The importance of micro segregation for mesophase formation: Thermotropic columnar mesophases of tetrahedral and other low-aspect-ratio organic materials

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The Importance of Micro Segregation for Mesophase Formation:

Thermotropic Columnar Mesophases of Tetrahedral and other

Low-Aspect-Ratio Organic Materials

Annegret Pegenau,^[a]Torsten Hegmann,^[a]Carsten Tschierske,*^[a]and Siegmar Diele^[b]

Abstract: Several low-aspect-ratio or-

ganic molecules [tetrahedral pentaery-

thritol derivatives, peracylated polyhy-

droxy compounds and aminoalcohols, a

tetraphenylmethane derivative, a tetra-

phenylstannane, and a tetrahedral zinc

bis(1,3-diketonate) all carrying long ali-

phatic chains] have been synthesized.

These compounds were investigated by

polarizing optical microscopy and differ-

ential scanning calorimetry, and some of

them by X-ray diffraction. Most com-

pounds show columnar liquid-crystalline

mesophases. Their mesogenic properties

are neither caused by a specific aniso-

metric shape of these molecules nor by a

strong amphiphilicity as known from

conventional liquid crystals. Instead

their mesogenity is mainly driven by

micro segregation of the incompatible

molecular parts (polar central regions

and lipophilic alkyl chains) into well-

organized different microdomains. It is

shown that, in analogy to block copoly-

mers, the mesophase stability rises on

enlarging the number of repeat units

connected with each other and on in-

creasing the degree of incompatibility

between the incompatible segments.

During the process of self-organization

the average conformation of the mole-

cules is changed in such a way that it

allows a most efficient packing of the

molecules. Consequently, rigid mole-

cules with a fixed tetrahedral geometry

are not mesogenic. The molecules de-

scribed herein can be regarded as the

most simple star-shaped low-aspect-ra-

tio block molecules that form liquid-

crystalline phases. They bridge the gap

between classical amphiphilic mesogens,

several nonconventional dendritic and

oligomeric liquid crystals, and mesomor-

phic block copolymers.

Keywords: block molecules ´ liquid

crystals ´ micro segregation ´ non-

covalent interactions ´ supramolec-

ular chemistry

mesophases can be found in different classes of compounds.

Most common are anisometric rod-shaped or disc-shaped

molecules, which consist of an anisometric central unit grafted

with flexible chains. Usually these chains are alkyl chains and

provide the mobility, whereas the order is provided by the

packing arrangement of the anisometric groups. Liquid-

crystalline phases are also formed by amphiphilic molecules

either in the pure state (thermotropic mesophases) or in their

aqueous solutions (lyotropic systems). Here supermolecular

aggregates are built up by the attractive forces between the

strongly polar groups of the amphiphiles, which can organize

in ordered structures. Most liquid-crystalline materials syn-

thesized up to now belong to one of these two rough structural

guidelines.

However, in the recent years mesomorphic properties have

been reported for some nonconventional molecules; these

have neither an anisometric shape nor belong to classical

amphiphiles. Their mesomorphic properties could not be

explained on the basis of these classical concepts. For

example, some linear and branched oligoamides and poly-

amides,^{[2, 3]}and some dendritic molecules^{[4, 5]}display thermo-

tropic liquid-crystalline behavior. Columnar mesomorphism

Introduction

The combination of order and mobility on a molecular level is

a typical feature of the liquid-crystalline (LC) state. It leads to

many applications, such as electro-optical displays and

temperature sensors, and it is an important prerequisite for

the existence of life (e.g. cell membranes). Therefore novel

LC materials are of great interest. Additionally, liquid-

crystalline mesophases are of general scientific interest

because they represent typical examples of artificial self-

organizing systems on a supramolecular level.^[1]

According to the molecular order nematic, smectic, colum-

nar, and cubic mesophases can be distinguished. These

[a] Prof. C. Tschierske, A. Pegenau, T. Hegmann

Institut für Organische Chemie

der Martin-Luther-Universität Halle-Wittenberg

D-06120 Halle, Kurt-Mothes-Str. 2 (Germany)

