1,1,1} with ICl in dichloromethane

gave iodo terphenyl 7{1,1,1}, which was contaminated with 5%

of a chlorinated iodo terphenyl, in which the chlorine is pre-

sumably located at the benzylic position of the propyl side

chain. If the reaction mixture was exposed to sunlight, the

amount of chlorinated by-product increased to 23%, indicating

that the chlorination takes place via a radical process. By

increasing solvent polarity and using acetonitrile instead of

dichloromethane, the chlorination reaction could be completely

suppressed even in the presence of sunlight. Moreover, the reac-

tion rate of the iododesilylation was found to be increased by

using acetonitrile as solvent.

Scheme 3 Synthesis of building blocks 2{1}, 2{2} and 2{5}: a) 1.

n-BuLi, THF; 2. B(OiPr)₃; 3. neopentyl glycol. b) 1. n-BuLi, THF;

2. TMSCl.

Optimisation

Library synthesis

When carrying out ﬁrst trial reactions, it became evident that

careful optimisation of each synthetic step was necessary to

translate the convergent bi-directional oligomer synthesis out-

lined in Scheme 1 into a combinatorial protocol. The pro-

pensity of o-ﬂuoroboronic acids to undergo deboronation

under Suzuki-coupling conditions could be overcome by using

the corresponding boronic esters instead and utilizing potas-

sium carbonate as a relatively weak base. When reacting halo-

genated benzene 1 with 1.0 eq. boronic ester 2, the Suzuki-

coupling exclusively occurred at the iodo-site of compound 1,

to yield bromo biphenyl 3. Because the following parallel syn-

thetic steps were to be carried out as a three step synthesis in

solution without puriﬁcation of the crude products, we put a lot

of eﬀort in optimising the reactions with respect to a complete

turnover of the starting materials as well as minimum con-

tamination of by-products. Unfortunately, the Suzuki reaction

of bromo biphenyl 3 with boronic ester 5 proceeded in only

about 80% conversion of starting material, and a mixture of

biphenyl 3 and terphenyl 6 was obtained. These circumstances

would spoil the synthesis, because in the following iododesilyl-

ation step, the leftover 3 would be converted into a diiodo

biphenyl that would in turn give rise to a diﬀerent than the

desired quaterphenyl in the following Suzuki-coupling. The

puriﬁcation of the resulting mixture of two diﬀerent quater-

phenyls 8 would be rather diﬃcult, if possible at all. Because

all eﬀorts to improve the yields of the reaction of biphenyl 3

with boronic ester 5 by variation of base [K₂CO₃, Cs₂CO₃,

Ba(OH)₂], catalyst [Pd(PPh₃)₄, Pd₂dba₃/PBu₃, PdCl₂(PPh₃)₂/

P(oTol)₃], amount of catalyst (1–5 mol%), amount of boronic

ester (1–2 equiv.), solvent (THF, dioxane, toluene) and condi-

tions (aqueous, non-aqueous) failed, we had to elongate the

With the optimised reaction conditions in hand, a library

composed of 225 p-quaterphenyls was prepared according to

Scheme 1. The library synthesis was initiated by building up the

inner biphenyl core of the tetramer in a combinatorial parallel

synthesis by palladium-catalysed Suzuki-coupling of com-

ponents 1{H} and TMS-protected phenylboronic esters 2{B},

using the system [Pd(PPh₃)₄]–potassium carbonate in dioxane.

From the 12 possible combinations of 1{H} and 2{B}, the

coupling 1{3} ϩ 2{1} was omitted, because the resulting bi-

phenyl 3{3,1} would ﬁnally lead to the identical p-quater-

phenyls that are already obtained from biphenyl 3{1,2}. The

biphenyls 3{H,B} were obtained in good yields of 68 to 95%

(mean 82%). The biphenyls 3{H,B} were then converted in

parallel into the corresponding iodinated biphenyls 4{H,B}

by metallation with n-BuLi and subsequent reaction with 1,2-

diiodoethane (49–95% yield, mean 85%). In order to further

accelerate the synthesis, the following three parallel synthetic

steps were carried out as a three step synthesis in solution with-

out puriﬁcation of the crude products, which was only possible

because of the fact that the optimised reaction condition reli-

ably ensured the complete turnover of all starting materials as

well as minimum contamination of by-products. In the next

step, in a combinatorial parallel synthesis 11 biphenyls 4{H,B}

were cross-coupled with ﬁve boronic esters 5{T } under the

optimised Suzuki reaction conditions to result in 49 TMS-

protected terphenyls 6{T,H,B} in a mean yield of 98% and a

mean purity of 99%. The number of 55 possible combinations

is reduced to 49 p-terphenyls 6{T,H,B}, because the Suzuki-

coupling did not tolerate more than two ortho ﬂuoro atoms in

the biphenyl moiety (vide supra). Therefore, the synthesis of the

terphenyls 6{2,3,1}, 6{2,3,2}, 6{2,3,5}, 6{5,4,1}, 6{5,4,2} and

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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6{5,4,5} was not attempted. In 49 parallel reactions, terphenyls

6{T,H,B} were iododesilylated using iodine chloride in aceto-

nitrile. The resulting iodinated terphenyls 7{T,H,B} turned out

to be poorly soluble in acetonitrile and therefore could easily be

isolated by ﬁltration in a mean yield of 89% and a mean purity

of 98%. In the last step, by combinatorial parallel Suzuki reac-

tions, 49 terphenyls 7{T,H,B} were cross-coupled with the ﬁve

boronic esters 5{T } to ﬁnally yield a library of 225 crude

p-quaterphenyls 8{T,H,B,T } comprising up to eight ﬂuoro

substituents at diﬀerent positions. The number of 245 possible

combinations of reactants is reduced to 225 p-quaterphenyls

8{T,H,B,T }, due to the symmetry of the inner biphenyl-cores

of biphenyls 4{1,1} and 4{3,2}.

Puriﬁcation and analytical quality control

Special emphasis has been put on the puriﬁcation of the ﬁnal

p-quaterphenyls 8{T,H,B,T }, because in contrast to libraries

of drug-like molecules, where for biological screening in general

purities of about 70–80% are satisfactory, in material libraries

purities of 99% and higher are required for the reliable screen-

ing of their physical properties, as the accuracy of physical

measurements crucially depends on purity.^5a–c,6bFor that

reason, a method was needed that would allow the reliable and

rapid puriﬁcation of the individual library members. The usage

of sequential automated semipreparative HPLC-MS, which we

successfully applied in the puriﬁcation of dye and conjugated

oligomer libraries,^5a,cwould have been very tedious in this case,

as the determination of the bulk-properties of liquid crystals

requires the puriﬁcation of larger (i.e. 40–50 mg) amounts of

material. Therefore, we developed a method for a rapid parallel

recrystallization (Fig. 2).

Fig. 3 Parallel recrystallization of quaterphenyls 8.

Fig. 4 Histogram representation of the isolated yields of quater-

phenyls 8. Absolute (grey columns) = number of compounds within the

speciﬁed yield range. Cumulated (black squares) = relative number of

compounds with at least the speciﬁed yield.

pressure chemical ionisation (APCI) was employed as the ionis-

ation technique, which allowed the detection of the [M ϩ H]^ϩ

ions of the quaterphenyls as the base peaks of the mass spectra.

A representative example (quaterphenyl 8{5,1,1,3}) of the

HPLC-MS purity control after the puriﬁcation is shown in

Fig. 5 and 6. Both the UV-absorbance trace (Fig. 5a) and the

total ion count (TIC) trace (Fig. 5b) show that no impurities are

present in the ﬁnal product.

Fig. 2 Device used for the parallel recrystallization of quaterphenyls

8.

Custom-made apparatus I consists of a crystallization ﬂask

and a mother-liquor collection ﬂask, that are held together via a

double thread connector. The two ﬂasks are separated by a ﬁlter

paper which is supported by a PE frit and an O-ring for sealing.

For the puriﬁcation, the crude product is recrystallized in the

crystallization ﬂask (II). After complete crystallization, the

setup is reversed (III) and put into a centrifuge. Upon centri-

fugation, the mother-liquor is transferred completely into the

mother-liquor collection ﬂask (IV). In contrast to other com-

mon means of puriﬁcation like distillation or chromatography,

this method can easily parallelised, as the number of parallel

puriﬁcations is only limited by the availability of the special

recrystallization ﬂasks and both, the recrystallization and

crystal separation can be carried out in parallel fashion using

standard equipment (Fig. 3).

Additionally, the recrystallization can be repeated several

times without eﬀort, until the desired purity is achieved. By

recrystallizing up to 30 compounds at the same time, the puriﬁ-

cation of the whole library was performed in a matter of days.

The overall yield of the last synthetic step ranged from 31 to

99% (mean 81%, Fig. 4) after puriﬁcation, the absolute amount

of puriﬁed product being in the range of 25–50 mg, which is

suﬃcient for the screening of the mesophase properties.

Fig. 5 HPLC-MS analysis of puriﬁed quaterphenyl 8{5,1,1,3}: a) UV

absorbance trace (UV detection at λ = 230 nm); b) total ion count (TIC)

trace (APCIϩ). The mass spectrum under the peak is identical to the

one displayed in Fig. 6.

As displayed by the corresponding mass spectrum under the

peak, the molecular ion [M ϩ H]^ϩof quaterphenyl 8{5,1,1,3}

showed the theoretical value of 445.5 amu (Fig. 6).

The purity and identity of the library members was checked

by sequential automated analytical HPLC-MS. Atmospheric-

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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minimised. This general synthetic scheme was applied to the

synthesis of 225 p-quaterphenyls by combinatorial parallel

synthesis. With the parallel recrystallization, a technique was

developed that allowed the rapid puriﬁcation of the individual

library members in quantities needed for the determination of

the bulk-properties of the materials. In this paper, we described

the ﬁrst four steps of a full combinatorial development process

leading to a novel class of LC materials.

Fig. 6 Mass spectrum of quaterphenyl 8{5,1,1,3}. The molecular ion

[M ϩ H]^ϩof this compound is 445.5 amu, which corresponds to the

theoretical value.

Experimental

General methods

Solvents and reagents were puriﬁed and dried by usual methods

prior to use. Unless otherwise stated, reactions were carried out

in ﬂame-dried glassware under an atmosphere of argon. Diethyl

ether and THF were continuously distilled from calcium

hydride and potassium, respectively. Melting points were

determined with a Büchi B-545 melting point apparatus and are

uncorrected. Gas chromatograms were recorded on a Varian

CP 3800 with a 30 m glass capillary column CP 5860, carrier

gas helium 5.0, detection Varian-FID ﬂame ionisation detector

or Saturn 2000 mass detector operating in the electron-impact

(EI) –mode. ¹H NMR spectra were recorded on a Bruker AMX

400 (400 MHz) spectrometer. Chemical shifts are expressed in

parts per million (δ) using residual solvent protons as internal

standard. ¹³C NMR spectra were recorded on a Bruker AMX

400 (101 MHz) spectrometer. Infrared spectra were recorded on

a Perkin-Elmer FTIR Spectrum 2000 spectrometer. Mass

spectra were recorded on a Varian MAT 711. Ions were gener-

ated by electron impact at 70 eV or by chemical ionisation by

using ethane as ionisation gas. Elemental analyses were per-

formed on an Elementar vario EL (limit of experimental error:

0.3%). HPLC analysis was accomplished using a Waters

HPLC system (MassLynx, Version 3.4; Waters 600E Multisol-

vent Delivery System; Waters 2700 Sample Manager; Waters

Fraction Collector II; Waters Reagent Manager; Acurate Flow-

stream Splitting Device ACM 10–50, LC Packings) equipped

with a photodiode array detector (Waters 996 PDA Detector)

coupled to a Platform-LC/detector (Micromass ZMD) operat-

ing with an APCI source. Conditions for LC analysis: Nucleosil

nitrophenyl column (Macherey-Nagel, 250 mm × 4 mm, 5 mm/

100 Å), eluent: CH₂Cl₂–n-hexane mixture 98 : 2 (isocratic), ﬂow

rate: 2.0 mL min^Ϫ1, injection volume: 20 µL, photodiode array

detection: scan range 250–500 nm. Conditions: positive ion

APCI, source block temperature 130 ЊC, APCI probe temper-

ature: 600 ЊC, cone voltage: 27 V, corona voltage: 3.5 kV,

extractor: 7 V, RF lens: 0.2 V, LM resolution: 15.0, HM reso-

lution: 14.8; ion energy: 0.8, multiplier: 650, desolvation gas

The puriﬁcation of all 225 library members furnished 213

compounds (corresponding to 95% of all library members) that

were pure by HPLC, 5 compounds in 99.0–99.9% purity, and 3

compounds in a purity of 98–99%, whereas 4 compounds were

only 95–97% pure. According to that, a total of 221 compounds

(corresponding to 98% of all library members) had a purity of

1

>98%. H and ¹³C NMR spectra were taken for 19 randomly

selected library members to provide additional structural char-

acterisation. These NMR spectra along with the mass spectra

and HPLC-chromatograms of all library members are given in

the supporting information.

Screening of the individual library members by automated

sequential DSC revealed that from 223 compounds investi-

gated, 219 novel LC materials had been discovered and quali-

tative correlations of the molecular structure with the LC

properties can be deduced (Fig. 7). 3 compounds showed a

purely smectic phase, 115 compounds smectic followed by

nematic phases, and 101 LC materials were purely nematogenic.

Within the library, several “hits” with very broad mesophasic

ranges up to 200 ЊC and melting points lower than 100 ЊC have

been identiﬁed, which makes them very suitable candidates

for LCD mixtures. Moreover, statistical analysis of the derived

data sets revealed unique quantitative structure–property

relationships (QSPR) for the LC materials that describe the

inﬂuence of the various ﬂuorine substituents on the physical

properties of the molecules and ﬁnally allow the rational design

of novel materials. In this respect, we found out that in order to

obtain reliable QSPRs material libraries comprising at least 150

members are necessary. These two ﬁnal steps of the combin-

atorial developmental cycle, screening and data analysis, will

be described in detail in a forthcoming paper.⁷

ﬂow: 433 L h^Ϫ1, cone gas ﬂow: 95 L h^Ϫ1

.

Parallel reactions

The combinatorial synthesis of terphenyls 6{T,H,B},

7{T,H,B} and quaterphenyls 8{T,H,B,T } was carried out in

parallel fashion. Parallel heating of the closed vials equipped

with magnetic stirring bars was achieved by inserting the

reaction vessels into a custom made aluminium block that was

put on top of a commercial temperature controlled magnetic

stirring hotplate. The setup allows parallel heating and mag-

netic stirring of up to 35 vials. Parallel shaking was performed

with an Advanced ChemTec PLS4 × 6 shaker. Parallel ﬁltration

was performed with a IST VacMaster parallel vacuum manifold

and Separtis SPE ﬁlter-syringes. Parallel evaporation of solvent

was performed with a Labconco RAID VAP model 79 000

parallel evaporator under reduced pressure. The synthesis of

biphenyls 3{H,B} and 4{H,B} was carried out in standard

glassware in a fume hood according to the general procedures

given below by using a large oil bath/cooling bath for parallel

thermostating.

Fig. 7 Mesogenity of the compounds of the material library. Number

of compounds with: C, only crystalline phase; S, only smectic phase;

N, only nematic mesophase; S & N, smectic and nematic mesophase.

Conclusions

In summary, an eﬃcient convergent synthesis of novel liquid

crystalline p-quaterphenyls has been developed. Three types of

building blocks were assembled by a sequence of iterative iodin-

ations and Suzuki-couplings and by exploiting a bi-directional

oligomer growth strategy, the number of synthetic steps was

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1614

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Materials

(m), 703 (m), 651 (s), 634 (m), 499 (m); δ_H(400.1 MHz, CDCl₃)

0.98 (t, J = 7.4 Hz, 3 H, CH₂–CH₃), 1.04 (s, 6 H, CMe₂), 1.69

(sextet, J = 7.5 Hz, 2 H, CH₂–CH₃), 2.63 (t, J = 7.7 Hz, 2 H,

Ar–CH₂), 3.79 (s, 4 H, 2 × OCH₂), 7.22 (d, ³J_HH= 8.1 Hz, 2 H,

Chemicals were purchased from commercial suppliers: 1,2-

dibromoethane (Merck), 1,2-diﬂuorobenzene 14 (Fluorochem),

1,2-diiodoethane (Merck), 1-bromo-3,5-diﬂuorobenzene 1{4}

(Fluorochem), 1-bromo-3-ﬂuoro-4-iodobenzene 1{2} (Fluoro-

chem), 4-bromo-3-ﬂuoro-1-iodobenzene 1{3} (Fluorochem),

p-bromoiodobenzene 1{1} (ABCR), 4-bromopropylbenzene 9

(Aldrich), allyl bromide (Merck), boron tribromide (Merck),

diisopropylamine (Merck), iodine chloride (Merck), potassium

carbonate (Merck), diatomenic earth: Isolute MH (Separtis),

copper() cyanide (Fluka), magnesium sulfate (Merck), N,N-

dimethylaminopyridine (Merck), sodium dithiosulfate (Merck),

n-butyllithium (1.6 M in n-hexane, Merck), neopentyl glycol

(Merck), palladium() acetate (Merck), phosphorus pentaoxide

(Merck), platinum dioxide (Merck), propanal (Merck), triiso-

propyl borate (Acros), trimethylsilyl chloride (Merck). Tetra-

kis(triphenylphosphino)palladium(0)¹²and 4-bromotrimethyl-

silylbenzene 21¹³were prepared according to literature

procedures.

3

H3,5), 7.77 (d, J_HH= 8.1 Hz, 2 H, H2,6); δ_C(100.6 MHz,

CDCl₃) 13.8 (CH₂–CH₃), 21.9 (CMe₂), 22.4 (CH₂–CH₃), 31.8

(CMe₂), 38.2 (Ar–CH₂), 72.2 (2 × OCH₂), 127.8 (C3,5), 133.8

(C2,6), 145.4 (C4); m/z (CI): 233 [MH^ϩ], 203.

1-Bromo-3-ﬂuoro-4-propylbenzene 11. To a solution of 151 g

(500 mmol) 1-bromo-3-ﬂuoro-4-iodobenzene 1{2} in 1 l dry

diethyl ether at Ϫ78 ЊC 313 ml (501 mmol) 1.6 M n-BuLi was

added dropwise. After 1.5 h 2.24 g (25.0 mmol) CuCN were

added and then 129 ml (151 g, 1.50 mol) allyl bromide was

added at such a rate that the temperature never exceeded

Ϫ70 ЊC. The mixture was allowed to reach room temperature

over night and diethyl ether and water were added. The organic

phase was washed with aq. ammonia, water and brine, dried

over MgSO₄and the solvent was removed under reduced pres-

sure. The oily residue was dissolved in 500 ml methanol, 500 mg

PtO₂were added and the stirred mixture was hydrogenated

at normal pressure for 12 h. The catalyst was ﬁltered oﬀ and

the solvent was removed under reduced pressure. Distillation

(bp 82 ЊC/11 mbar) yielded 69.9 g (64%) alkylbenzene 11

(Found: C, 49.80; H, 4.64. C₉H₁₀BrF requires C, 49.51; H,

4.50%); ν_max(KBr)/cm^Ϫ13070 (w), 2963 (s), 2933 (m), 2872 (m),

1605 (m), 1576 (m), 1485 (s), 1462 (m), 1403 (m), 1262 (m), 1220

(m), 1182 (w), 1129 (m), 1066 (w), 883 (m), 860 (m), 817 (m),

796 (w), 779 (w), 729 (w), 627 (w), 579 (w), 548 (w), 485 (w), 450

(w); δ_H(400.1 MHz, CDCl₃) 0.95 (t, J = 7.3 Hz, 3 H, CH₂–CH₃),

1.63 (sextet, J = 7.5 Hz, 2 H, CH₂–CH₃), 2.57 (t, J = 7.6 Hz, 2 H,

Ar–CH₂), 7.05 (t, J = 8.1 Hz, 1 H, H2), 6.17–7.21 (m, 2 H,

H5,6); δ_C(100.6 MHz, CDCl₃) 13.7 (CH₂–CH₃), 23.1 (CH₂–

General procedures (GPs)

GP1: Synthesis of boronic esters 5{1}–5{5}, 2{1}, 2{2} and

2{5}. To a solution of halogenated benzene 1{H} in dry THF

(1.5 ml per mmol) at Ϫ78 ЊC 1.1 eq. 1.6 M n-BuLi were added.

After 15 min. 1.3 eq. triisopropyl borate were added dropwise

and allowed to reach room temperature over night. Water,

diethyl ether and 1 eq. conc. HCl were added. The organic

phase was washed with water and brine and the solvent

was removed in vacuo. The oily residue was dissolved in THF

(0.3 ml mmol^Ϫ1) and 1 eq. neopentyl glycol and MgSO₄(0.5 g

mmol^Ϫ1) were added. After stirring for 1 h the solvent was

removed in vacuo and to the oily residue hexanes were added

(0.30 ml mmol^Ϫ1). Precipitated neopentyl glycol was removed

by ﬁltration. From the ﬁltrate at Ϫ25 ЊC analytically pure

boronic ester crystallised.

2

CH₃), 30.6 (Ar–CH₂), 118.7 (d, J_CF= 25.8 Hz, C2), 119.3

3

4

(d, J_CF= 9.1 Hz, C1), 127.0 (d, J_CF= 3.8 Hz, C6), 128.5

2

3

(d, J_CF= 16.3 Hz, C4), 131.7 (d, J_CF= 6.1 Hz, C5), 161.0

1

(d, J_CF= 249.4 Hz, C3); m/z (EI) 218, 216 [M^ϩ], 189, 187

[M^ϩ–C₂H₅], 108 [M^ϩ–C₂H₅–Br].

GP2: Synthesis of biphenyls 3{H,B} by Suzuki coupling. To a

solution of 50.0 mmol halogenated benzene 1{H}, 50.0 mmol

boronic ester and 2.31 g (2.00 mmol) [Pd(PPh₃)₄] in 100 ml

degassed dioxane, a solution of 16.6 g (120 mmol) K₂CO₃in

50 ml degassed water was added and reﬂuxed under argon until

reaction control by GC revealed complete reaction. The organic

phase was washed with water and brine, dried over MgSO₄

and ﬁltered over a silica plug. If necessary, the crude product

was puriﬁed by Kugelrohr distillation. Solid products were

recrystallised from hexanes at Ϫ25 ЊC.

2-(3-Fluoro-4-propylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane

5{3}. According to GP1, but using diethyl ether instead of THF

as solvent, from 74.2 g (342 mmol) 1-bromo-3-ﬂuoro-4-

propylbenzene 11 was obtained 38.7 g (46%) boronic ester 5{3}

(Found: C, 67.23; H, 8.06. C₁₄H₂₀BFO₂requires C, 67.36; H,

8.01%); ν_max(KBr)/cm^Ϫ12962 (m), 2934 (m), 2873 (m), 1621

(w), 1560 (w), 1505 (w), 1482 (m), 1424 (m), 1398 (m), 1377 (m),

1342 (m), 1318 (s), 1250 (w), 1222 (m), 1179 (w), 1134 (m), 1110

(m), 988 (w), 944 (w), 896 (w), 833 (w), 812 (w), 779 (w), 728

(w), 701 (m), 678 (m), 645 (w), 551 (w), 503 (w), 479 (w), 456

(w); δ_H(400.1 MHz, CDCl₃) 0.97 (t, J = 7.4 Hz, 3 H, CH₂–CH₃),

1.03 (s, 6 H, CMe₂), 1.66 (sextet, J = 7.5 Hz, 2 H, CH₂–CH₃),

2.65 (t, J = 7.7 Hz, 2 H, Ar–CH₂), 3.77 (s, 4 H, 2 × OCH₂),

7.18 (t, ³J_HH≈ ⁴J_FH≈ 7.4 Hz, 1 H, H5), 7.43 (d, ³J_FH= 10.7 Hz,

GP3: Synthesis of iodobiphenyls 4{H,B}. To a solution of

bromobiphenyl 3{H,B} in dry THF (3 ml mmol^Ϫ1) at Ϫ78 ЊC

1.1 eq. 1.6 M n-BuLi were added. After 15 min. 1.3 eq. 1,2-

diiodoethane were added as a solid and the mixture was allowed

to reach room temperature within one hour. Water and diethyl

ether were added and the organic phase was washed with water,

satd. Na₂S₂O₅and brine, dried over MgSO₄and ﬁltered over a

silica plug. If necessary, the crude product was puriﬁed by

Kugelrohr distillation. All products were recrystallised from

hexanes at Ϫ25 ЊC.

3

1 H, H2), 7.50 (d, J_HH= 7.5 Hz, 1 H, H6); δ_C(100.6 MHz,

CDCl₃) 13.8 (CH₂–CH₃), 21.8 (CMe₂), 23.2 (CH₂–CH₃), 31.1

(Ar–CH₂), 31.8 (CMe₂), 72.3 (2 × OCH₂), 119.9 (d, ²J_CF= 20.5

4

3

Hz, C2), 129.2 (d, J_CF= 3.0 Hz, C6), 130.0 (d, J_CF= 4.6 Hz,

2

1

C5), 132.0 (d, J_CF= 16.3 Hz, C4), 161.0 (d, J_CF= 244.8 Hz,

C3); m/z (CI) 251, 250, 249 [MH^ϩ], 231 [MH^ϩϪ HF], 221,

207, 117.

Synthesis of boronic ester-building blocks 5{1}–5{5} and 2{1},

2{2} and 2{5}

1-(4-Bromo-2,6-diﬂuorophenyl)-propan-1-ol 12. To a solution

of 96.5 g (500 mmol) 1-bromo-3,5-diﬂuorobenzene 1{4} in

500 ml dry THF at Ϫ78 ЊC 501 mmol LDA (freshly prepared

from 55.7 g (550 mmol) diisopropylamine and 313 ml

(501 mmol) 1.6 M n-BuLi) was added dropwise. After 1.5 h

46.7 ml (37.8 g, 650 mmol) propanal was added at such a rate

that the temperature never exceeded Ϫ70 ЊC . The mixture was

allowed to reach room temperature and diethyl ether and water

were added. The organic phase was washed with water and

2-(4-Propylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane 5{1}.

According to GP1, from 55.9 g (281 mmol) 4-bromopropyl-

benzene 9 was obtained 37.8 g (58%) boronic ester 5{1}; mp

86.3 ЊC (Found: C, 72.44; H, 9.12. C₁₄H₂₁BO₂requires C, 72.42;

H, 9.03%); ν_max(KBr)/cm^Ϫ13078 (w), 3046 (w), 3026 (w), 2962

(s), 2934 (s), 2872 (m), 1611 (s), 1560 (w), 1482 (m), 1420 (m),

1381 (m), 1344 (m), 1317 (s), 1249 (m), 1218 (w), 1183 (w), 1130

(s), 1020 (m), 967 (w), 934 (w), 915 (w), 837 (m), 809 (m), 745

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1615

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brine, dried over MgSO₄and the solvent was removed under

reduced pressure. Distillation (bp 66 ЊC/10^Ϫ3mbar) yielded

112 g (89%) alcohol 12 (Found: C, 43.06; H, 3.61. C₉H₉BrF₂O

requires C, 43.35; H, 3.88%); ν_max(KBr)/cm^Ϫ13373 (m), 3093

(w), 2969 (m), 2936 (m), 2879 (w), 1645 (s), 1579 (m), 1467 (m),

1417 (s), 1379 (w), 1331 (w), 1284 (w), 1241 (w), 1185 (m), 1094

(m), 1053 (m), 1008 (s), 974 (w), 906 (w), 859 (m), 842 (m), 743

(w), 607 (w), 584 (w), 538 (w), 516 (w); δ_H(400.1 MHz, CDCl₃)

0.88 (t, J = 7.5 Hz, 3 H, CH₂–CH₃), 1.72–1.82 (m, 1 H, CH_aH_b–

CH₃), 1.86–1.98 (m, 1 H, CH_aH_b–CH₃), 2.84 (d, J = 7.7 Hz, 1 H,

OH ), 4.85 (q, J = 7.5, 1 H, CH–OH), 7.02 (d, line distance

7.8 Hz, AAЈ-part of a AAЈXXЈ-spectrum, 2 H, H3,5); δ_C(100.6

MHz, CDCl₃) 10.1 (CH₂–CH₃), 29.8 (CH₂–CH₃), 67.6 (d,

³J_CF= 1.9 Hz, CH-OH), 115.5 (d, line distance 30.4 Hz, AAЈ-

(KBr)/cm^Ϫ13361 (s), 2971 (s), 2937 (m), 2881 (w), 1627 (w),

1596 (w), 1486 (s), 1383 (w), 1362 (w), 1329 (w), 1276 (m), 1202

(m), 1095 (w), 1064 (w), 1046 (w), 958 (m), 877 (w), 825 (w), 786

(w), 749 (m), 726 (m), 700 (w), 667 (w), 599 (w); δ_H(400.1 MHz,

CDCl₃) 0.94 (t, J = 7.4 Hz, 3 H, CH₂–CH₃), 1.73–1.88 (m, 2 H,

CH₂–CH₃), 2.10 (d, J = 4.3 Hz, 1 H, OH ), 4.96 (dd, J = 11.1 Hz,

J = 6.4 Hz, 1 H, CH–OH), 7.02–7.10 (m, 2 H, Ar–H ), 7.19–

7.23, (m, 1 H, Ar–H); δ_C(100.6 MHz, CDCl₃) 9.8 (CH₂–CH₃),

30.8 (CH₂–CH₃), 69.4 (CH–OH), 115.8 (d, ²J_CF= 17.1 Hz, C4),

121.9 (t, J = 3.4 Hz) and 124.1 (dd, J = 6.8 Hz, J = 4.6 Hz,

1

C5,6), 134.0 (d, J = 10.2 Hz, C1), 147.8 (dd, J_CF= 247.1 Hz,

²J_CF= 12.9 Hz) and 150.3 (dd, ¹J_CF= 247.9 Hz, ²J_CF= 12.9 Hz,

C2,3); m/z (EI) 172 [M^ϩ], 115, 95.

2

part of a AAЈXXЈ-spectrum, C3,5), 118.8 (t, J_CF= 16.9 Hz,

1,2-Diﬂuoro-3-propylbenzene 16. The experimental procedure

was as described for the preparation of compound 13. Quanti-

ties: 184 g (1.30 mol) phosphorus pentaoxide, 75.0 g (436

mmol) 1-(2,3-diﬂuorophenyl)propan-1-ol 15, 500 mg PtO₂.

Yield: 46.3 g (68%) alkylbenzene 16; bp 40–43 ЊC/11 mbar

(Found: C, 69.22; H, 6.45. C₉H₁₀F₂requires C, 69.30; H,

6.39%); ν_max(KBr)/cm^Ϫ13051 (w), 2965 (m), 2935 (m), 2874

(m), 1627 (m), 1595 (m), 1489 (s), 1382 (w), 1342 (w), 1280 (m),

1203 (m), 1160 (w), 1102 (w), 1054 (w), 980 (w), 893 (w),

856 (w), 825 (w), 775 (m), 725 (m), 695 (w), 681 (w), 589 (w),

558 (w), 520 (w); δ_H(400.1 MHz, CDCl₃) 0.96 (t, J = 7.6 Hz,

3 H, CH₂–CH₃), 1.60–1.69 (m, 2 H, CH₂–CH₃), 2.64 (t, J =

7.6 Hz, 2 H, Ar–CH₂), 6.91–7.02, (m, 3 H, Ar–H ); δ_C(100.6

MHz, CDCl₃) 13.7 (CH₂–CH₃), 23.2 (CH₂–CH₃), 30.8

(Ar–CH₂), 114.5 (d, ²J_CF= 17.1 Hz, C6), 123.5 (dd, J = 6.8 Hz,

J = 4.6 Hz) and 125.2 (t, J = 3.6 Hz, C4,5), 131.9 (d, J = 12.9 Hz,

3

1

C1), 120.7 (t, J_CF= 12.9 Hz, C4), 150.3 (dd, J_CF= 251.8 Hz,

²J_CF= 10.1 Hz, C2,6); m/z (CI) 251, 253 [MH^ϩ], 235, 233 [MH^ϩ-

H₂O], 223, 221, 207, 205.

5-Bromo-1,3-diﬂuoro-2-propylbenzene 13. A suspension of

177 g (1.30 mol) phosphorus pentaoxide in 500 ml pentane and

105 g (418 mmol) 1-(4-bromo-2,6-diﬂuorophenyl)propan-1-ol

12 was stirred overnight. The solution was decanted from

P₄O₁₀, ﬁltered over basic alumina, 500 mg PtO₂were added and

the stirred mixture was hydrogenated at normal pressure for

12 h. The catalyst was ﬁltered oﬀ and the solvent was removed

under reduced pressure. Distillation (bp 75 ЊC/11 mbar) yielded

70.5 g (72%) alkylbenzene 13 (Found: C, 45.99; H, 3.86.

C₉H₉BrF₂requires C, 46.02; H, 3.90%); ν_max(KBr)/cm^Ϫ13096

(w), 2966 (s), 2936 (m), 2874 (m), 1618 (s), 1577 (m), 1505 (w),

1475 (s), 1416 (s), 1383 (w), 1344 (w), 1282 (w), 1226 (w), 1188

(w), 1113 (s), 1079 (w), 1038 (w), 994 (s), 866 (s), 842 (s), 771

(w), 694 (w), 580 (m), 512 (w); δ_H(400.1 MHz, CDCl₃) 0.94 (t,

J = 7.4 Hz, 3 H, CH₂–CH₃), 1.59 (sextet, J = 7.4 Hz, 2 H, CH₂–

CH₃), 2.60 (t, J = 7.5 Hz, 2 H, Ar–CH₂), 7.02 (d, line distance

6.8 Hz, AAЈ-part of a AAЈXXЈ-spectrum, 2 H, H4,6); δ_C(100.6

MHz, CDCl₃) 13.6 (CH₂–CH₃), 22.5 (CH₂–CH₃), 24.0 (d,

³J_CF= 1.9 Hz, Ar–CH₂), 114.9 (d, line distance 30.0 Hz, AAЈ-

1

2

C3), 149.1 (dd, J_CF= 245.6 Hz, J_CF= 12.1 Hz) and 150.6

(dd, ¹J_CF= 247.1 Hz, ²J_CF= 13.3 Hz, C1,2); m/z (EI) 156 [M^ϩ],

127 [M^ϩϪ C₂H₅].

2-(2,3-Diﬂuoro-4-propylphenyl)-5,5-dimethyl[1,3,2]dioxabor-

inane 5{5}. According to GP1 from 42.3 g (271 mmol) 1,2-

diﬂuoro-3-propylbenzene 16 was obtained 56.3 g (78%) boronic

ester 5{5}; mp 26.7 ЊC (Found: C, 62.72; H, 7.14. C₁₄H₁₉BF₂O₂

requires C, 62.61; H, 7.05%); ν_max(KBr)/cm^Ϫ12963 (s), 2936 (s),

2874 (m), 1632 (w), 1481 (s), 1449 (s), 1377 (w), 1340 (m), 1319

(s), 1253 (m), 1191 (w), 1144 (m), 1097 (w), 1058 (w), 1011 (w),

971 (w), 869 (w), 818 (w), 693 (w), 669 (w); δ_H(400.1 MHz,

CDCl₃) 0.94 (t, J = 7.3 Hz, 3 H, CH₂–CH₃), 1.03 (s, 6 H, CMe₂),

1.64 (sextet, J = 7.5 Hz, 2 H, CH₂–CH₃), 2.64 (t, J = 7.8 Hz, 2 H,

2

part of a AAЈXXЈ-spectrum, C4,6), 117.4 (t, J_CF= 20.5 Hz,

3

1

C2), 118.7 (t, J_CF= 12.7 Hz, C5), 161.5 (dd, J_CF= 249.9 Hz,

²J_CF= 10.4 Hz, C1,3); m/z (CI) 237, 235 [MH^ϩ], 207, 205

[MH^ϩ–C₂H₅], 189, 136.

2-(3,5-Diﬂuoro-4-propylphenyl)-5,5-dimethyl[1,3,2]dioxabor-

inane 5{4}. According to GP1, but using diethyl ether instead of

THF as solvent, from 66.6 g (283 mmol) 5-bromo-1,3-diﬂuoro-

2-propylbenzene 13 was obtained 36.7 g (48%) boronic ester

5{4}; mp 40.0 ЊC (Found: C, 62.72; H, 7.14. C₁₄H₁₉BF₂O₂

requires C, 62.61; H, 7.20%); ν_max(KBr)/cm^Ϫ12966 (s), 2937

(m), 2899 (m), 2874 (m), 1628 (w), 1569 (m), 1483 (m), 1429

(m), 1381 (m), 1332 (s), 1253 (s), 1191 (w), 1109 (s), 1045 (w),

1000 (m), 984 (m), 912 (w), 868 (m), 811 (m), 709 (m), 689 (s),

583 (w), 550 (w), 493 (m), 443 (w); δ_H(400.1 MHz, CDCl₃) 0.94

(t, J = 7.4 Hz, 3 H, CH₂–CH₃), 1.00 (s, 6 H, CMe₂), 1.61 (sextet,

J = 7.5 Hz, 2 H, CH₂–CH₃), 2.65 (t, J = 7.5 Hz, 2 H, Ar–CH₂),

3.74 (s, 4 H, 2 × OCH₂), 7.26 (d, line distance 8.3 Hz, AAЈ-part

of a AAЈXXЈ-spectrum, 2 H, H2,6); δ_C(100.6 MHz, CDCl₃)

13.7 (CH₂–CH₃), 21.8 (CMe₂), 22.7 (CH₂–CH₃), 24.4 (Ar–

CH₂), 31.8 (CMe₂), 72.3 (2 × OCH₂), 115.6 (d, line distance

24.3 Hz, AAЈ-part of a AAЈXXЈ-spectrum, C2,6), 120.3 (t,

²J_CF= 20.7 Hz, C4), 161.3 (dd, ¹J_CF= 246.7 Hz, ³J_CF= 8.4 Hz,

C3,5); m/z (CI) m/z = 269, 268, 267 [MH^ϩ], 249 [MH^ϩϪ HF],

239.

3

Ar–CH₂), 3.78 (s, 4 H, 2 × OCH₂), 6.90 (ddd, J_HH= 7.5 Hz,

⁴J_FH= 6.3 Hz, ⁵J_FH= 1.1 Hz, 1 H, H5), 7.34 (ddd, ³J_HH= 7.5 Hz,

⁴J_FH= 5.6 Hz, ⁵J_FH= 1.7 Hz, 1 H, H5); δ_C(100.6 MHz, CDCl₃)

13.6 (CH₂–CH₃), 21.8 (CMe₂), 23.1 (CH₂–CH₃), 30.9 (Ar–

CH₂), 31.8 (CMe₂), 72.4 (2 × OCH₂), 125.6 (t, J_CF= 3.6 Hz)

3

4

and 129.5 (dd, J_CF= 7.4 Hz, J_CF= 4.7 Hz, C5,6), 134.2 (d,

²J_CF= 12.9 Hz, C4), 149.0 (dd, ¹J_CF= 245.8 Hz, ²J_CF= 14.6 Hz,

1

2

C3), 154.6 (dd, J_CF= 251.3 Hz, J_CF= 12.5 Hz, C2); m/z (CI)

269, 268, 267 [MH^ϩ].