Fax : ( 49)345-55-27030

E-mail: coqfx@mlucom6.urz.uni-halle.de

[b] Dr. S. Diele

Institut für Physikalische Chemie

der Martin-Luther-Universität Halle-Wittenberg

D-06108 Halle, Mühlpforte 1 (Germany)

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FULL PAPER

was found for a few octahedral metal complexes^[6]and for the

so called diabolo compounds.^[7]We have synthesized pentaer-

ythritol tetrabenzoates, such as compound 1d, which can form

columnar mesophases.^[8]These molecules can be regarded as

consisting of a tetrahedral central core to which a varying

number of alkyl chains is grafted through aromatic linking

units. In a preliminary communication we have pointed out the

importance of micro segregation for their mesomorphic proper-

ties and proposed a cylinder model for the organization of the

molecules in the columnar mesophases of these compounds.^[8]

In the meanwhile the same model was used to explain the

mesomorphism of polyamides and some dendrimers.^{[3d, 4, 5]}

Though micro segregation was realized to be a main reason

for the transition from the nematic phase to the smectic

phases and it is well known as driving force for the formation

of lyotropic and thermotropic mesophases of strongly amphi-

philic molecules.^[9]The directed design of mesogenic materials

without anisometric rigid units and without a strong amphi-

philicity is a new approach in liquid crystal chemistry.

Herein we report on systematic structural variations at

these novel low-aspect-ratio materials. For this purpose we

have synthesized molecules related to 1d. We have changed

Scheme 1. Synthesis of the amide 2. Reagents and conditions: i) LiAlH₄,

Et₂O, 208C, 4 h, then H₂O; ii) 3,4-(C₁₀H₂₁O)₂PhCOOH, CMC, DMAP,

CH₂Cl₂, 208C, 72 h; iii) EtOH, H₂O, PPTS, reflux, 5 h.

The pentaerythritol derivative 4, which combines three

acyloxy groups with one ether unit, was prepared according to

Scheme 2. At first, selective protection of three of the hydroxy

the number and length of the alkyl chains. The ester groups in

the polar centers of these molecules were replaced by more-

polar amide groups or by less-polar ether units. Furthermore,

we have changed the number of repeat units and the topology

of their connection and we have synthesized some rigid

tetrahedral molecules. These investigations were carried out

to evaluate the importance of micro segregation for meso-

phase formation of low-molecular-weight organic molecules.

Results and Discussion

Synthesis: Most compounds (1, 3, 12 ± 14, and 17 ± 26) were

obtained in a straight forward manner by acylation of commer-

cially available polyhydroxy compounds and polyhydroxy-

amines with an excess of substituted benzoic acid by the use of

a water-soluble carbodiimide [N-cyclohexyl-N'-(2-morpholi-

noethyl)carbodiimide methyl-p-toluenesulfonate, CMC] in

the presence of 4-(dimethylamino)pyridine (DMAP).^[10]

The amide 2 was synthesized according to Scheme 1. Ethyl-

5-cyano-2-nonyl-1,3-dioxan-5-carboxylate^[11](I) was reduced

to 5-aminomethyl-5-hydroxymethyl-2-nonyl-1,3-dioxan II. Af-

ter acylation of the amino group and the hydroxy group, the

protecting acetal group was cleaved and the diol III was

benzoylated to give the amide 2.

Scheme 2. Synthesis of compound 4. Reagents and conditions:

i) CH₃C(OEt)₃, TosOH, PhMe, reflux, 5 h; ii) 1. NaH, 3,4-

(C₁₀H₂₁O)₂PhCH₂Br, DMF, 5 h, 508C, then 208C, 12 h; 2. HCl, H₂O,

EtOH, 208C, 1 h; iii) 3,4-(C₁₀H₂₁O)₂PhCOOH, CMC, DMAP, CH₂Cl₂,

208C, 72 h.

groups of pentaerythritol was achieved by formation of the

bicyclic orthoacetate IV.^[12]Etherification with 3,4-didecyloxy-

benzyl bromide^[13](obtained from ethyl 3,4-didecyloxyben-

[14]

zoate by reduction with LiAlH₄and subsequent treatment

with PBr₃^[15]) followed by acidolytic cleavage of the protecting

group afforded the triol V, which after acylation gave the

triester 4.