1-Bromo-3-ﬂuoro-4-trimethylsilylbenzene 17. To a solution of

301 g (1.00 mol) 1-bromo-3-ﬂuoro-4-iodobenzene 1{2} in 1 l

dry diethyl ether 625 ml (1.00 mol) 1.6 M n-BuLi were added

at Ϫ78 ЊC. After 1 h 164 ml (141 g, 1.30 mol) TMSCl and

6.36 g (50.0 mmol) N,N-dimethylaminopyridine were added at

Ϫ78 ЊC. The mixture was allowed to reach room temperature

over night and diethyl ether and water were added. The organic

phase was washed with water and brine, dried over MgSO₄and

the solvent was removed under reduced pressure. Distillation

(bp 90–91 ЊC/11 mbar) yielded 236 g (96%) silylbenzene 17

(Found: C, 43.73; H, 4.89. C₉H₁₂BrFSi requires C, 43.85; H,

4.93%); ν_max(KBr)/cm^Ϫ13059 (w), 2959 (m), 2900 (w), 1586 (s),

1552 (s), 1529 (w), 1468 (m), 1407 (m), 1380 (s), 1323 (w), 1252

(s), 1200 (s), 1154 (w), 1128 (m), 1089 (w), 1061 (m), 872 (s), 843

(s), 813 (m), 762 (m), 705 (w), 692 (w), 631 (w), 577 (w), 545 (w),

452 (w); δ_H(400.1 MHz, CDCl₃) 0.30 (s, 9 H, SiMe₃), 7.16 (d,

1-(2,3-Diﬂuorophenyl)propan-1-ol 15. The experimental pro-

cedure was as described for the preparation of compound 12.

Quantities: 54.8 g (480 mmol) 1,2-diﬂuorobenzene 14, 300 ml

(480 mmol) 1.6 M n-BuLi, 47.7 ml (36.2 g, 624 mmol) propanal.

Yield: 79.1 g (96%) alcohol 15; bp 68–70 ЊC / 12 mbar (Found:

C, 62.78; H, 5.85. C₉H₁₀F₂O requires C, 62.66; H, 5.96%); ν_max

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1616

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³J_FH= 8.32 Hz, 1 H, H2), 7.22–7.27 (m, 2 H, H5,6); δ_C(100.6

(s, 6 H, CMe₂), 1.63 (sextet, J = 7.5 Hz, 2 H, CH₂–CH₃), 2.58 (t,

2

MHz, CDCl₃) Ϫ1.2 (SiMe₃), 118.4 (d, J_CF= 29.6 Hz, C2),

J = 7.7 Hz, 2 H, Ar–CH₂), 3.78 (s, 4 H, 2 × OCH₂), 6.83 (dd,

³J_FH= 10.9 Hz, ⁴J_HH=1.0 Hz, 1 H, H3), 6.94 (dd, ³J_HH= 7.6 Hz,

⁴J_HH= 1.0 Hz, 1 H, H5) 7.63 (t, ³J_HH≈ ⁴J_FH≈ 7.1 Hz, 1 H, H6);

δ_C(100.6 MHz, CDCl₃) 13.6 (CH₂–CH₃), 21.8 (CMe₂), 24.0

(CH₂–CH₃), 31.7 (CMe₂), 37.7 (Ar–CH₂), 72.3 (2 × OCH₂),

115.1 (d, ²J_CF= 24.3 Hz, C3), 123.7 (d, ⁴J_CF= 2.7 Hz, C5), 135.9

124.0 (d, ³J_CF= 9.9 Hz, C1), 125.2 (d, ²J_CF= 30.7 Hz, C4), 127.1

4

3

(d, J_CF= 3.4 Hz, C6), 136.0 (d, J_CF= 12.5Hz, C5), 167.1

1

(d, J_CF= 245.2 Hz, C3); m/z (EI) 248, 246 [M^ϩ], 233, 231,

[M^ϩϪ CH₃], 151 [M^ϩϪ HBr], 105, 103, 77, 47.

3

1-(3-Fluoro-4-trimethylsilylphenyl)propan-1-ol 18. The experi-

mental procedure was as described for the preparation of

compound 12. Quantities: 124 g (503 mmol) 1-bromo-3-ﬂuoro-

4-trimethylsilylbenzene 17, 345 ml (552 mmol) 1.6 M n-BuLi,

50.0 ml (40.0 g, 689 mmol) propanal. Yield: 90.1 g (79%)

alcohol 18; bp 119 ЊC / 12 mbar) (Found: C, 63.67; H, 8.46.

C₁₂H₁₉FOSi requires C, 63.53; H, 8.57%); ν_max(KBr)/cm^Ϫ13366

(br s), 2936 (s), 2900 (m), 2878 (m), 1613 (m), 1555 (m), 1484

(w), 1460 (w), 1402 (s), 1253 (s), 1223 (m), 1138 (w), 1094 (w),

1068 (m), 1044 (w), 1017 (w), 980 (w), 950 (w), 845 (s), 762 (m),

717 (w), 695 (w), 636 (w); δ_H(400.1 MHz, CDCl₃) 0.31 (s, 9 H,

(d, J_CF= 8.7 Hz, C6), 148.2 (d, J_CF= 8.4 Hz, C4), 167.3

1

(d, J_CF= 249.4 Hz, C2); m/z (CI) 251, 250, 249 [MH^ϩ], 231

[MH^ϩϪ HF].

2-(4-Trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane

2{1}. According to GP1 from 128 g (558 mmol) 4-bromo-1-

trimethylsilylbenzene 21 was obtained 106 g (63%) boronic

ester 2{1}; mp 74.7 ЊC (Found: C, 64.12; H, 8.84. C₁₄H₂₃BO₂Si

requires C, 63.99; H, 8.79%); ν_max(KBr)/cm^Ϫ13063 (w), 3016

(w), 2957 (s), 2895 (m), 1685 (w), 1600 (m), 1535 (w), 1501 (m),

1482 (m), 1418 (s), 1382 (m), 1346 (s), 1319 (s), 1262 (m),

1245 (m), 1191 (w), 1140 (s), 1101 (s), 1020 (w), 966 (w), 837 (s),

816 (s), 757 (m), 729 (m), 687 (m), 667 (w), 648 (m), 625 (w),

560 (w), 498 (w), 476 (w); δ_H(400.1 MHz, CDCl₃) 0.32 (s, 9 H,

SiMe₃), 1.03 (s, 6 H, CMe₂), 3.79 (s, 4 H, 2 × OCH₂), 7.55

3

SiMe₃), 0.93 (t, J_HH= 7.5 Hz, 3 H, CH₂–CH₃), 1.70–1.83 (m,

3

2 H, CH₂–CH₃), 1.99 (br. s, 1 H, OH ), 4.59 (d, J_HH= 6.5 Hz,

3

4

1 H, CH–OH), 6.99 (dd, J_FH= 9.6 Hz, J_HH= 1.4 Hz, 1 H,

H2), 7.09 (dd, ³J_HH= 7.5 Hz, ⁵J_FH= 0.7 Hz, 1 H, H6), 7.36 (dd,

³J_HH= 7.5 Hz, ⁴J_FH= 5.8 Hz, 1 H, H5); δ_C(100.6 MHz, CDCl₃)

Ϫ1.07 (SiMe₃), 10.0 (CH₂–CH₃), 30.8 (CH₂–CH₃), 75.3 (CH–

OH), 112.2 (d, ²J_CF= 26.1 Hz, C2), 121.3 (d, ⁴J_CF= 2.3 Hz, C6),

3

(d, J_HH= 7.7 Hz, 2 H, H3,5), 7.80 (d, J_HH= 7.7 Hz, 2 H,

H2,6); δ_C(100.6 MHz, CDCl₃) Ϫ1.2 (SiMe₃), 21.9 (CMe₂), 31.9

(CMe₂), 72.3 (2 × OCH₂), 132.5 and 133.0 (C2,3,5,6) 143.3

(C4); m/z (EI) 262 [M^ϩ], 247 [M^ϩϪ CH₃], 177.

2

3

125.0 (d, J_CF= 30.7 Hz, C4), 135.1 (d, J_CF= 11.8 Hz, C5),

148.7 (d, ³J_CF= 7.6 Hz, C1), 167.6 (d, ¹J_CF= 241.0 Hz, C3); m/z

(EI) 226 [M^ϩ], 197 [M^ϩϪ C₂H₅], 73.

2-(3-Fluoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxa-

borinane 2{2}. According to GP1, but using diethyl ether

instead of THF as solvent, from 156 g (632 mmol) 1-bromo-3-

ﬂuoro-4-trimethylsilylbenzene 17 was obtained 93.5 g (53%)

boronic ester 2{2}; mp 69.1 ЊC (Found: C, 60.01; H, 7.91.

C₁₄H₂₂BFO₂Si requires C, 59.98; H, 7.88%); ν_max(KBr)/cm^Ϫ1

2961 (s), 2903 (m), 2874 (m), 1612 (w), 1532 (m), 1483 (s), 1422

(s), 1384 (s), 1342 (s), 1316 (s), 1269 (m), 1249 (s), 1184 (m),

1120 (m), 1071 (s), 986 (m), 936 (w), 894 (m), 869 (m), 836 (s),

761 (m), 717 (m), 674 (s), 630 (w), 540 (w), 515 (w), 493 (w);

δ_H(400.1 MHz, CDCl₃) 0.31 (s, 9 H, SiMe₃), 0.99 (s, 6 H, CMe₂),

3.74 (s, 4 H, 2 × OCH₂), 7.36–7.40 (m, 2 H, H2,5), 7.54

2-Fluoro-4-propyl-1-trimethylsilylbenzene 19. The experi-

mental procedure was as described for the preparation of

compound 13. Quantities: 142 g (705 mmol) phosphorus penta-

oxide, 85.1 g (376 mmol) 1-(3-ﬂuoro-4-trimethylsilylphenyl)-

propan-1-ol 18, 1.00 g PtO₂. Yield: 41.2 g (52%) alkylbenzene

19; bp 90 ЊC/11 mbar) (Found: C, 68.51; H, 9.10. C₁₂H₁₉FSi

requires C, 68.61; H, 9.19%); ν_max(KBr)/cm^Ϫ13062 (w), 2960

(m), 2933 (m), 2901 (w), 2872 (w), 1614 (m), 1552 (w), 1486 (w),

1462 (w), 1403 (m), 1252 (m), 1227 (w), 1143 (w), 1073 (w),

950 (w), 844 (s), 762 (w), 714 (w), 694 (w), 663 (w), 628 (w),

546 (w); δ_H(400.1 MHz, CDCl₃) 0.31 (s, 9 H, SiMe₃), 0.96 (t,

J = 7.4 Hz, 3 H, CH₂–CH₃), 1.65 (sextet, J = 7.5 Hz, 2 H,

3

(d, J_HH= 7.1 Hz, 1 H, H6); δ_C(100.6 MHz, CDCl₃) Ϫ1.1

(SiMe₃), 21.8 (CMe₂), 31.8 (CMe₂), 72.3 (2 × OCH₂), 119.3

CH₂–CH₃), 2.59 (t, J = 7.7 Hz, 2 H, Ar–CH₂), 6.83 (dd, ³J_FH

=

(d, J_CF= 23.9 Hz, C2), 127.7 (d, J_CF= 30.4 Hz, C4), 128.9

4 3

2

4

3

9.7 Hz, J_HH= 1.1 Hz, 1 H, H3), 6.96 (d, J_HH= 7.4 Hz, 1 H,

H5), 7.30 (dd, ³J_HH= 7.4 Hz, ⁴J_FH= 6.1 Hz, 1 H, H6); δ_C(100.6

MHz, CDCl₃) Ϫ0.99 (SiMe₃), 13.8 (CH₂–CH₃), 24.2 (CH₂–

(d, J_CF= 2.7 Hz, C6), 134.3 (d, J_CF= 10.6 Hz, C5), 167.3

1

(d, J_CF= 241.0 Hz, C3); m/z (CI) 281 [MH^ϩ], 280 [M^ϩ], 265

[M^ϩϪ CH₃], 261 [M^ϩϪ F], 223, 209, 195, 189.

2

CH₃), 37.7 (Ar–CH₂), 114.6 (d, J_CF= 25.4 Hz, C3), 122.7

2

4

(d, J_CF= 30.4 Hz, C1), 124.0 (d, J_CF= 2.7 Hz, C5), 134.8 (d,

1,2-Diﬂuoro-3-trimethylsilylbenzene 22. To a solution of

114 g (1.00 mol) 1,2-diﬂuorobenzene 14 in 1 l dry THF 625 ml

(1.00 mol) 1.6 M n-BuLi were added at Ϫ78 ЊC. After 1 h 140 ml

(120 g, 1.10 mol) TMSCl was added at Ϫ78 ЊC. The mixture

was allowed to reach room temperature overnight and diethyl

ether and water was added. The organic phase was washed with

water and brine, dried over MgSO₄and the solvent was

removed under reduced pressure. Distillation (bp 100–102 ЊC/

70 mbar) yielded 170 g (91%) silylbenzene 22 (Found: C, 58.03;

H, 6.49. C₉H₁₂SiF₂requires C, 58.04; H, 6.57%); ν_max(KBr)/

cm^Ϫ12959 (s), 2926 (m), 2874 (w), 1613 (w), 1582 (w), 1450 (s),

1412 (w), 1292 (w), 1266 (s), 1252 (s) 1219 (w), 1185 (m), 1146

(w), 1059 (w), 907 (w), 843 (s), 782 (w), 759 (m), 695 (w), 642

(w), 602 (w), 561 (w); δ_H(400.1 MHz, CDCl₃) 0.34 (s, 9 H,

SiMe₃), 7.03–7.18 (m, 3 H); δ_C(100.6 MHz, CDCl₃) Ϫ1.1

(SiMe₃), 118.2 (d, ²J_CF= 17.8 Hz, C6), 124.3 (dd, ³J_CF= 5.7 Hz,

³J_CF= 11.8 Hz, C6), 146.8 (d, J_CF= 8.0 Hz, C4), 167.6 (dd,

3

¹J_CF= 240.6 Hz, C2); m/z (CI) 210 [M^ϩ], 195 [M^ϩϪ CH₃], 191

[M^ϩϪ F], 73.

2-(2-Fluoro-4-propylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane

5{2}. To a solution of 31.8 g (151 mmol) 2-ﬂuoro-4-propyl-1-

trimethylsilylbenzene 19 in 200 ml dry dichloromethane 15.8 ml

(41.6 g, 166 mmol) BBr₃were added at room temperature.

After 30 min a solution of 39.4 g (278 mmol) 2,2-dimethyl-

1,3-propanediol in 100 ml dichloromethane was added. After

30 min satd. KHCO₃was added until neutralization. The

organic phase was washed with water and brine and dried over

MgSO₄, ﬁltered and the solvent removed under reduced

pressure. The oily residue was dissolved in 100 ml hexanes. Pre-

cipitated excess 2,2-dimethyl-1,3-propanediol was removed by

ﬁltration. From the ﬁltrate the boronic ester 5{2} crystallized at

Ϫ25 ЊC. Yield: 26.1 g (69%); mp 71.8 ЊC (Found: C, 67.23; H,

8.06. C₁₄H₂₀BFO₂requires C, 67.36; H, 8.01%); ν_max(KBr)/cm^Ϫ1

2962 (s), 2934 (s), 2874 (s), 1623 (m), 1560 (w), 1483 (s), 1422

(s), 1382 (m), 1340 (s), 1313 (s), 1254 (m), 1145 (m), 1106 (w),

1054 (w), 1034 (w), 999 (w), 946 (w), 866 (w), 819 (m), 738 (w),

707 (w), 663 (w), 632 (w), 555 (w), 505 (w), 488 (w), 456 (w);

δ_H(400.1 MHz, CDCl₃) 0.93 (t, J = 7.4 Hz, 3 H, CH₂–CH₃), 1.03

3

⁴J_CF= 3.8 Hz, C5), 129.31 (d, J_CF= 5.7 Hz, C4), 129.32 (d,

²J_CF= 14.0 Hz, C3), 150.2 (dd, ¹J_CF= 250.5 Hz, ²J_CF= 15.6 Hz,

1

2

C1), 154.4 (dd, J_CF= 241.4 Hz, J_CF= 10.7 Hz, C2); m/z (EI)

186 [M^ϩ], 171[M^ϩϪ CH₃], 143, 105, 103, 79, 77.

2-(2,3-Diﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]di-

oxaborinane 2{2}. According to GP1 from 169 g (910 mmol)

1,2-diﬂuoro-3-trimethylsilylbenzene 22 was obtained 251 g

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1617

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(87%) boronic ester 2{5}; mp 74.7 ЊC (Found: C, 56.39; H, 7.10.

C₁₄H₂₁BF₂O₂Si requires C, 56.15; H, 6.91%); ν_max(KBr)/cm^Ϫ1

2964 (s), 2908 (m), 2875 (m), 1622 (m), 1481 (s), 1434 (s), 1407

(m), 1377 (m), 1340 (m), 1313 (s), 1251 (s), 1224 (m), 1172 (w),

1129 (m), 1059 (m), 1006 (m), 988 (w), 933 (w), 910 (m), 832 (s),

744 (m), 699 (m), 662 (m), 616 (w), 563 (w), 546 (w), 526 (w),

493 (w); δ_H(400.1 MHz, CDCl₃) 0.32 (s, 9 H, SiMe₃), 1.03 (s, 6

C3); m/z (EI) 324, 322 [M^ϩ], 309, 307 [M^ϩϪ CH₃], 247, 245

[M^ϩϪ CH₃SiF], 228 [M^ϩϪ Br], 213, 199, 165 [M^ϩϪ CH₃Ϫ

CH₃SiF Ϫ HBr], 77.

3-Fluoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{1,2}. According

to GP3 from 12.5

g (38.8 mmol) 4Ј-bromo-3-ﬂuoro-4-

trimethylsilylbiphenyl 3{1,2} was obtained 12.8 g (89%) iodo

biphenyl 4{1,2}; mp 74.0 ЊC (Found: C, 48.66; H, 4.36. C₁₅H₁₆-

FISi requires C, 48.61; H, 4.35%); ν_max(KBr)/cm^Ϫ12956 (w),

1607 (m), 1534 (m), 1496 (s), 1469 (m), 1402 (w), 1378 (m),

11299 (w), 1247 (m), 1179 (m), 1139 (w), 1084 (w), 1060 (w),

1002 (w), 893 (w), 844 (s), 808 (s), 760 (m), 710 (w), 623 (w), 544

(w), 494 (w), 457 (w), 434 (w); δ_H(400.1 MHz, CDCl₃) 0.36 (s,

3

H, CMe₂), 3.79 (s, 4 H, 2 × OCH₂), 7.07 (ddd, J_HH= 7.4 Hz,

5

3

⁴J_HF= 4.1 Hz, J_HF= 0.9 Hz, 1 H, H5), 7.40 (ddd, J_HH

=

7.3 Hz,⁴J_HF= 4.7 Hz, J_HF= 0.8 Hz 1 H, H6); δ_C(100.6 MHz,

CDCl₃) Ϫ1.2 (SiMe₃), 21.7 (CMe₂), 31.7 (CMe₂), 72.4 (2 ×

OCH₂), 128.4 (dd, ³J_CF= 9.5 Hz, ⁴J_CF= 4.3 Hz, C5), 130.1 (dd,

³J_CF= 6.0 Hz, ⁴J_CF= 3.6 Hz, C6), 131.5 (d, ²J_CF= 27.2 Hz, C4),

154.0 (dd, J_CF= 254.2 Hz, J_CF= 15.3 Hz, C3), 154.4 (dd,

¹J_CF= 241.3 Hz, ²J_CF= 13.4 Hz, C2); m/z (CI) 299 [MH^ϩ], 283

[M^ϩϪ CH₃], 279 [M^ϩϪ F], 241, 213, 197, 183, 69.

5

1

2

3

4

9 H, SiMe₃), 7.18 (dd, J_FH= 9.7 Hz, J_HH= 1.5 Hz, 1 H, H2),

7.30–7.33 (m, 3 H), 7.46 (dd, ³J_HH= 7.6 Hz, ⁴J_FH= 5.9 Hz, 1 H,

H5), 7.78 (d, line distance 8.6 Hz, AAЈ-part of a AAЈXXЈ-

system, 2 H, H3Ј,5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃), 93.7

2

4

(C4Ј), 113.0 (d, J_CF= 26.9 Hz, C2), 122.1 (d, J_CF= 2.7 Hz,

Parallel synthesis of biphenyls 3{H,B} and 4{H,B}

C6), 125.4 (d, ²J_CF= 30.4 Hz, C4), 128.8 (C2Ј,6Ј), 135.7 (d, ³J_CF

The reactions were carried out using standard glassware. Up to

four reaction vessels were heated/cooled simultaneously in a

large oil bath/dewar.

4

= 12.1 Hz, C5), 138.0 (C3Ј,5Ј), 139.4 (d, J_CF= 2.7 Hz, C1Ј),

143.4 (d, ³J_CF= 8.4 Hz, C1), 167.8 (d, ¹J_CF= 241.4 Hz, C3); m/z

(EI) 370 [M^ϩ], 355 [M^ϩϪ CH₃], 293 [M^ϩϪ (CH₃)₂SiF], 228

[M^ϩϪ CH₃Ϫ I], 228 [M^ϩϪ 2CH₃Ϫ I], 165 [M^ϩϪ (CH₃)₂SiF

Ϫ HI].

4Ј-Bromo-4-trimethylsilylbiphenyl 3{1,1}. According to GP2

from p-bromoiodbenzene 1{1} and 2-(4-trimethylsilylphenyl)-

5,5-dimethyl[1,3,2]dioxaborinane 2{1} was obtained bromo bi-

phenyl 3{1,1} 13.1 g (86%); mp 97–99 ЊC; lit.¹⁴mp 91–93 ЊC

(Found: C, 59.01; H, 5.61. C₁₅H₁₇BrSi requires C, 59.09; H,

5.57%); ν_max(KBr)/cm^Ϫ13063 (w), 3019 (w), 2955 (m), 2894(w),

1475 (w), 1379 (w), 1246 (m), 1112 (m), 1071 (m), 999 (m), 834

(s), 804 (s), 755 (s), 623 (m), 544 (m), 497 (s); δ_H(400.1 MHz,

CDCl₃) 0.34 (s, 9 H, SiMe₃), 7.46–7.50 (m, 2 H, H2Ј,6Ј), 7.55–

7.63 (m, 6 H, H2,3,3Ј,5,5Ј,6); δ_C(100.6 MHz, CDCl₃) Ϫ1.1

(SiMe₃), 121.6 (C4Ј), 126.2 (C2,6), 128.7, (C2Ј,6Ј), 131.9

(C3Ј,5Ј), 133.9 (C3,5), 139.8 and 140.0 and 140.3 (C1,1Ј,4); m/z

(EI) 306, 304 [M^ϩ], 291, 289 [M^ϩϪ CH₃].

4Ј-Bromo-2,3-diﬂuoro-4-trimethylsilylbiphenyl 3{1,5}.

According to GP2 from p-bromoiodbenzene 1{1} and 2-

(2,3-diﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxa-

borinane 2{5} was obtained bromo biphenyl 3{1,5} 15.0 g

(88%); mp 64.0 ЊC (Found: C, 52.79; H, 4.43. C₁₅H₁₅BrF₂Si

requires C, 52.91; H, 4.45%); ν_max(KBr)/cm^Ϫ13032 (w), 2958

(w), 2898 (w), 1614 (w), 1587 (w), 1539 (w), 1499 (w), 1470 (w),

1436 (s), 1388 (m), 1311 (w), 1279 (w), 1252 (m), 1223 (m), 1153

(m), 1098 (w), 1071 (w), 1008 (w), 914 (m), 891 (w), 838 (s), 806

(m), 763 (m), 740 (w), 715 (w), 696 (w), 652 (w), 630 (w), 607

(w), 555 (w), 555 (w), 527 (w), 485 (w), 432 (w); δ_H(400.1 MHz,

CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.12–7.19 (m, 2 H, H5,6), 7.40–

7.44 (m, 2 H, H2Ј,6Ј), 7.57–7.60 (m, 2 H, H3Ј,5Ј); δ_C(100.6

4Ј-Iodo-4-trimethylsilylbiphenyl 4{1,1}. According to GP3

from 10.2 g (33.4 mmol) 4Ј-bromo-4-trimethylsilylbiphenyl

3{1,1} was obtained 10.4 g (88%) iodo biphenyl 4{1,1}; subl.

120 ЊC/10^Ϫ3mbar; mp 111–112 ЊC (Found: C, 51.14; H,

4.86. C₁₅H₁₇ISi requires C, 51.26; H, 5.02%); ν_max(KBr)/cm^Ϫ1

3065(w), 3017 (w), 2953 (w), 2894 (w), 1596 (w), 1474 (m), 1377

(w), 1245 (m), 1112 (m), 997 (m), 843 (s), 803 (s), 756 (s), 621

(w), 494(m); δ_H(400.1 MHz, CDCl₃) 0.31 (s, 9 H, SiMe₃), 7.34

(d, line distance 8.3 Hz, AAЈ-part of a AAЈXXЈ-system, 2 H,

H2,6), 7.49–7.61 (m, 4 H, H2Ј,3Ј,5Ј,6Ј), 7.77 (d, line distance 8.4

Hz, XXЈ-part of a AAЈXXЈ-system, 2 H, H3,5); δ_C(100.6 MHz,

CDCl₃) Ϫ1.1 (SiMe₃), 93.1 (C4Ј), 126.2 (C2,6), 129.0, (C2Ј,6Ј),

133.9 (C3,5), 137.9 (C3Ј,5Ј), 139.9 and 140.4 and 140.7

(C1,1Ј,4); m/z (EI) 352 [M^ϩ], 337 [M^ϩϪ CH₃].

3

MHz, CDCl₃) Ϫ1.1 (SiMe₃), 122.5 (C4Ј), 124.8 (d, J_CF= 3.0

Hz, C6), 128.4 (d, ²J_CF= 26.2 Hz, C4), 129.0 (dd, ²J_CF= 11.4 Hz,

4

³J_CF= 5.3 Hz, C5), 130.5 (d, J_CF= 3.0 Hz, C2Ј,6Ј), 130.7 (d,

²J_CF= 10.2 Hz, C1), 131.8 (C3Ј,5Ј), 133.7 (d, ³J_CF= 2.2 Hz, C1Ј),

1

2

147.4 (dd, J_CF= 252.2 Hz, J_CF= 17.3 Hz, C2), 155.0 (dd,

¹J_CF= 241.8 Hz, J_CF= 11.8 Hz, C3); m/z (EI) 342, 340 [M^ϩ],

2

246, 165.

2,3-Diﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{1,5}. Accord-

ing to GP3 from 15.0 g (44.0 mmol) 4Ј-bromo-2,3-diﬂuoro-4-

trimethylsilylbiphenyl 3{1,5} was obtained 16.2 g (95%) iodo

biphenyl 4{1,5}; mp 89.1 ЊC (Found: C, 46.60; H, 3.89.

C₁₅H₁₅F₂ISi requires C, 46.67; H, 3.91%); ν_max(KBr)/cm^Ϫ13029

(w), 2957 (w), 2896 (w), 1619 (w), 1584 (w), 1497 (w), 1468 (w),

1436 (s), 1385 (m), 1308 (w), 1278 (w), 1252 (m), 1221 (m), 1150

(w), 1195 (w), 1058 (w), 1004 (w), 913 (s), 842 (s), 810 (s), 764

(m), 740 (w), 708 (w), 654 (w), 634 (w), 608 (w), 527 (w);

δ_H(400.1 MHz, CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.12–7.19 (m, 2 H,

H5,6), 7.29 (d, line distance 7.1 Hz, AAЈ-part of a AAЈXXЈ-

spectrum, 2 H, H2Ј,6Ј), 7.79 (d, line distance 9.0 Hz, XXЈ-part

of a AAЈXXЈ-spectrum, 2 H, H3Ј,5Ј); δ_C(100.6 MHz, CDCl₃)

Ϫ1.1 (SiMe₃), 94.2 (C4Ј), 124.7 (dd, ³J_CF= 2.8 Hz, ⁴J_CF= 1.3 Hz,

4Ј-Bromo-3-ﬂuoro-4-trimethylsilylbiphenyl 3{1,2}. According

to GP2 from p-bromoiodbenzene 1{1} and 2-(3-ﬂuoro-4-tri-

methylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane 2{2} was

obtained bromo biphenyl 3{1,2} 12.9 g (80%); bp 100 ЊC / 10^Ϫ3

mbar; mp 56.8 ЊC (Found: C, 55.73; H, 4.99. C₁₅H₁₆BrFSi

requires C, 55.87; H, 5.08%); ν_max(KBr)/cm^Ϫ13062 (w),

2960 (w), 2900 (w), 1609 (m), 1569 (m), 1538 (m), 1498 (m),

1471 (m), 1405 (m), 1383 (m), 1299 (w), 1254 (m), 1179 (m),

1140 (w), 1106 (w), 1086 (m), 1072 (m), 1028 (w), 1009 (m),

950 (w), 893 (s), 877 (m), 844 (s), 813 (s), 764 (s), 712 (m), 696

(w), 630 (m), 550 (w), 500 (m), 461 (w), 447 (w); δ_H(400.1 MHz,

CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.19 (dd, ³J_FH= 9.7 Hz, ⁴J_HH= 1.3

Hz, 1 H, H2), 7.33 (dd, ³J_HH= 7.6 Hz, ⁴J_HH= 1.3 Hz, 1 H, H6),

7.43–7.49 (m, 3 H), 7.56–7.60 (m, 2 H); δ_C(100.6 MHz, CDCl₃)

2

3

C6), 128.4 (dd, J_CF= 27.3 Hz, J_CF= 1.5 Hz, C4), 129.0 (dd,

³J_CF= 11.4 Hz, J_CF= 5.3 Hz, C5), 130.6 (d, J_CF= 3.0 Hz,

4

2

3

C2Ј,6Ј), 130.8 (d, J_CF= 10.6 Hz, C1), 134.3 (d, J_CF= 3.0 Hz,

C1Ј), 137.7 (C3Ј,5Ј), 147.4 (dd, ¹J_CF= 252.8 Hz, ²J_CF= 17.1 Hz,

1

2

C2), 155.0 (dd, J_CF= 241.8 Hz, J_CF= 11.8 Hz, C3); m/z (EI)

388 [M^ϩ], 373 [M^ϩϪ CH₃], 246 [M^ϩϪ CH₃Ϫ I], 165, 77.

2

Ϫ1.1 (SiMe₃), 113.0 (d, J_CF= 26.9 Hz, C2), 122.2 (C6), 122.2

2

(C4Ј), 125.3 (d, J_CF= 30.7 Hz, C4), 128.6 (C2Ј,6Ј), 132.0

4Ј-Bromo-2Ј-ﬂuoro-4-trimethylsilylbiphenyl 3{2,1}. According

to GP2 from 1-bromo-3-ﬂuoro-4-iodobenzene 1{2} and 2-(4-

(C3Ј,5Ј), 135.6 (d, ³J_CF= 12.1 Hz, C5), 138.8 (d, ⁴J_CF= 2.7 Hz,

3

1

C1Ј), 143.3 (d, J_CF= 8.4 Hz, C1), 167.8 (d, J_CF= 241.4 Hz,

trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane

2{1}

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1618

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was obtained bromo biphenyl 3{2,1} 11.6 g (72); bp 110 ЊC/10^Ϫ3

mbar; mp 43.7 ЊC (Found: C, 55.73; H, 4.99. C₁₅H₁₆BrFSi

requires C, 55.85; H, 4.99%); ν_max(KBr)/cm^Ϫ12958 (w), 1600

(w), 1564 (w), 1504 (w), 1474 (m), 1436 (w), 1405 (w), 1379 (m),

1314 (w), 1245 (m), 1207 (m), 1127 (w), 1108 (w), 1070 (w), 1002

(w), 870 (m), 834 (s), 805 (s), 755 (s), 725 (m), 694 (m), 624 (w),

570 (m), 539 (w), 508 (w), 464 (w), 433 (w); δ_H(400.1 MHz,

CDCl₃) 0.30 (s, 9 H,), 7.31–7.35 (m, 3 H), 7.48–7.50 (m, 2 H),

7.59–7.61 (m, 2 H); δ_C(100.6 MHz, CDCl₃) Ϫ1.2 (SiMe₃), 119.7

(d, ²J_CF= 26.2 Hz, C3Ј), 121.3 (d, ³J_CF= 9.5 Hz, C4Ј), 127.7 (d,

⁴J_CF= 3.8 Hz, C5Ј), 128.0 (C2,6), 131.7 (d, ³J_CF= 4.2 Hz, C6Ј),

133.6 (C3,5), 133.7 (d, ²J_CF= 19.7 Hz, C1Ј), 135.1 (d, ³J_CF= 1.1

(d, ³J_CF= 8.4 Hz, C4Ј), 115.0 (dd, ²J_CF= 27.5 Hz, ⁴J_CF= 3.2 Hz,

C2), 124.1 (t, ⁴J_CF= ⁴J_CFЈ= 3.0 Hz, C6), 125.6 (d, ²J_CF= 25.4 Hz,

2

C3Ј), 126.0 (d, J_CF= 30.4 Hz, C4), 127.6 (dd, J_CF= 13.1 Hz,

⁴J_CF= 2.5 Hz, C1Ј), 131.7 (d, ⁴J_CF= 3.8 Hz, C5Ј), 133.8 (d, ³J_CF

=

3

4.2 Hz, C6Ј), 135.3 (d, J_CF= 12.1 Hz, C5), 137.9 (dd, J_CF

8.7 Hz, ³J_CF= 1.1 Hz, C1), 159.2 (d, ¹J_CF= 254.3, C2Ј), 167.4 (d,

¹J_CF= 241.0 Hz, C3); m/z (EI) 388 [M^ϩ], 373 [M^ϩϪ CH₃], 246

[M^ϩϪ CH₃Ϫ I], 246 [M^ϩϪ Br], 183 [M^ϩϪ CH₃Ϫ CH₃SiF Ϫ

HBr], 165.

4Ј-Bromo-2,3,2Ј-triﬂuoro-4-trimethylsilylbiphenyl 3{2,5}.

According to GP2 from 1-bromo-3-ﬂuoro-4-iodobenzene 1{2}

and 2-(2,3-diﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]-

dioxaborinane 2{5} was obtained bromo biphenyl 3{2,5} 15.8 g

(88%); mp 78.0 ЊC (Found: C, 50.15; H, 3.93. C₁₅H₁₄BrF₃Si

requires C, 50.20; H, 3.92%); ν_max(KBr)/cm^Ϫ13032 (w), 2958

(w), 2897 (w), 1498 (w), 1470 (w), 1436 (s), 1387 (m), 1311 (w),

1279 (w), 1252 (m), 1222 (m), 1153 (m), 1097 (w), 1070 (m),

1008 (m), 962 (w), 914 (m), 891 (w), 837 (s), 806 (s), 763 (m), 740

(w), 715 (w), 696 (w), 652 (w), 630 (w), 606 (w), 555 (w), 527 (w),

485 (w), 432 (w); δ_H(400.1 MHz, CDCl₃) 0.36 (s, 9 H, SiMe₃),

7.09 (ddt, ³J_HH= 7.6 Hz, ⁴J_FH= 5.6 Hz, ⁵J_FH= ⁵J_FЈH= 0.9 Hz, 1

H, H6), 7.17 (ddd, ³J_HH= 7.6 Hz, ⁴J_FH= 4.5 Hz, ⁵J_FH= 1.4 Hz, 1

H, H5), 7.26 (td, ³J_HH= ⁴J_FH= 8.0 Hz, ⁵J_HH= 0.6 Hz, 1 H, H6Ј),

7.35–7.39 (m, 2 H, H3Ј,5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1

1

Hz, C1), 140.4 (C4), 159.6 (d, J_CF= 252.8 Hz, C2Ј); m/z (EI)

324, 322 [M^ϩ], 309, 307 [M^ϩϪ CH₃].

2Ј-Fluoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{2,1}. According

to GP3 from 11.0 g (34.2 mmol) 4Ј-bromo-2Ј-ﬂuoro-4-tri-

methylsilylbiphenyl 3{2,1} resulted 10.0 g (80%) iodo biphenyl

4{2,1}; mp 39.8 ЊC (Found: C, 48.66; H, 4.36. C₁₅H₁₆FISi

requires C, 48.45; H, 4.38%); ν_max(KBr)/cm^Ϫ12955 (w), 1598

(m), 1561 (m), 1504 (w), 1472 (s), 1400 (m), 1379 (s), 1248 (s),

1206 (m), 1128 (w), 1108 (m), 1063 (w), 1002 (w), 949 (w), 859

(s), 833 (s), 805 (s), 754 (m), 725 (m), 663 (w), 622 (w), 572 (m),

533 (w), 505 (w), 461 (w), 423 (w); δ_H(400.1 MHz, CDCl₃) 0.33

(s, 9 H,), 7.18 (t, ³J_HH= ⁴J_FH= 8.1 Hz, 1 H, H6Ј), 7.51–7.58 (m,

4 H), 7.62–7.64 (m, 2 H); δ_C(100.6 MHz, CDCl₃) Ϫ1.2 (SiMe₃),

92.0 (d, ³J_CF= 8.0 Hz, C4Ј), 125.4 (d, ²J_CF= 25.4 Hz, C3Ј), 128.0

(d, ⁴J_CF= 3.0 Hz, C2,6), 128.8 (d, ²J_CF= 13.3 Hz, C1Ј), 131.9 (d,

³J_CF= 3.8 Hz, C6Ј), 133.6 (C3,5), 133.7 (d, ⁴J_CF= 3.8 Hz, C5Ј),

2

(SiMe₃), 119.7 (d, J_CF= 25.4 Hz, C3Ј), 121.7 (dd, J_CF= 15.6

Hz, ³J_CF= 3.0 Hz, C1Ј), 122.8 (d, ³J_CF= 9.5 Hz, C4Ј), 125.4 (d,

²J_CF= 12.1 Hz, C1), 125.7 (br. s, C6), 127.6 (d, J_CF= 3.8 Hz,

4

3

4

C5Ј), 128.8 (dd, J_CF= 11.2 Hz, J_CF= 5.1 Hz, C5), 129.3 (d,

3

1

3

4

135.2 (d, J_CF= 1.1 Hz, C1), 140.5 (C4), 159.3 (d, J_CF= 253.6

Hz, C2Ј); m/z (EI) 370 [M^ϩ], 355 [M^ϩϪ CH₃], 228 [M^ϩϪ CH₃

Ϫ I].

²J_CF= 26.9 Hz, C4), 132.4 (dd, J_CF= 3.4 Hz, J_CF= 1.9 Hz,

C6Ј), 147.5 (dd, ¹J_CF= 253.2 Hz, ²J_CF= 16.3 Hz, C2), 154.7 (dd,

¹J_CF= 242.2 Hz, ²J_CF= 11.46 Hz, C3), 159.5 (d, ¹J_CF= 253.6 Hz,

C2Ј); m/z (EI) 360, 358 [M^ϩ], 345, 343 [M^ϩϪ CH₃], 264

[M^ϩϪ CH₃Ϫ Br], 183, 164, 77.

4Ј-Bromo-2Ј,3-diﬂuoro-4-trimethylsilylbiphenyl 3{2,2}.

According to GP2 from 1-bromo-3-ﬂuoro-4-iodobenzene 1{2}

and

2-(3-ﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]-

2,3,2Ј-Triﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{2,5}.

dioxaborinane 2{2} was obtained bromo biphenyl 3{2,2} 12.5 g

(73%); bp 100 ЊC/10^Ϫ3mbar; mp 25.0 ЊC (Found: C, 52.79; H,

4.43. C₁₅H₁₅BrF₂Si requires C, 53.01; H, 4.51%); ν_max(KBr)/

cm^Ϫ13069 (w), 2958 (m), 2900 (w), 1612 (s), 1570 (m), 1538 (m),

1500 (m), 1472 (s), 1411 (m), 1384 (s), 1306 (m), 1251 (s), 1213

(m), 1178 (m), 1142 (w), 1125 (w), 1072 (m), 1130 (w), 902 (s),

845 (s), 812 (s), 763 (m), 713 (w), 696 (w), 632 (m), 583 (w), 547

(w), 451 (w); δ_H(400.1 MHz, CDCl₃) 0.39 (s, 9 H, SiMe₃), 7.19

(dt, ³J_FH= 9.6 Hz, ⁴J_HH= ⁵J_FH= 1.4 Hz, 1 H, H2), 7.30–7.40 (m,

4 H), 7.50 (dd, ³J_HH= 7.6 Hz, ⁴J_FH= 5.9 Hz, 1 H, H5); δ_C(100.6

According to GP3 from 15.8 g (44.0 mmol) 4Ј-bromo-2,3,2Ј-

triﬂuoro-4-trimethylsilylbiphenyl 3{2,5} was obtained 15.1 g

(84%) iodo biphenyl 4{2,5}; mp 76.0 ЊC (Found: C, 44.35; H,

3.47. C₁₅H₁₄F₂ISi requires C, 44.34; H, 6.52%); ν_max(KBr)/cm^Ϫ1

3096 (w), 2957 (w), 2898 (w), 1623 (w), 1599 (w), 1567 (w), 1544

(w), 1500 (w), 1466 (m), 1433 (s), 1394 (m), 1313 (w), 1251 (m),

1220 (m), 1149 (w), 1086 (w), 1064 (w), 1027 (w), 916 (m), 895

(w), 841 (s), 812 (m), 761 (m), 740 (w), 699 (w), 646 (w), 610 (w),

568 (w), 532 (w), 485 (w), 452 (w); δ_H(400.1 MHz, CDCl₃) 0.37

3

(s, 9 H, SiMe₃), 7.08–7.13 (m, 2 H, H6,6Ј), 7.17 (ddd, J_HH

=

2

4

5

MHz, CDCl₃) Ϫ1.1 (SiMe₃), 115.0 (dd, J_CF= 27.3 Hz,

7.7 Hz, J_FH= 4.5 Hz, J_FH= 1.4 Hz, 1 H, H5), 7.55–7.59 (m,

2

⁴J_CF= 3.4 Hz, C2), 119.9 (d, J_CF= 26.2 Hz, C3Ј), 121.9 (d,

2 H, H3Ј,5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃), 93.6 (d,

³J_CF= 9.5 Hz, C4Ј), 124.1 (t, ⁴J_CF= ⁴J_CFЈ= 2.8 Hz, C6), 126.0 (d,

³J_CF= 8.0 Hz, C4Ј), 122.3 (dd, J_CF= 15.6 Hz, J_CF= 3.0 Hz,

2

3

4

2

²J_CF= 30.7 Hz, C4), 127.8 (d, J_CF= 3.8 Hz, C5Ј), 131.4 (d,

C1Ј), 125.4 (d, J_CF= 25.0 Hz, C3Ј), 125.5 (d, J_CF= 12.1 Hz,

C1), 125.7 (br. s, C6), 128.8 (dd, ³J_CF= 11.2 Hz, ⁴J_CF= 5.1 Hz,

2

³J_CF= 4.2 Hz, C6Ј), 133.7 (d, J_CF= 19.7 Hz, C1Ј), 135.3 (d,

3

2

3

³J_CF= 12.1 Hz, C5), 137.8 (dd, J_CF= 8.7 Hz, J_CF= 1.1 Hz,

C1), 159.4 (d, ¹J_CF= 253.2, C2Ј), 167.4 (d, ¹J_CF= 241.0 Hz, C3);

m/z (EI) 342, 340 [M^ϩ], 327, 325 [M^ϩϪ CH₃], 246 [M^ϩϪ Br],

165.

C5), 129.3 (d, J_CF= 27.3 Hz, C4), 132.6 (dd, J_CF= 3.2 Hz,

⁴J_CF= 2.1 Hz, C6Ј), 133.6 (d, J_CF= 3.8 Hz, C5Ј), 147.5 (dd,

4

¹J_CF= 253.7 Hz, ²J_CF= 17.3 Hz, C2), 154.7 (dd, ¹J_CF= 242.0 Hz,

²J_CF= 11.6 Hz, C3), 159.2 (d, J_CF= 255.1 Hz, C2Ј); m/z

1

(CI) 407 [MH^ϩ], 406 [M^ϩ], 391 [M^ϩϪ CH₃], 387, 308, 280

[MH^ϩϪ I].

2Ј,3-Diﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{2,2}. Accord-

ing to GP3 from 11.9 g (35.0 mmol) 4Ј-bromo-2Ј,3-diﬂuoro-4-

trimethylsilyl-biphenyl 3{2,2} was obtained 11.7 g (86%) iodo

biphenyl 4{2,2}; mp 53.2 ЊC (Found: C, 46.40; H, 3.89. C₁₅H₁₅-

F₂ISi requires C, 46.61; H, 4.01%); ν_max(KBr)/cm^Ϫ13059 (w),

2957 (w), 2897 (w), 1611 (m), 1562 (m), 1535 (w), 1496 (w), 1468

(m), 1407 (m), 1380 (s), 1303 (w), 1250 (m), 1208 (m), 1178 (m),

1132 (w), 1082 (w), 1065 (w), 1028 (w), 898 (s), 842 (s), 809 (s),

762 (m), 711 (w), 662 (w), 630 (w), 578 (w), 542 (w), 517 (w), 447

(w); δ_H(400.1 MHz, CDCl₃) 0.36 (s, 9 H, SiMe₃), 7.14–7.18 (m,

2 H), 7.29 (dt, ³J_HH= 7.6 Hz, ⁴J_HH= ⁵J_FH= 1.6 Hz, 1 H, H6), 7.47

4Ј-Bromo-3,3Ј-diﬂuoro-4-trimethylsilylbiphenyl 3{3,2}.

According to GP2 from 4-bromo-3-ﬂuoro-1-iodobenzene 1{3}

and

2-(3-ﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]-

dioxaborinane 2{2} was obtained bromo biphenyl 3{3,2} 13.5 g

(79%) bp 140 ЊC / 10^Ϫ3mbar; mp 46.9 ЊC (Found: C, 52.79; H,

4.43. C₁₅H₁₅BrF₂Si requires C, 52.88; H, 4.50%); ν_max(KBr)/

cm^Ϫ13038 (w), 2960 (w), 2900 (w), 1608 (m), 1574 (w), 1538

(m), 1498 (w), 1469 (m), 1415 (w), 1385 (m), 1313 (w), 1248 (m),

1211 (m), 1138 (w), 1086 (w), 1049 (m), 1027 (w), 948 (m), 842

(s), 809 (s), 760 (s), 713 (m), 696 (m), 628 (m), 594 (w), 551 (w),

498 (w); δ_H(400.1 MHz, CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.18 (dd,

³J_FH= 9.7 Hz, ⁴J_HH= 1.6 Hz, 1 H, H2Ј), 7.24 (ddd, ³J_FH= 8.2 Hz,

3

4

3

(dd, J_HH= 7.6 Hz, J_FH= 5.8 Hz, 1 H, H5), 7.54 (dd, J_FH

=

10.0 Hz, ⁴J_HH= 1.6 Hz, 1 H, H2), 7.57 (dd, ³J_FH= 8.1 Hz, ⁴J_HH

2.0 Hz, 1 H, H3Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃), 92.7

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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⁴J_HH= 2.0 Hz, ⁵J_HH= 0.5 Hz, 1 H, H2), 7.31–7.35 (m, 2 H), 7.48

(dd, ³J_HH= 7.6 Hz, ⁴J_FH= 5.9 Hz, 1 H, H5), 7.61 (dd, ³J_HH= 8.3

(s), 1143 (m), 1096 (w), 1024 (m), 969 (w), 901 (w), 877 (m), 841

(m), 805 (m), 763 (w), 737 (w), 698 (w), 651 (w), 617 (w), 601

(w), 567 (w), 495 (w), 456 (w), 416 (w); δ_H(400.1 MHz, CDCl₃)

4

Hz, J_FH= 7.1 Hz, 1 H, H5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1

(SiMe₃), 108.5 (d, ²J_CF= 20.9 Hz, C4Ј), 113.0 (d, ²J_CF= 27.3 Hz,

C2), 114.9 (d, ²J_CF= 23.2 Hz, C2Ј), 122.2 (d, ⁴J_CF= 2.7 Hz, C6),

123.7 (d, ⁴J_CF= 3.4 Hz, C6Ј), 126.1 (d, ²J_CF= 30.7 Hz, C4), 133.9

0.37 (s, 9 H, SiMe₃), 7.10 (dt, J_FH= 8.2 Hz, J_HH= J_FH= 1.6

3

4

5

3

Hz, 1 H, H2Ј), 7.13–7.20 (m, 2 H), 7.27 (dt, J_HH= 8.5 Hz,

5

3

⁴J_HH= J_FH= 1.5 Hz, 1 H, H6Ј), 7.82 (dd, J_HH= 8.5 Hz,

3

(C5Ј), 135.8 (d, J_CF= 12.1 Hz, C5), 141.3 (dd, J_CF= 7.2 Hz,

⁴J_CF= 2.3 Hz, C1), 142.2 (dd, ³J_CF= 8.4 Hz, ⁴J_CF= 1.9 Hz, C1Ј),

159.4 (d, ¹J_CF= 247.5, C3Ј), 167.8 (d, ¹J_CF= 241.4 Hz, C3); m/z

(EI) 342, 340 [M^ϩ], 327, 325 [M^ϩϪ CH₃], 265, 263 [M^ϩϪ CH₃

Ϫ CH₃SiF], 246 [M^ϩϪ Br], 183 [M^ϩϪ CH₃Ϫ CH₃SiF Ϫ HBr],

165, 77.

⁴J_FH= 6.6 Hz, 1 H, H5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃),

2

81.0 (d, J_CF= 25.8 Hz, C4Ј), 116.1 (dd, J_CF= 25.1 Hz,

⁴J_CF= 3.4 Hz, C2Ј), 124.6 (dd, ³J_CF= 3.0 Hz, ⁴J_CF= 0.8 Hz, C6),

4

2

126.2 (t, J_CF= J_CFЈ= 3.2 Hz, C6Ј), 129.1 (dd, J_CF= 27.3 Hz,

³J_CF= 1.1 Hz, C4), 129.1 (dd, J_CF= 11.0 Hz, J_CF= 5.3 Hz,

3

4

C5), 129.7 (br. d, ²J_CF= 10.6 Hz, C1), 137.1 (dd, ³J_CF= 7.4 Hz,

³J_CF= 2.5 Hz, C1Ј), 139.5 (d, J_CF= 1.9 Hz, C5Ј), 147.4 (dd,

3

3,3Ј-Diﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{3,2}. Accord-

ing to GP3 from 10.3 g (30.3 mmol) 4Ј-bromo-3,3Ј-diﬂuoro-4-

trimethylsilylbiphenyl 3{3,2} was obtained 10.9 g (93%) iodo

biphenyl 4{3,2}; mp 50.1 ЊC (Found: C, 46.40; H, 3.89. C₁₅H₁₅-

F₂ISi requires C, 46.64; H, 3.98%); ν_max(KBr)/cm^Ϫ13064 (w),

2956 (w), 2899 (w), 1608 (m), 1568 (w), 1536 (m), 1496 (w), 1463

(m), 1412 (w), 1385 (m), 1312 (w), 1249 (m), 1207 (m), 1168 (w),

1135 (w), 1083 (w), 1042 (w), 1019 (w), 948 (m), 844 (s), 807 (s),

761 (s), 711 (m), 662 (w), 626 (w), 591 (w), 550 (w); δ_H(400.1

¹J_CF= 253.4 Hz, ²J_CF= 17.3 Hz, C2), 155.0 (dd, ¹J_CF= 242.2 Hz,

²J_CF= 11.8 Hz, C3), 161.8 (d, ¹J_CF= 245.6 Hz, C3Ј); m/z (EI) 406

[M^ϩ], 391 [M^ϩϪ CH₃], 264 [M^ϩϪ CH₃Ϫ I], 198, 183, 164, 77.

3Ј,5Ј-Diﬂuoro-4-trimethylsilylbiphenyl 3{4,1}. According to

GP2 from 1-bromo-3,5-diﬂuorobenzene 1{4} and 2-(4-tri-

methylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane 2{1} was

obtained biphenyl 3{4,1} 11.4 g (87%); bp 165 ЊC / 14 mbar

(Found: C, 68.67; H, 6.15. C₁₅H₁₆F₂Si requires C, 68.93; H,

6.19%); ν_max(KBr)/cm^Ϫ13069 (w), 3022 (w), 2957 (m), 2898 (w),

1622 (s), 1597 (s), 1548 (w), 1460 (w), 1441 (w), 1386 (w), 1340

(m), 1205 (w), 1116 (s), 989 (m), 841 (s), 817 (s), 758 (m), 722

(w), 703 (w), 985 (w), 624 (w), 605 (w), 567 (w), 534 (w), 510 (w),

488 (w), 434 (w); δ_H(400.1 MHz, CDCl₃) 0.36 (s, 9 H, SiMe₃),

3

MHz, CDCl₃) 0.36 (s, 9 H, SiMe₃), 7.13 (dd, J_HH= 8.2 Hz,

⁴J_HH= 2.1 Hz, 1 H, H6Ј), 7.18 (dd, ³J_FH= 9.7 Hz, ⁴J_HH= 1.4 Hz,

1 H, H2), 7.27 (dd, ³J_FH= 9.3 Hz, ⁴J_HH= 2.1 Hz, 1 H, H2Ј), 7.32

(dd, ³J_HH= 7.6 Hz, ⁴J_HH= 1.4 Hz, 1 H, H6), 7.47 (dd, ³J_HH= 7.6

Hz, ⁴J_FH= 5.9 Hz, 1 H, H5), 7.80 (dd, ³J_HH= 8.2 Hz, ⁴J_FH= 6.6

Hz, 1 H, H5Ј); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃), 80.4 (d,

3

4

6.81 (tt, J_FH= 8.8 Hz, J_HH= 2.1 Hz, 1 H, H4Ј), 7.14 (d, line

distance 6.6 Hz, AAЈ-part of a AAЈXXЈ-system, 2 H, H2Ј,6Ј),

7.57 (d, line distance 8.1 Hz, AAЈ-part of a AAЈXXЈ-system,

2 H, H2,6) 7.65 (d, line distance 8.1 Hz, XXЈ-part of a

AAЈXXЈ-system, 2 H, H3,5); δ_C(100.6 MHz, CDCl₃) Ϫ1.2

2

²J_CF= 25.8 Hz, C4Ј), 113.0 (d, J_CF= 27.3 Hz, C2), 114.1

(d, ²J_CF= 24.7 Hz, C2Ј), 122.1 (d, ⁴J_CF= 2.7 Hz, C6), 124.2 (d,

2

⁴J_CF= 3.0 Hz, C6Ј), 126.1 (d, J_CF= 31.1 Hz, C4), 135.8

3

(d, J_CF= 12.1 Hz, C5), 139.7 (d, J_CF= 1.9 Hz, C5Ј), 142.2

(dd, ³J_CF= 8.4 Hz, ⁴J_CF= 1.9 Hz, C1), 142.4 (dd, ³J_CF= 7.2 Hz,

2

(SiMe₃), 102.5 (t, J_CF= 25.4 Hz, C4Ј), 109.9 (d, line distance

⁴J_CF= 2.3 Hz, C1Ј), 162.1 (d, J_CF= 245.6 Hz, C3), 167.8 (d,

25.4 Hz, AAЈ-part of a AAЈXXЈ-system, C2Ј,6Ј), 126.3 (C2,6),

1

¹J_CF= 241.4, C3Ј); m/z (EI) 388 [M^ϩ], 373 [M^ϩϪ CH₃], 246

[M^ϩϪ CH₃Ϫ I], 246 [M^ϩϪ Br], 183 [M^ϩϪ CH₃Ϫ CH₃SiF Ϫ

HBr], 165, 77.

134.0 (C3,5), 139.2 (t, J_CF= 2.5 Hz, C1), 141.0 (C4), 144.5 (t,

4

³J_CF= 9.5 Hz, C1Ј), 163.3 (dd, ¹J_CF= 248.1 Hz, ³J_CF= 13.0 Hz,

C3Ј,5Ј); m/z (EI) 262 [M^ϩ], 249 [M^ϩϪ CH₃], 168.

4Ј-Bromo-2,3,3Ј-triﬂuoro-4-trimethylsilylbiphenyl 3{3,5}.

According to GP2 from 4-bromo-3-ﬂuoro-1-iodobenzene 1{3}

and 2-(2,3-diﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]-

dioxaborinane 2{5} was obtained bromo biphenyl 3{3,5} 12.2 g

(68%); bp 125 ЊC/10^Ϫ3mbar; mp 67.7 ЊC (Found: C, 50.15; H,

3.93. C₁₅H₁₄BrF₃Si requires C, 50.09; H, 3.96%); ν_max(KBr)/

cm^Ϫ12959 (m), 2900 (w), 1620 (w), 1574 (w), 1544 (w), 1498 (w),

1470 (w), 1435 (m), 1388 (m), 1320 (w), 1287 (w), 1248 (w), 1223

(w), 1201 (w), 1146 (w), 1094 (w), 1036 (m), 968 (w), 898 (w),

841 (s), 809 (s), 760 (m), 734 (w), 694 (w), 650 (w), 566 (w), 548

(w); δ_H(400.1 MHz, CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.13–7.24 (m,

3 H), 7.33 (ddd, ³J_FH= 9.7 Hz, ⁴J_HH= 1.7 Hz, ⁵J_FH= 1.5 Hz, 1 H,

H2Ј), 7.63 (dd, ³J_HH= 8.3 Hz, ⁴J_FH= 7.3 Hz, 1 H, H5Ј); δ_C(100.6

3Ј,5Ј-Diﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{4,1}.

According to GP3 from 9.41 g (35.9 mmol) 3Ј,5Ј-diﬂuoro-4-

trimethylsilylbiphenyl 3{4,1} was obtained 12.3 g (88%) iodo

biphenyl 4{4,1}; bp 156 ЊC/10^Ϫ3mbar; mp 57.3 ЊC (Found: C,

46.40; H, 3.89. C₁₅H₁₅F₂ISi requires C, 46.42; H, 3.98%); ν_max

(KBr)/cm^Ϫ13062 (w), 3018 (w), 2954 (m), 2896 (w), 1603 (m),

1576 (m), 1538 (m), 1460 (w), 1443 (w), 1418 (m), 1383 (m),

1340 (w), 1249 (m), 1202 (w), 1109 (w), 1072 (w), 1022 (s), 841

(s), 845 (s), 757 (s), 721 (m), 692 (m), 623 (m), 595 (w), 561 (w),

530 (w), 492 (w); δ_H(400.1 MHz, CDCl₃) 0.33 (s, 9 H, SiMe₃),

7.14 (d, line distance 7.3 Hz, AAЈ-part of a AAЈXXЈ-system,

2 H, H2Ј,6Ј), 7.54 (d, line distance 8.3 Hz, AAЈ-part of a

AAЈXXЈ-system, 2 H, H2,6) 7.63 (d, line distance 8.2 Hz, XXЈ-

part of a AAЈXXЈ-system, 2 H, H3,5); δ_C(100.6 MHz, CDCl₃)

2

MHz, CDCl₃) Ϫ1.2 (SiMe₃), 109.0 (d, J_CF= 20.9 Hz, C4Ј),

2

4

2

116.9 (dd, J_CF= 23.5 Hz, J_CF= 3.4 Hz, C2Ј), 124.6 (dd,

Ϫ1.2 (SiMe₃), 69.2 (t, J_CF= 29.6 Hz, C4Ј), 109.8 (d, line dis-

³J_CF= 3.0 Hz, ⁴J_CF= 0.8 Hz, C6), 125.7 (t, ⁴J_CF≈ ⁴J_CFЈ≈ 3.4 Hz,

tance 28.1 Hz, AAЈ-part of a AAЈXXЈ-system, C2Ј,6Ј), 126.0

2

3

4

C6Ј), 129.1 (dd, J_CF= 27.3 Hz, J_CF= 1.1 Hz, C4), 129.1 (dd,

(C2,6), 134.1 (C3,5), 139.4 (t, J_CF= 2.3 Hz, C1), 141.4 (C4),

³J_CF= 11.4 Hz, J_CF= 5.3 Hz, C5), 129.6 (dd, J_CF= 9.9 Hz,

144.5 (t, J_CF= 9.1 Hz, C1Ј), 163.0 (dd, J_CF= 246.3 Hz,

³J_CF= 6.8 Hz, C3Ј,5Ј); m/z (EI) 388 [M^ϩ], 373 [M^ϩϪ CH₃], 246

[M^ϩϪ CH₃Ϫ I], 186.

4

2

3

1

³J_CF= 1.1 Hz, C1), 133.6 (C5Ј), 136.0 (dd, J_CF= 7.6 Hz,

3

³J_CF= 2.7 Hz, C1Ј), 147.4 (dd, ¹J_CF= 253.4 Hz, ²J_CF= 17.3 Hz,

1

2

C2), 155.0 (dd, J_CF= 242.4 Hz, J_CF= 11.6 Hz, C3), 159.0

(d, J_CF= 247.5 Hz, C3Ј); m/z (EI) 360, 358 [M^ϩ], 345, 343

3,3Ј,5Ј-Triﬂuoro-4-trimethylsilylbiphenyl 3{4,2}. According to

GP2 from 1-bromo-3,5-diﬂuorobenzene 1{4} and 2-(3-ﬂuoro-

4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborinane 2{2}

was obtained biphenyl 3{4,2} 13.3 g (95%); bp 152 ЊC/14 mbar;

mp 56.5 ЊC (Found: C, 64.26; H, 5.39. C₁₅H₁₅F₃Si requires C,

64.45; H, 5.39%); ν_max(KBr)/cm^Ϫ13094 (w), 2954 (m), 2898 (w),

1614 (s), 1595 (s), 1546 (m), 1498 (w), 1458 (m), 1391 (m), 1337

(w), 1253 (s), 1221 (m), 1162 (m), 1141 (w), 1114 (s), 1085 (m),

1053 (w), 986 (s), 958 (w), 844 (s), 794 (m), 752 (w), 713 (w), 692

(w), 641 (w), 625 (w), 593 (w), 505 (w); δ_H(400.1 MHz, CDCl₃)

0.37 (s, 9 H, SiMe₃), 6.81 (tt, ³J_FH= 8.8 Hz, ⁴J_HH= 2.3 Hz, 1 H,

1

[M^ϩϪ CH₃], 264 [M^ϩϪ CH₃Ϫ Br], 198, 183, 164.

4Ј-Iodo-2,3,3Ј-triﬂuoro-4-trimethylsilylbiphenyl 4{3,5}.

According to GP3 from 11.6 g (32.3 mmol) 4Ј-bromo-2,3,3Ј-

triﬂuoro-4-trimethylsilylbiphenyl 3{3,5} was obtained 11.7 g

(89%) iodo biphenyl 4{3,5}; bp 170 ЊC/10^Ϫ3mbar; mp 46.8 ЊC

(Found: C, 44.35; H, 3.47. C₁₅H₁₄F₃ISi requires C, 44.29; H,

3.54%); ν_max(KBr)/cm^Ϫ13069 (w), 3031 (w), 2958 (m), 2898 (w),

1617 (w), 1595 (w), 1567 (m), 1540 (m), 1493 (m), 1465 (m),

1437 (s), 1390 (s), 1319 (w), 1285 (m), 1250 (s), 1221 (s), 1204

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1620

View Article Online

H4Ј), 7.10 (d, line distance 6.3 Hz, AAЈ-part of a AAЈXXЈ-

distance 8.1 Hz, AAЈ-part of a AAЈXXЈ-system, 2 H, H2Ј,6Ј),

3

4

system, 2 H, H2Ј,6Ј), 7.18 (dd, J_FH= 9.6 Hz, J_HH= 1.5 Hz,

7.13–7.21 (m, 2 H); δ_C(100.6 MHz, CDCl₃) Ϫ1.2 (SiMe₃), 70.7

3

4

2

1 H, H2), 7.32 (dd, J_HH= 7.6 Hz, J_HH= 1.5 Hz, 1 H, H6),

(t, J_CF= 29.4 Hz, C4Ј), 111.8 (d, line distance 25.7 Hz, AAЈ-

3

4

3

7.49 (dd, J_HH= 7.6 Hz, J_FH= 6.0 Hz, 1 H, H5); δ_C(100.6

MHz, CDCl₃) Ϫ1.1 (SiMe₃), 103.1 (t, J_CF= 25.4 Hz, C4Ј),

part of a AAЈXXЈ-system, C2Ј,6Ј), 124.4 (d, J_CF= 3.0 Hz,

2

C6), 128.8 (br. d, ²J_CF= 9.9 Hz, C1), 129.3 (dd, ³J_CF= 11.4 Hz,

2

3

109.9 (d, line distance 26.2 Hz, AAЈ-part of a AAЈXXЈ-system,

⁴J_CF= 5.3 Hz, C5), 129.8 (dd, J_CF= 27.3 Hz, J_CF= 1.1 Hz,

2

4

C2Ј,6Ј), 113.2 (d, J_CF= 27.3 Hz, C2), 122.3 (d, J_CF= 2.7 Hz,

C4), 137.8 (t, ³J_CF= 10.1 Hz, C1Ј), 147.4 (dd, ¹J_CF= 254.3 Hz,

2

3

1

2

C6), 126.4 (d, J_CF= 30.7 Hz, C4), 135.8 (d, J_CF= 12.1 Hz,

²J_CF= 17.5 Hz, C2), 155.0 (dd, J_CF= 242.5 Hz, J_CF

=

3

4

C5), 142.1 (dt, J_CF= 8.4 Hz, J_CF= 2.5 Hz, C1), 143.2 (td,

11.8 Hz, C3), 162.7 (dd, ¹J_CF= 246.7 Hz, ³J_CF= 6.5 Hz, C3Ј,5Ј);

m/z (EI) 424 [M^ϩ], 409 [M^ϩϪ CH₃], 282, [M^ϩϪ CH₃Ϫ I], 201,

182, 77.

³J_CF= 9.6 Hz, J_CF= 2.5 Hz, C1Ј), 163.4 (dd, J_CF= 248.2 Hz,

³J_CF= 12.9 Hz, C3Ј,5Ј), 167.8 (d, ¹J_CF= 241.4 Hz, C3); m/z (EI)

280 [M^ϩ], 265 [M^ϩϪ CH₃], 203 [M^ϩϪ CH₃Ϫ CH₃SiF], 183,

165, 138, 77.

4

1

Library synthesis

1. Suzuki-coupling yielding terphenyls 6{T,H,B}. The com-

binatorial synthesis was carried out by reaction of each of the

terminal boronic esters 5{1}–5{5} with each of the biphenyls

4{1,1}, 4{1,2}, 4{1,5}, 4{2,1}, 4{2,2}, 4{2,5}, 4{3,2}, and

4{3,5} and by reaction of the boronic esters 5{1}, 5{3} and

5{4} with the biphenyls 4{4,1}, 4{4,2} and 4{4,5}.

3,3Ј,5Ј-Triﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{4,2}.

According to GP3 from 9.71 g (34.6 mmol) 3,3,5Ј-triﬂuoro-4-

trimethylsilylbiphenyl 3{4,2} 12.7 g (90%) was obtained iodo

biphenyl 4{4,2}; bp 119 ЊC/10^Ϫ3mbar; mp 76.1 ЊC (Found: C,

44.35; H, 3.47. C₁₅H₁₄F₃ISi requires C, 44.30; H, 3.54%); ν_max

(KBr)/cm^Ϫ13065 (w), 2950 (m), 2896 (w), 1610 (m), 1578 (m),

1499 (w), 1458 (w), 1426 (w), 1386 (m), 1266 (w), 1246 (m), 1224

(w), 1208 (w), 1167 (w), 1137 (w), 1090 (w), 1059 (m), 1021 (s),

961 (m), 880 (m), 859 (s), 843 (s), 825 (s), 805 (m), 759 (m), 712

(w), 694 (w), 615 (w), 561 (m), 545 (w), 529 (w), 511 (w), 450

(w); δ_H(400.1 MHz, CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.11 (d, line

distance 7.1 Hz, AAЈ-part of a AAЈXXЈ-system, 2 H, H2Ј,6Ј),

In each of 49 closed vials under argon 2.50 mmol biphenyl

4{H,B} was reacted with 3.75 mmol boronic ester 5{T }, 4.50

ml (9.00 mmol) of a 2 M K₂CO₃-solution, 0.500 ml (0.038

mmol, 1 mol%) of a 76 mM Pd(OAc)₂solution in acetone with

20 ml degassed acetone as solvent with magnetic stirring for

12 h at 80 ЊC. Subsequently the solvent was removed under

reduced pressure. To the residue 10 ml H₂O were added and

the mixture was extracted with dichloromethane (5 ml). The

organic phase was ﬁltered over diatomenic earth, 2 ml 30%

H₂O₂and some iPrOH were added, until the mixture became a

homogeneous solution (ca. 10 ml iPrOH). After 6 h stirring at rt

excess H₂O₂was destroyed by addition of 3 ml 5 M NaOH.

After stirring for another 12 h, the solvent was removed under

reduced pressure. To the residue 10 ml H₂O were added and the

mixture was extracted with dichloromethane (3 × 5 ml). The

organic phases were puriﬁed by solid phase extraction (SPE).

The custom-made SPE cartridges consisted of a 10 ml SPE

syringe with a PE frit, a glass-ﬁbre ﬁlter, ca. 2 ml SiO₂, and ca. 1

ml diatomenic earth. GC control showed that the turnover of

biphenyl was 100% in all cases. The main impurity appeared to

be the homo-coupling product of the boronic esters.

3

4

7.17 (dd, J_FH= 9.5 Hz, J_HH= 1.4 Hz, 1 H, H2), 7.32 (dd,

³J_HH= 7.6 Hz, ⁴J_HH= 1.4 Hz, 1 H, H6), 7.49 (dd, ³J_HH= 7.6 Hz,

⁴J_FH= 5.8 Hz, 1 H, H5); δ_C(100.6 MHz, CDCl₃) Ϫ1.1 (SiMe₃),

2

70.0 (t, J_CF= 29.4 Hz, C4Ј), 109.8 (d, line distance 28.5 Hz,

2

AAЈ-part of a AAЈXXЈ-system, C2Ј,6Ј), 113.0 (d, J_CF= 27.7

Hz, C2), 122.1 (d, ⁴J_CF= 3.0 Hz, C6), 126.9 (d, ²J_CF= 30.7 Hz,

3

C4), 135.9 (d, J_CF= 12.1 Hz, C5), 141.3 (dt, J_CF= 8.4 Hz,

⁴J_CF= 2.5 Hz, C1), 143.1 (td, ³J_CF= 9.2 Hz, ⁴J_CF= 2.4 Hz, C1Ј),

163.0 (dd, J_CF= 246.7 Hz, J_CF= 6.5 Hz, C3Ј,5Ј), 167.8 (d,

¹J_CF= 241.8 Hz, C3); m/z (EI) 406 [M^ϩ], 391 [M^ϩϪ CH₃], 329,

264 [M^ϩϪ CH₃Ϫ I], 201, 183, 164, 77.

1

3

2,3,3Ј,5Ј-Tetraﬂuoro-4-trimethylsilylbiphenyl 3{4,5}. Accord-

ing to GP2 from 1-bromo-3,5-diﬂuorobenzene 1{4} and 2-(2,3-

diﬂuoro-4-trimethylsilylphenyl)-5,5-dimethyl[1,3,2]dioxaborin-

ane 2{5} was obtained biphenyl 3{4,5} 12.2 g (82%); bp 150 ЊC/

13 mbar (Found: C, 60.39; H, 4.73. C₁₅H₁₄F₄Si requires C,

60.46; H, 4.77%); ν_max(KBr)/cm^Ϫ13092 (w), 2960 (m), 2902 (w),

1623 (m), 1596 (m), 1551 (w), 1497 (w), 1457 (m), 1482 (s), 1347

(m), 1284 (w), 1254 (m), 1217 (m), 1142 (w), 1121 (s), 986 (m),

903 (w), 842 (s), 796 (m), 766 (m), 742 (w), 690 (w), 653 (w), 627

(w), 605 (w), 561 (w), 509 (w); δ_H(400.1 MHz, CDCl₃) 0.38 (s,

2. Iododesilyation yielding terphenyls 7{T,H,B}. In 49 vials

2.00 mmol of each of the terphenyls 6{T,H,B} was dissolved in

4 ml abs. acetonitrile, 1.20 ml (6.00 mmol) of a 5 M solution of

ICl in MeCN was added and the mixture shaken vigorously for

1 h at rt. Subsequently, the product was precipitated by addition

of water (10 ml) and 2 M Na₂S₂O₅(10 ml). The product

7{T,H,B} was removed by ﬁltration, washed with water and

dried under vacuum.

3

4

9 H, SiMe₃), 6.84 (tt, J_FH= 8.9 Hz, J_HH= 2.3 Hz, 1 H, H4Ј),

7.06–7.11 (m, 2 H), 7.13–7.21 (m, 2 H); δ_C(100.6 MHz, CDCl₃)

2

Ϫ1.2 (SiMe₃), 103.5 (t, J_CF= 25.2 Hz, C4Ј), 111.9 (d, line dis-

tance 22.8 Hz, AAЈ-part of a AAЈXXЈ-system, C2Ј,6Ј), 124.6

3. Suzuki-coupling yielding quaterphenyls 8{T,H,B,T}. The

combinatorial synthesis was carried out by reaction of 5{1}

with 7{1,1,1}, 7{1,3,2}, 7{2,3,2}, 7{3,1,1}, 7{3,3,2}, 7{5,1,1}

and 7{5,3,2}; of 5{2} with 7{1,1,1}, 7{1,3,2}, 7{2,3,2},

7{2,1,1}, 7{4,1,1} and 7{4,3,2}; of 5{3} with 7{2,1,1}, 7{3,1,1},

7{3,3,2}, 7{5,1,1} and 7{5,3,2}; of 5{4} with 7{1,1,1}, 7{1,3,2},

7{2,3,2}, 7{3,1,1}, 7{3,3,2}, 7{4,1,1} and 7{4,3,2}; of 5{5} with

7{2,1,1}, 7{4,1,1}, 7{4,3,2}, 7{5,1,1} and 7{5,3,2}. The remain-

ing 39 terphenyls were reacted in all possible combinations with

the boronic 5{1}–5{5}.

In each of 225 closed vials under argon 0.100 mmol terphenyl

7{T,H,B} was reacted with 0.150 mmol boronic ester 5{T },

0.200 ml (0.400 mmol) of a 2 M K₂CO₃solution, 20 µl (1.52

µmol, 1 mol%) of a 76 mM Pd(OAc)₂solution in acetone with

2 ml degassed acetone as solvent with magnetic stirring for 12 h

at 80 ЊC. Subsequently, the solvent was removed under reduced

pressure. To the residue 2 ml H₂O were added and the mixture

was extracted with dichloromethane (3 × 2 ml). The organic

phases were puriﬁed by SPE ﬁltration. The custom-made SPE

3

(d, J_CF= 2.7 Hz, C6), 128.5 (d, J_CF= 6.8 Hz, C5), 129.1

(dd, ²J_CF= 11.0 Hz, ³J_CF= 5.3 Hz, C1), 133.8 (d, ²J_CF= 19.4 Hz,

3

C4), 137.8 (td, J_CF= 10.2 Hz, J_CF= 3.3 Hz, C1Ј), 147.5 (dd,

¹J_CF= 253.9 Hz, ²J_CF= 17.5 Hz, C2), 155.0 (dd, ¹J_CF= 242.5 Hz,

²J_CF= 11.8 Hz, C3), 163.0 (dd, ¹J_CF= 248.2 Hz, ³J_CF= 12.9 Hz,

C3Ј,5Ј); m/z (EI) 298 [M^ϩ], 283 [M^ϩϪ CH₃], 201, [M^ϩϪ CH₃Ϫ

HF Ϫ CH₃SiF], 81, 77.

2,3,3Ј,5Ј-Tetraﬂuoro-4Ј-iodo-4-trimethylsilylbiphenyl 4{4,5}.

According to GP3 from 3.51 g (11.8 mmol) 2,3,3Ј,5Ј-tetra-

ﬂuoro-4-trimethylsilylbiphenyl 3{4,5} was obtained 2.45 g

(49%) iodo biphenyl 4{4,5}; mp 66.9 ЊC (Found: C, 42.47; H,

3.09. C₁₅H₁₄F₄ISi requires C, 42.61; H, 3.23%); ν_max(KBr)/cm^Ϫ1

3040 (w), 2960 (w), 2901 (w), 1611 (m), 1576 (s), 1543 (m), 1495

(w), 1438 (s), 1404 (s), 1281 (w), 1252 (m), 1205 (m), 1140 (m),

1106 (w), 1037 (w), 1019 (s), 989 (m), 953 (w), 903 (w), 840 (s),

819 (s), 761 (m), 693 (w), 662 (w), 626 (w), 605 (w), 556 (m), 518

(w); δ_H(400.1 MHz, CDCl₃) 0.37 (s, 9 H, SiMe₃), 7.10 (d, line

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1621

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cartridges consisted of a 5 ml SPE syringe with a PE frit, a

glass-ﬁbre ﬁlter, ca. 1 ml SiO₂, and ca. 0.5 ml diatomenic earth.

The crude products were recrystallised twice from nonane. The

purity and identity of the quaterphenyls 8{T,H,B,T } was

veriﬁed by HPLC-MS.

2 H), 7.23–7.37 (m, 5 H), 7.65–7.71 (m, 4 H); δ_C(100.6 MHz,

CDCl₃) 13.78, 13.82, 22.7, 23.3, 24.2, 30.8, 111.1 (d, line dis-

tance 25.1 Hz, AAЈ–part of a AAЈXXЈ–spectrum), 113.6 (d,

J_CF= 23.5 Hz), 118.0 (t, J_CF= 20.7 Hz), 122.3 (d, J_CF= 3.0 Hz),

124.3 (t, J_CF= 3.4 Hz), 124.8 (t, J_CF= 3.6 Hz), 127.1, 127.7 (d,

J_CF= 9.5 Hz), 128.8 (d, J_CF= 16.3 Hz), 129.3 (d, J_CF= 2.7 Hz),

130.1 (dd, J_CF= 8.7 Hz, J_CF= 1.9 Hz), 131.1 (d, J_CF= 5.7 Hz),

133.5, 133.9 (td, J_CF= 10.3 Hz, J_CF= 2.0 Hz), 139.9 (d, J_CF= 8.0

NMR and mass-spectrometric characterization of selected

library members

Hz), 140.0 (d, J_CF= 2.3 Hz), 148.5 (dd, J_CF= 252.6 Hz, J_CF

=

2,3,2Ј,3Ј,2Љ,3ٞ-Hexaﬂuoro-4,4ٞ-dipropyl[1,4Ј:1Ј,1Љ:4Љ,1ٞ]-

16.1 Hz), 148.6 (dd, J_CF= 251.8 Hz, J_CF= 15.4 Hz), 161.5 (d, J_CF

= 246.0 Hz), 161.6 (dd, J_CF= 245.6 Hz, J_CF= 9.5 Hz); m/z

(APCIϩ, CH₂Cl₂, hexane) 481.5 [M ϩ H]^ϩ.

quaterphenyl 8{3,2,3,5}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH

7.3 Hz, 3 H), 1.02 (t, J_HH= 7.1 Hz, 3 H), 1.70 (sextet, J_HH

7.6 Hz, 2 H), 1.71 (sextet, J_HH= 7.6 Hz, 2 H), 2.68 (t, J_HH

=

7.6 Hz, 2 H), 2.72 (t, J_HH= 7.4 Hz, 2 H), 7.03–7.13 (m, 2 H),

7.21–7.36 (m, 5 H), 7.40–7.52 (m, 3 H); δ_C(100.6 MHz, CDCl₃)

13.78, 13.81, 23.1, 23.3, 30.81, 30.84, 113.7 (d, J_CF= 23.5 Hz),

114.3 (d, J_CF= 23.2 Hz), 121.1 (dd, J_CF= 15.4 Hz, J_CF= 2.5 Hz),

121.5 (dd, J_CF= 12.5 Hz, J_CF= 2.3 Hz), 122.3 (d, J = 3.0 Hz),

122.6 (d, J_CF= 3.0 Hz), 124.4 (dd, J_CF= 11.8 Hz, J_CF= 1.9 Hz),

124.9 (t, J_CF= 4.4 Hz), 125.0 (br. s), 125.1 (br. s), 125.5 (br. s),

125.6 (br. s), 129.4 (d, J_CF= 16.7 Hz), 131.2 (d, J_CF= 6.1 Hz),

131.7, 132.3 (d, J_CF= 13.3 Hz), 138.8 (dd, J_CF= 8.0 Hz,

J_CF= 1.9 Hz), 142.6 (dd, J_CF= 8.0 Hz, J_CF= 1.9 Hz), 148.1 (dd,

J_CF= 250.9 Hz, J_CF= 14.0 Hz), 148.41 (dd, J_CF= 253.6 Hz,

J_CF= 16.3 Hz), 148.45 (dd, J_CF= 253.2 Hz, J_CF= 15.6 Hz), 149.4

(dd, J_CF= 246.3 Hz, J_CF= 12.9 Hz), 160.0 (d, J_CF= 249.4 Hz),

161.5 (d, J_CF= 245.2 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 499.5

[M ϩ H]^ϩ.

3,5,2Љ,3Љ,2ٞ,3ٞ-Hexaﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]qua-

terphenyl 8{4,1,3,5}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH

=

7.0 Hz, 3 H), 1.02 (t, J_HH= 7.1 Hz, 3 H), 1.67 (sextet,

J_HH= 7.6 Hz, 2 H), 1.72 (sextet, J_HH= 7.6 Hz, 2 H), 2.70

(t, J_HH= 7.1 Hz, 2 H), 2.72 (t, J_HH= 7.5 Hz, 2 H), 7.03–7.33

(m, 6 H), 7.64–7.69 (m, 4 H); δ_C(100.6 MHz, CDCl₃) 13.76,

13.77, 22.8, 23.16, 24.2, 30.8, 109.5 (d, J_CF= 27.3 Hz), 117.1 (t,

J_CF= 20.9 Hz), 121.6 (dd, J_CF= 12.0 Hz, J_CF= 2.5 Hz), 123.7

(dd, J_CF= 12.3 Hz, J_CF= 2.5 Hz), 124.5 (t, J_CF= 3.2 Hz),

124.9 (t, J_CF= 4.4 Hz), 125.0 (br. s), 125.7 (br. s), 127.0, 129.5 (d,

J_CF= 3.0 Hz), 130.2 (d, J_CF= 10.6 Hz), 132.2 (d, J_CF= 13.3 Hz),

134.2, 138.9 (t, J_CF= 2.5 Hz), 140.0 (t, J_CF= 9.9 Hz), 148.1 (dd,

J_CF= 250.7 Hz, J_CF= 14.2 Hz), 148.4 (dd, J_CF= 250.5 Hz,

J_CF= 14.0 Hz), 148.6 (dd, J_CF= 251.3 Hz, J_CF= 14.0 Hz), 149.4

(dd, J_CF= 246.7 Hz, J_CF= 12.9 Hz), 161.9 (dd, J_CF= 246.0 Hz,

J_CF= 10.2 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 499.5 [M ϩ H]^ϩ.

2Ј,3Ј,2Љ-Triﬂuoro-4,4ٞ-dipropyl[1,4Ј:1Ј,1Љ:4Љ,1ٞ]quaterphenyl

8{1,2,3,1}. δ_H(400.1 MHz, CDCl₃) 1.007 (t, J_HH= 7.3 Hz, 3 H),

1.013 (t, J_HH= 7.3 Hz, 3 H), 1.72 (sextet, J_HH= 7.5 Hz, 2 H),

1.73 (sextet, J_HH= 7.5 Hz, 2 H), 2.67 (t, J_HH= 7.6 Hz, 2 H), 2.68

(t, J_HH= 7.5 Hz, 2 H), 7.23–7.32 (m, 6 H), 7.43–7.58 (m, 7 H);

δ_C(100.6 MHz, CDCl₃) 13.84, 13.87, 24.4, 24.5, 37.7, 37.8,

114.2 (d, J_CF= 23.2 Hz), 120.8 (dd, J_CF= 15.2 Hz, J_CF= 2.3 Hz),

122.6 (d, J_CF= 3.4 Hz), 123.8 (d, J_CF= 12.5 Hz), 124.5

(t, J_CF= 3.4 Hz), 125.6 (br. s), 126.9, 128.74, 128.76, 129.1,

2,3,2Љ,3Љ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]quaterphe-

nyl 8{5,1,3,1}. δ_H(400.1 MHz, CDCl₃) 1.01 (t, J_HH= 7.3 Hz,

3 H), 1.02 (t, J_HH= 7.3 Hz, 3 H), 1.721 (sextet, J_HH= 7.5 Hz,

2 H), 1.724 (sextet, J_HH= 7.5 Hz, 2 H), 2.68 (t, J_HH= 7.8 Hz,

2 H), 2.71 (t, J_HH= 7.6 Hz, 2 H), 7.03 (ddd, J = 7.8 Hz,

J = 6.7 Hz, J = 1.1 Hz, 1 H), 7.18 (ddd, J = 8.2 Hz, J = 6.8 Hz,

J = 1.5 Hz, 1 H), 7.30–7.32 (m, 4 H), 7.54 (d, J = 8.0 Hz, 2 H),

7.67–7.71 (m, 4 H); δ_C(100.6 MHz, CDCl₃) 13.8, 13.9, 23.2,

24.4, 30.8, 37.8, 124.2 (dd, J_CF= 3.8 Hz, J_CF= 2.7 Hz), 124.5 (t,

J_CF= 3.4 Hz), 124.7 (t, J_CF= 3.4 Hz), 124.9 (t, J_CF= 4.3 Hz),

127.8 (d, J_CF= 10.2 Hz), 128.7 (br. s), 128.8, 128.99 (br. s),

129.04 (d, J_CF= 3.0 Hz), 130.1 (dd, J_CF= 7.2 Hz, J_CF= 3.8 Hz),

131.0 (d, J_CF= 13.7 Hz), 131.9, 134.2, 134.8 (br. s), 142.9, 148.1

(dd, J_CF= 248.6 Hz, J_CF= 13.3 Hz), 148.5 (dd, J_CF= 250.9 Hz,

J_CF= 15.6 Hz), 148.6 (dd, J_CF= 251.3 Hz, J_CF= 15.6 Hz), 149.6

(dd, J_CF= 244.3 Hz, J_CF= 11.6 Hz), the increased intensity of

the signal at δ = 128.8 indicates that two carbon resonances

coincide here; m/z (APCIϩ, CH₂Cl₂, hexane) 463.5 [M ϩ H]^ϩ.

130.7 (d, J_CF= 10.6 Hz), 131.6 (br. s), 131.9, 136.7 (d, J_CF

=

1.9 Hz), 142.9 (d, J_CF= 12.9 Hz), 143.6 (d, J_CF= 8.4 Hz), 148.3

(dd, J_CF= 249.6 Hz, J_CF= 13.9 Hz), 148.7 (dd, J_CF= 250.1 Hz,

J_CF= 14.4 Hz), 160.0 (d, J_CF= 249.4 Hz), the increased intensity

of the signal at δ = 128.76 indicates, that two carbon resonances

coincide here; m/z (APCIϩ, CH₂Cl₂, hexane) 445.5 [M ϩ H]^ϩ.

3,5,2Ј,2Љ,3Љ,3ٞ-Hexaﬂuoro-4,4ٞ-dipropyl[1,4Ј:1Ј,1Љ:4Љ,1ٞ]-

quaterphenyl 8{4,2,3,3}. δ_H(400.1 MHz, CDCl₃) 1.00 (t,

J_HH= 7.4 Hz, 3 H), 1.01 (t, J_HH= 7.3 Hz, 3 H), 1.67 (sextet,

J_HH= 7.4 Hz, 2 H), 1.71 (sextet, J_HH= 7.3 Hz, 2 H), 2.69

(t, J_HH= 6.6 Hz, 2 H), 2.71 (t, J_HH= 6.3 Hz, 2 H), 7.10–7.16 (m,

2 H), 7.22–7.33 (m, 5 H), 7.37–7.45 (m, 2 H), 7.49–7.52 (m,

1 H); δ_C(100.6 MHz, CDCl₃) 13.7, 13.8, 22.7, 23.2, 24.2, 30.9,

109.5 (d, line distance 28.1 Hz, AAЈ–part of a AAЈXXЈ–

spectrum), 114.3 (d, J_CF= 23.5 Hz), 115.6 (dd, J_CF= 24.1 Hz,

J_CF= 3.2 Hz), 117.8 (t, J_CF= 20.9 Hz), 121.8 (dd, J_CF= 15.6 Hz,

J_CF= 2.3 Hz), 122.5 (d, J_CF= 3.4 Hz), 124.0 (d, J_CF= 12.5 Hz),

124.3 (t, J_CF= 3.2 Hz), 124.4 (t, J_CF= 3.2 Hz), 125.7 (br. s),

129.6 (br. s), 129.8 (br. s), 130.9 (d, J_CF= 5.7 Hz), 131.9 (dd,

J_CF= 3.4 Hz, J_CF= 2.3 Hz), 133.7 (d, J_CF= 8.4 Hz), 138.9 (dd,

3,5,3ٞ,5ٞ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]quater-

phenyl 8{5,1,1,5}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH= 7.4 Hz,

6 H), 1.67 (sextet, J_HH= 7.4 Hz, 4 H), 2.70 (t, J_HH= 7.5 Hz, 4 H),

7.11–7.17 (m, 4 H), 7.63–7.73 (m, 8 H); δ_C(100.6 MHz, CDCl₃)

13.8, 22.8, 24.2, 109.3 (d, line distance 27.7 Hz, AAЈ–part of a

AAЈXXЈ–spectrum), 116.9 (t, J_CF= 20.9 Hz), 127.2, 127.5,

138.2 (d, J_CF= 2.5 Hz), 140.1, 140.2 (t, J_CF= 9.9 Hz), 161.9 (dd,

J_CF= 245.8 Hz, J_CF= 10.4 Hz); (APCIϩ, CH₂Cl₂, hexane):

m/z = 463.5 [M ϩ H]^ϩ.

J_CF= 10.1 Hz, J_CF= 2.0 Hz), 141.4 (dd, J_CF= 8.1 Hz, J_CF

=

3,5,2Ј,2Љ,3ٞ,5ٞ-Hexaﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]-

quaterphenyl 8{4,3,2,4}. δ_H(400.1 MHz, CDCl₃) 1.00 (t,

J_HH= 7.4 Hz, 6 H), 1.67 (sextet, J_HH= 7.4 Hz, 4 H), 2.71 (d,

J_HH= 7.5 Hz, 4 H), 7.09–7.15 (m, 4 H), 7.40–7.53 (m, 6 H);

δ_C(100.6 MHz, CDCl₃) 13.8, 22.8, 24.2, 111.5 (d, line distance

2.4 Hz), 148.3 (dd, J_CF= 250.5 Hz, J_CF= 14.0 Hz), 148.6 (dd,

J_CF= 250.9 Hz, J_CF= 14.0 Hz), 160.1 (d, J_CF= 250.1 Hz), 161.1

(d, J_CF= 245.2 Hz), 161.9 (dd, J_CF= 246.5 Hz, J_CF= 10.4 Hz);

m/z (APCIϩ, CH₂Cl₂, hexane) 499.5 [M ϩ H]^ϩ.

31.5 Hz, AAЈ–part of a AAЈXXЈ–spectrum), 114.7 (d, J_CF

=

3,2Љ,3Љ,3ٞ,5ٞ-Pentaﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]qua-

terphenyl 8{3,1,3,4}. δ_H(400.1 MHz, CDCl₃) 1.010 (t,

J_HH= 7.3 Hz, 3 H), 1.012 (t, J_HH= 7.4 Hz, 3 H), 1.68 (sextet,

J_HH= 7.5 Hz, 2 H), 1.70 (sextet, J_HH= 7.5 Hz, 2 H), 2.68

(t, J_HH= 7.8 Hz, 2 H), 2.72 (t, J_HH= 7.4 Hz, 2 H), 7.10–7.16 (m,

24.3 Hz), 117.6 (t, J_CF= 20.9 Hz), 122.9 (d, J_CF= 3.4 Hz), 126.5

(dt, J_CF= 13.0 Hz, J_CF= 2.6 Hz), 130.7 (d, J_CF= 3.8 Hz), 134.5

(t, J_CF= 10.4 Hz), 140.9 (dd, J_CF= 8.2 Hz, J_CF= 1.7 Hz), 160.0

(d, J_CF= 249.8 Hz), 161.5 (dd, J_CF= 245.6 Hz, J_CF= 10.2 Hz);

m/z (APCIϩ, CH₂Cl₂, hexane) 499.5 [M ϩ H]^ϩ.

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

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2Ј-Fluoro-4,4ٞ-dipropyl[1,4Ј:1Ј,1Љ:4Љ,1ٞ]quaterphenyl

1.020 (t, J_HH= 7.3 Hz, 3 H), 1.73 (sextet, J_HH= 7.5 Hz, 2 H),

8{1,2,1,1}. δ_H(400.1 MHz, CDCl₃) 1.013 (t, J_HH= 7.4 Hz, 3 H),

1.016 (t, J_HH= 7.3 Hz, 3 H), 1.72 (sextet, J_HH= 7.5 Hz, 2 H),

1.73 (sextet, J_HH= 7.5 Hz, 2 H), 2.67 (br. t, J_HH= 7.8 Hz, 4 H),

7.30 (br. d, J = 8.0 Hz, 4 H), 7.43 (dd, J = 12.2 Hz, J = 1.7 Hz,

1 H), 7.48 (dd, J = 8.0 Hz, J = 1.8 Hz, 1 H), 7.54–7.60 (m, 5 H),

7.67–7.72 (m, 4 H); δ_C(100.6 MHz, CDCl₃) 13.85, 13.88, 24.50,

1.73 (sextet, J_HH= 7.5 Hz, 2 H), 2.67 (br. t, J_HH= 7.6 Hz, 4 H),

7.29–7.31 (m, 4 H), 7.44–7.60 (m, 7 H), 7.70 (s, 4 H); δ_C(100.6

MHz, CDCl₃) 13.88, 13.90, 24.49, 24.53, 37.7, 37.8, 114.4 (d,

J_CF= 23.9 Hz), 122.7 (d, J_CF= 3.0 Hz), 126.8, 127.2, 127.4,

127.7 (d, J_CF= 13.7 Hz), 128.6, 128.77, 128.80, 129.0, 130.9 (d,

J_CF= 4.2 Hz), 132.8 (d, J_CF= 1.5 Hz), 137.8, 138.1 (d, J_CF

=

24.53, 37.71, 37.72, 114.4 (d, J_CF= 23.5 Hz), 122.7 (d, J_CF

=

1.9 Hz), 140.7, 141.5 (d, J_CF= 7.6 Hz), 142.2 (d, J_CF= 20.9 Hz),

160.1 (d, J_CF= 247.5 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 409.5

[M ϩ H]^ϩ.

3.0 Hz), 126.8, 126.9, 127.01, 127.02 (d, J_CF= 13.3 Hz), 128.9,

129.1, 129.3 (d, J_CF= 3.0 Hz), 130.8 (d, J_CF= 4.2 Hz), 134.2 (d,

J_CF= 1.1 Hz), 136.9 (d, J_CF= 1.9 Hz), 138.0, 140.4, 142.0, 142.3

(d, J_CF= 8.0 Hz), 142.6, 160.1 (d, J_CF= 247.9 Hz); m/z (APCIϩ,

CH₂Cl₂, hexane) 409.5 [M ϩ H]^ϩ.

2,3,2Љ,3ٞ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]quaterphe-

nyl 8{5,1,2,2}. δ_H(400.1 MHz, CDCl₃) 1.02 (br t, J_HH

7.4 Hz, 6 H), 1.712 (sextet, J_HH= 7.5 Hz, 2 H), 1.715 (sextet,

J_HH= 7.5 Hz, 2 H), 2.69 (t, J_HH= 7.5 Hz, 2 H), 2.71 (t, J_HH

=

3,5,2Ј-Triﬂuoro-4,4ٞ-dipropyl[1,4Ј:1Ј,1Љ:4Љ,1ٞ]quaterphenyl

8{4,2,1,1}. δ_H(400.1 MHz, CDCl₃) 1.007 (t, J_HH= 7.3 Hz, 3 H),

1.011 (t, J_HH= 7.4 Hz, 3 H), 1.68 (sextet, J_HH= 7.1 Hz, 2 H),

1.72 (sextet, J_HH= 7.5 Hz, 2 H), 2.66 (t, J_HH= 7.8 Hz, 2 H),

2.71 (t, J_HH= 7.5 Hz, 2 H), 7.10–7.17 (m, 2 H), 7.29 (br. d,

J = 8.2 Hz, 2 H), 7.37 (dd, J = 11.8 Hz, J = 1.7 Hz, 1 H), 7.42

(dd, J = 8.0 Hz, J = 1.8 Hz, 1 H), 7.55–7.59 (m, 3 H), 7.66–

7.71 (m, 4 H); δ_C(100.6 MHz, CDCl₃) 13.8, 13.9, 22.8,

=

7.2 Hz, 2 H), 7.02 (ddd, J = 8.1 Hz, J = 6.7 Hz, J = 1.4 Hz, 1 H),

7.17 (ddd, J = 8.2 Hz, J = 6.9 Hz, J = 1.5 Hz, 1 H), 7.28–7.34

(m, 3 H), 7.43–7.55 (m, 3 H), 7.64–7.72 (m, 4 H); δ_C(100.6

MHz, CDCl₃) 13.76, 13.85, 23.2, 23.3, 30.8, 30.9, 114.6 (d,

J_CF= 23.9 Hz), 115.6 (dd, J_CF= 23.7 Hz, J_CF= 3.6 Hz), 122.9 (d,

J_CF= 3.0 Hz), 124.1 (dd, J_CF= 3.6 Hz, J_CF= 2.8 Hz), 124.3 (t,

J_CF= 3.2 Hz), 124.9 (t, J_CF= 4.4 Hz), 126.8 (dd, J_CF= 13.3 Hz,

J_CF= 1.9 Hz), 127.0, 127.7 (d, J_CF= 10.2 Hz), 129.0 (d,

J_CF= 16.3 Hz), 129.4 (d, J_CF= 3.4 Hz), 130.7 (d, J_CF= 6.1 Hz),

130.8 (d, J_CF= 4.2 Hz), 131.0 (d, J_CF= 13.7 Hz), 134.7 (br. s),

24.2, 24.5, 37.7, 109.4 (d, J_CF= 27.7 Hz), 114.4 (d, J_CF

24.3 Hz), 117.4 (t, J_CF= 21.1 Hz), 122.6 (d, J_CF= 3.4 Hz),

126.9, 127.1, 128.3 (d, J_CF= 13.7 Hz), 129.0, 129.3 (d, J_CF

=

3.4 Hz), 131.0 (d, J_CF= 4.2 Hz), 133.8 (d, J_CF= 1.1 Hz), 137.9,

139.1 (td, J_CF= 10.0 Hz, J_CF= 2.0 Hz), 140.0 (dt, J_CF= 8.0 Hz,

J_CF= 2.5 Hz), 140.7, 142.1, 160.1 (d, J = 248.2 Hz), 161.9 (dd,

J_CF= 246.3 Hz, J_CF= 10.2 Hz); m/z (APCIϩ, CH₂Cl₂, hexane)

445.5 [M ϩ H]^ϩ.

134.8 (d, J_CF= 1.1 Hz), 138.8 (d, J_CF= 1.9 Hz), 141.8 (d, J_CF=

8.4 Hz), 148.1 (dd, J_CF= 248.6 Hz, J_CF= 13.3 Hz), 149.6

(dd, J_CF= 244.3 Hz, J_CF= 11.6 Hz), 160.0 (d, J_CF= 248.2 Hz),

161.1 (d, J_CF= 244.4 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 463.5

[M ϩ H]^ϩ.

3,5,2Ј,2Љ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]quaterphe-

nyl 8{1,2,2,4}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH= 7.3 Hz,

3 H), 1.02 (t, J_HH= 7.3 Hz, 3 H), 1.69 (sextet, J_HH= 7.5 Hz, 2 H),

1.71 (sextet, J_HH= 7.5 Hz, 2 H), 2.66 (t, J_HH= 7.7 Hz, 2 H), 2.71

(t, J_HH= 7.6 Hz, 2 H), 7.11–7.16 (m, 2 H), 7.30 (br. d, J = 8.2 Hz,

2 H), 7.40–7.57 (m, 8 H); δ_C(100.6 MHz, CDCl₃) 13.79, 13.84,

3,2Ј,2Љ,3Љ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]quaterphe-

nyl 8{3,3,3,1}. δ_H(400.1 MHz, CDCl₃) 1.01 (t, J_HH= 7.3 Hz,

3 H), 1.02 (t, J_HH= 7.3 Hz, 3 H), 1.71 (sextet, J_HH= 7.5 Hz, 2 H),

1.72 (sextet, J_HH= 7.5 Hz, 2 H), 2.67 (t, J_HH= 7.9 Hz, 2 H), 2.69

(t, J_HH= 7.6 Hz, 2 H), 7.29–7.34 (m, 7 H), 7.41–7.47 (m, 2 H),

7.52–7.56 (m, 3 H); δ_C(100.6 MHz, CDCl₃) 13.86, 13.87, 23.3,

24.5, 30.9, 37.8, 115.7 (dd, J_CF= 23.9 Hz, J_CF= 3.4 Hz), 116.6

(d, J_CF= 24.3 Hz), 124.3 (q, J_CF= 3.3 Hz), 124.8 (d, J_CF= 3.8

Hz), 124.9 (d, J_CF= 3.4 Hz), 127.5 (d, J_CF= 1.9 Hz), 127.6 (d,

J_CF= 2.3 Hz), 127.7 (d, J_CF= 5.3 Hz), 127.8 (d, J_CF= 1.9 Hz),

128.7, 128.8, 129.2 (d, J_CF= 16.3 Hz), 130.6 (d, J_CF= 3.8 Hz),

22.8, 24.2, 24.5, 37.7, 111.5 (d, J_CF= 27.7 Hz), 114.6 (d, J_CF

23.5 Hz), 116.7 (dd, J_CF= 24.1 Hz, J_CF= 3.6 Hz), 117.4 (t, J_CF

=

20.9 Hz), 122.9 (d, J_CF= 3.4 Hz), 125.0 (t, J_CF= 3.2 Hz), 125.5

(dd, J_CF= 13.1 Hz, J_CF= 1.7 Hz), 126.0 (d, J_CF= 12.9 Hz),

126.8, 129.1, 130.2 (d, J_CF= 3.4 Hz), 130.5 (d, J_CF= 3.4 Hz),

134.8 (t, J_CF= 10.1 Hz), 136.6 (d, J_CF= 1.9 Hz), 137.4 (d, J_CF

8.7 Hz), 142.9, 143.2 (d, J_CF= 8.0 Hz), 159.5 (d, J_CF= 249.0 Hz),

160.0 (d, J_CF= 248.6 Hz), 161.5 (dd, J_CF= 245.6 Hz, J_CF

10.6 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 463.5 [M ϩ H]^ϩ.

=

130.7 (d, J_CF= 5.7 Hz), 131.7 (d, J_CF= 0.8 Hz), 134.6 (d, J_CF=

8.4 Hz), 135.8 (d, J_CF= 8.7 Hz), 143.1, 148.55 (dd, J_CF= 251.3

Hz, J_CF= 15.6 Hz), 148.60 (dd, J_CF= 252.0 Hz, J_CF= 15.9 Hz),

159.6 (d, J_CF= 248.6 Hz), 161.1 (d, J_CF= 244.8 Hz); m/z

(APCIϩ, CH₂Cl₂, hexane) 463.5 [MϩH]^ϩ.

=

3,2Ј,2Љ,2ٞ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,1Љ:4Љ,1ٞ]quater-

phenyl 8{2,2,2,3}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH= 7.2 Hz,

3 H), 1.02 (t, J_HH= 7.3 Hz, 3 H), 1.71 (br. sextet, J_HH= 7.5 Hz,

4 H), 2.65 (t, J_HH= 7.8 Hz, 2 H), 2.69 (t, J_HH= 7.7 Hz, 2 H),

7.02 (dd, J = 11.9 Hz, J = 1.5 Hz, 1 H), 7.07 (dd, J = 7.9 Hz,

J = 1.6 Hz, 1 H), 7.28–7.34 (m, 3 H), 7.38–7.48 (m, 5 H), 7.51–

7.56 (m, 2 H); δ_C(100.6 MHz, CDCl₃) 13.7, 13.9, 23.3, 24.2,

30.9, 37.5, 115.7 (dd, J_CF= 23.9 Hz, J_CF= 3.4 Hz), 116.2 (d,

2Ј,2Љ,3Љ,2ٞ,3ٞ-Pentaﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]qua-

terphenyl 8{1,3,3,5}. δ_H(400.1 MHz, CDCl₃) 1.00 (t, J_HH

=

7.3 Hz, 3 H), 1.02 (t, J_HH= 7.2 Hz, 3 H), 1.716 (sextet,

J_HH= 7.5 Hz, 2 H), 1.719 (sextet, J_HH= 7.5 Hz, 2 H), 2.67

(t, J_HH= 7.6 Hz, 2 H), 2.72 (t, J_HH= 7.4 Hz, 2 H), 7.03–7.13 (m,

2 H), 7.23 (br. t, J = 7.6 Hz, 1 H), 7.29–7.34 (m, 3 H), 7.41–7.46

(m, 2 H), 7.53–7.58 (m, 3 H); δ_C(100.6 MHz, CDCl₃) 13.8, 13.9,

23.2, 24.5, 30.9, 37.8, 116.6 (dd, J_CF= 24.7 Hz, 3.4 Hz), 121.5,

(d, J_CF= 14.4 Hz), 124.0 (dd, J_CF= 12.3 Hz, J_CF= 2.5 Hz), 124.4

(dd, J_CF= 3.4 Hz, J_CF= 3.0 Hz), 124.8 (t, J_CF= 3.2 Hz), 124.9 (t,

J_CF= 4.4 Hz), 125.0 (t, J_CF= 1.9 Hz), 125.8 (t, J_CF= 1.9 Hz),

128.7, 128.8 (d, J_CF= 3.0 Hz), 129.0 (d, J_CF= 13.7 Hz), 129.3

(dd, J_CF= 10.4 Hz, J_CF= 1.7 Hz), 130.8 (d, J_CF= 4.2 Hz), 132.3

J_CF= 22.4 Hz), 116.7 (ddd, J_CF= 23.9 Hz, J_CF= 3.4 Hz, J_CF

1.9 Hz), 124.341 (d, J_CF= 6.5 Hz), 124.342, 124.5 (d, J_CF

=

1.9 Hz), 124.7 (d, J_CF= 3.0 Hz), 124.9 (t, J_CF= 3.2 Hz), 125.0 (t,

J_CF= 3.2 Hz), 126.2 (dd, J_CF= 12.9 Hz, J_CF= 1.9 Hz), 127.1 (dd,

J_CF= 13.3 Hz, J_CF= 1.9 Hz), 129.0 (d, J_CF= 16.3 Hz), 130.0 (d,

J_CF= 3.4 Hz), 130.2 (d, J_CF= 3.4 Hz), 130.4 (d, J_CF= 3.8 Hz),

130.7 (d, J_CF= 5.7 Hz), 134.7 (dd, J_CF= 8.4 Hz, J_CF= 1.1 Hz),

136.7 (dd, J_CF= 8.5 Hz, J_CF= 0.9 Hz), 137.6 (dd, J_CF= 8.5 Hz,

J_CF= 0.9 Hz), 145.3 (d, J_CF= 7.6 Hz), 159.60 (d, J_CF= 248.2

Hz), 159.61 (d, J_CF= 248.6 Hz), 159.7 (d, J_CF= 248.2 Hz),

161.1 (d, J_CF= 244.4 Hz); m/z (APCIϩ, CH₂Cl₂, hexane) 463.5

[M ϩ H]^ϩ.

(d, J_CF= 13.3 Hz), 132.5 (d, J_CF= 1.5 Hz), 134.9 (dd, J_CF

=

8.9 Hz, J_CF= 1.7 Hz), 142.6, 148.1 (dd, J_CF= 250.7 Hz,

J_CF= 14.2 Hz), 148.4 (dd, J_CF= 250.9 Hz, J_CF= 14.0 Hz), 148.6

(dd, J_CF= 251.7 Hz, J_CF= 14.0 Hz), 149.4 (dd, J_CF= 246.5 Hz,

J_CF= 12.7 Hz), 159.7 (d, J_CF= 247.9 Hz); m/z (APCIϩ, CH₂Cl₂,

hexane) 481.5 [M ϩ H]^ϩ.

2Ј-Fluoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]quaterphenyl

8{1,1,2,1}. δ_H(400.1 MHz, CDCl₃) 1.016 (t, J_HH= 7.4 Hz, 3 H),

2Ј,6Ј,2Љ,3Љ,2ٞ-Pentaﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]qua-

terphenyl 8{1,4,3,2}. δ_H(400.1 MHz, CDCl₃) 1.003 (t, J_HH=

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1623

View Article Online

7.3 Hz, 3 H), 1.004 (t, J_HH= 7.3 Hz, 3 H), 1.71 (sextet, J_HH

=

Acknowledgements

7.5 Hz, 2 H), 1.72 (sextet, J_HH= 7.5 Hz, 2 H), 2.66 (br. t,

J_HH= 7.6 Hz, 4 H), 7.04 (dd, J = 11.2, J = 1.3 Hz, 1 H), 7.08 (dd,

J = 7.8 Hz, J = 1.6 Hz, 1 H), 7.23–7.27 (m, 3 H), 7.29–7.36 (m,

4 H), 7.44–7.46 (m, 2 H); δ_C(100.6 MHz, CDCl₃) 13.8, 13.9,

24.2, 24.4, 37.6, 37.9, 112.2 (d, line distance 28.5 Hz, AAЈ–part

of a AAЈXXЈ–spectrum), 115.9 (d, J_CF= 21.6 Hz), 118.3 (t,

J_CF= 18.8 Hz), 119.1 (dd, J_CF= 15.4 Hz, J_CF= 2.5 Hz), 124.0

(dd, J_CF= 3.6 Hz, J_CF= 2.5 Hz), 124.4 (d, J_CF= 3.0 Hz), 125.7

(d, J_CF= 12.9 Hz), 125.9, 126.1 (br. s), 127.9 (d, J_CF= 9.9 Hz),

128.5, 130.1, 130.9 (dd, J_CF= 3.2 Hz, J_CF= 2.1 Hz), 135.1 (dd,

J_CF= 11.0 Hz, J_CF= 2.7 Hz), 143.1, 146.2 (d, J_CF= 7.6 Hz),

We are grateful to the Fonds der Chemischen Industrie and

the BMBF for a Kekulé grant to O. D. We also would like to

thank Dr Peer Kirsch and Dr Detlef Pauluth (Merck KGaA

Darmstadt) for continual helpful discussions.

References

1 Combinatorial Chemistry

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Synthesis, Analysis, Screening,

ed. G. Jung, Wiley-VCH, Weinheim, 1999.

2 For review, see: B. Jandeleit, D. J. Schaefer, T. S. Powers,

H. W. Turner and W. H. Weinberg, Angew. Chem., Int. Ed., 1999, 38,

2494–2532.

3 (a) T. Bein, Angew. Chem., Int. Ed., 1999, 38, 323–326; (b) M. T.

Reetz, Angew. Chem., Int. Ed., 2001, 40, 284–310; (c) S. Senkan,

Angew. Chem., Int. Ed., 2001, 40, 312–329.

148.3 (dd, J_CF= 251.5 Hz, J_CF= 14.2 Hz), 148.7 (dd, J_CF

=

251.3 Hz, J_CF= 14.0 Hz), 159.7 (d, J_CF= 249.0 Hz), 160.1 (dd,

J_CF= 248.2 Hz, J_CF= 8.4 Hz); m/z (APCIϩ, CH₂Cl₂, hexane)

481.5 [M ϩ H]^ϩ.

4 (a) S. Brocchini, K. James, V. Tangpasuthadol and J. Kohn, J. Am.

Chem. Soc., 1997, 119, 4553–4554; (b) M. S. Bratcher, M. S. DeClue,

A. Grunnet-Jepsen, D. Wright, B. R. Smith, W. E. Moerner and

J. S. Siegel, J. Am. Chem. Soc., 1998, 120, 9680–9681; (c) D. J.

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6 (a) P. Bäuerle, O. Deeg, D. Pauluth and P. Kirsch Ger. Pat. Appl.

10211597.4 (15.3.2002).; (b) O. Deeg, P. Kirsch, D. Pauluth and

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7 O. Deeg, P. Kirsch, D. Pauluth and P. Bäuerle J. Comb. Chem.

submitted.

8 For review, see: (a) P. J. Collins and M. Hird, Introduction to Liquid

Crystals, Taylor & Francis, London, 1997; (b) Handbook of Liquid

Crystals, Vol 2a, eds. D. Demus, J. Goodby, G. W. Gray, H.-W. Spieß

and V. Vill, Wiley-VCH, Weinheim, 1998.

3,2Ј,6Ј,2Љ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]quaterphe-

nyl 8{3,4,2,1}. δ_H(400.1 MHz, CDCl₃) 1.01 (t, J_HH= 7.3 Hz,

3 H), 1.02 (t, J_HH= 7.3 Hz, 3 H), 1.72 (br. sextet, J_HH= 7.5 Hz,

4 H), 2.67 (t, J_HH= 7.8 Hz, 2 H), 2.70 (t, J_HH= 7.8 Hz, 2 H),

7.20–7.31 (m, 7 H), 7.39 (dd, J = 11.7 Hz, J = 1.8 Hz, 1 H),

7.44 (dd, J = 8.0 Hz, J = 1.8 Hz, 1 H), 7.52–7.57 (m, 3 H);

δ_C(100.6 MHz, CDCl₃) 13.9, 23.2, 24.5, 30.9, 37.8, 110.1 (d,

J_CF= 27.7 Hz), 114.4 (d, J_CF= 24.7 Hz), 116.5 (t, J_CF= 18.4 Hz),

117.1 (d, J_CF= 23.9 Hz), 122.6 (d, J_CF= 3.4 Hz), 125.8 (br. s),

128.0 (d, J_CF= 8.7 Hz), 128.7, 128.8 (d, J_CF= 3.0 Hz), 129.1 (d,

J_CF= 13.7 Hz), 129.7 (d, J_CF= 16.3 Hz), 130.5 (d, J_CF= 5.7 Hz),

131.2 (d, J_CF= 4.2 Hz), 132.4 (d, J_CF= 1.1 Hz), 139.1 (dt,

J_CF= 8.2 Hz, J_CF= 2.1 Hz), 141.0 (td, J_CF= 10.0 Hz, J_CF

2.0 Hz), 142.7, 160.1 (d, J_CF= 248.6 Hz), 160.3 (dd, J_CF

=

248.8 Hz, J_CF= 7.8 Hz), 160.8 (d, J_CF= 244.4 Hz), the increased

intensity of the signal at δ = 13.9 indicates that two carbon

resonances coincide here; m/z (APCIϩ, CH₂Cl₂, hexane) 463.5

[M ϩ H]^ϩ.

9 (a) H. Kobayashi, S. Yamada, E. Chino, M. Yazaki, H. Iisaka and

Y. Tsuchiya, Seiko Epson Corp. (Japan), Eur. Pat. Appl. EP

0730019A1, 4.9.1996; (b) D. Coates, J. A. Jenner, V. Reiﬀenrath

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2Ј,6Ј,3ٞ,5ٞ-Tetraﬂuoro-4,4ٞ-dipropyl[1,1Ј:4Ј,4Љ:1Љ,1ٞ]quater-

phenyl 8{1,4,1,4}. δ_H(400.1 MHz, CDCl₃) 0.99 (br. t, J_HH

7.4 Hz, 6 H), 1.67 (sextet, J_HH= 7.6 Hz, 2 H), 1.69 (sextet, J_HH

7.7 Hz, 2 H), 2.65 (t, J_HH= 7.7 Hz, 2 H), 2.69 (t, J_HH= 7.6 Hz, 2

H), 7.12 (d, line distance 8.5 Hz, AAЈ–part of a AAЈXXЈ–

spectrum, 2 H), 7.24–7.30 (m, 4 H), 7.43 (d, line distance 8.1.

Hz, AAЈ–part of a AAЈXXЈ–spectrum, 2 H), 7.61–7.67 (m,

4 H); δ_C(100.6 MHz, CDCl₃) 13.8, 13.9, 22.8, 24.2, 24.4, 37.9,

109.4 (d, line distance 27.7 Hz, AAЈ–part of a AAЈXXЈ–

spectrum), 110.0 (d, line distance 27.7 Hz, AAЈ–part of a

=

10 For review, see: M. Hird and K. J. Toyne, Mol. Cryst. Liq. Cryst.,

1998, 232, 1–67.

11 M. Hird, G. W. Gray and K. J. Toyne, Mol. Cryst. Liq. Cryst., 1991,

206, 187–204.

AAЈXXЈ–spectrum), 117.1 (t, J_CF= 21.1 Hz), 117.4 (t, J_CF

18.8 Hz), 126.2, 127.3, 127.4, 128.4, 130.1, 138.3 (t, J_CF

2.5 Hz), 139.0 (t, J_CF= 2.5 Hz), 139.9 (t, J_CF= 9.9 Hz), 141.2 (t,

J_CF= 10.1 Hz), 142.9, 160.4 (dd, J_CF= 247.9 Hz, J_CF= 8.4 Hz),

161.9 (dd, J_CF= 246.3, J_CF= 10.2 Hz); m/z (APCIϩ, CH₂Cl₂,

hexane) 463.5 [M ϩ H]^ϩ.

=

12 D. R. Coulson, Inorg. Synth., 1990, 28, 107–108.

13 D. Rehm, B. Ziemer and G. Szeimies, Eur. J. Org. Chem, 1999, 9,

2079–2086.

14 A. L. Allred and L. W. Bush, J. Am. Chem. Soc., 1968, 90, 3352–

3360.

O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 6 0 9 – 1 6 2 4

1624

Article Doi

Combinatorial organic materials research (COMR): design, synthesis and screening of a 225-membered materials library of liquid crystalline fluorinated p-quaterphenyls

DOI: 10.1039/b212107g

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