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Micro Segregation

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Scheme 3. Synthesis of the pentaerythritol derivatives 5 ± 7, 15 and 16. Reagents and conditions i) 3,4-(C₁₀H₂₁O)₂PhCHO_,PPTS, benzene, reflux, 20 h; ii) 1.

NaBH₄, CF₃COOH, THF, 08C, then 208C, 4 h; 2. KOH, H₂O, 208C, 5 min; iii) 4-R¹-3-R²-5-R³PhCOOH, CMC, DMAP, CH₂Cl₂, 208C, 72h; iv) NaH, 3,4-

(C₁₀H₂₁O)₂PhCH₂Br, DMF, 508C, 5 h, then 208C, 12 h; v) 3,4-(C₁₀H₂₁O)₂PhCOOH, CMC, DMAP, CH₂Cl₂, 208C, 72 h.

The compounds 5 ± 7, 15, and 16 were prepared as outlined

in Scheme 3. At first the spiroacetal VI was synthesized,^[16]

which was subsequently cleaved to give the dibenzyl ether VII

by reduction with NaBH₄in the presence of trifluoro acetic

acid.^[17]The diol VII was acylated with appropriately sub-

stituted benzoic acids to give the compounds 5, 15, and 16.

Etherification of VII with three equivalents of 3,4-didecyloxy-

benzyl bromide yields a mixture of the triether VIII (from

which compound 6 was obtained) and the tetraether 7, which

could be separated by preparative centrifugal thin-layer

chromatography with a Chromatotron (Harrison Research).

The tetraphenylmethane derivative 9 was obtained by

Pd⁰-catalyzed cross-coupling^[18]of tetrakis(4-bromophenyl)-

methane^[19]with 3,4-didecyloxyphenylboronic acid^[20]as shown

in Scheme 4. To synthesize the tetraphenylstannane 10, 3,4-

didecyloxyphenyl bromide was subjected to a metal halogen

exchange that afforded the corresponding lithiated species,

which afterwards was treated with SnCl₄to yield 10.^[21]For the

preparation of 11, the sodium salt of 1,3-bis(3,4-didecyloxy-

phenyl)-1,3-propanedione^[22]was treated with ZnCl₂´ Et₂O in

refluxing glyme.

Pentaerythritol tetrakis(3,4-dialkoxybenzoates): The phase

transition temperatures and associated enthalpy values of the

pentaerythritol 3,4-dialkoxybenzoates 1 are given in Table 1.

Most of the compounds 1 show liquid-crystalline properties.

On cooling of these compounds from the isotropic liquid state

a spherulithic texture can be observed between crossed

polarizers, which on slight shearing turns into a nonspecific

birefringent texture. These are typical features of columnar

mesophases.

Scheme 4. Synthesis of the tetraphenylmethane derivative 9. Reagents and

conditions: i) Br₂, cat. Fe, CCl₄, 30 ± 358C, 8 h, then 20 h, reflux; ii) 3,4-

(C₁₀H₂₁O)₂PhB(OH)₂, Pd(PPh₃)₄, NaHCO₃, DME, reflux, 8 h.

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Table 1. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of the pentaerythritol tetrakis(3,4-dialkoxybenzoa-

tes) 1.

Figure 1. DSC heating and cooling traces of compound 1d (10 Kmin ¹).

R

K

´

Col

±

I

´

responding to 0.45 nm and three sharp scatterings in the

small-angle region with a ratio of their positions 1:3^0.5:2 which

confirms a hexagonal columnar organization in this meso-

phase (Col_h). The lattice parameter a_hexis nearly independent

1a

1b

1c

1d

1e

1 f

1g

OC₆H₁₃

45

35.3

55

88.9

55

68.6

54

102.3

14

22.0

24

40.4

58

±

OC₈H₁₇

OC₉H₁₉

OC₁₀H₂₁

OC₁₁H₂₃

OC₁₂H₂₅

OC₁₆H₃₃

´

(´

´

31)

´

3.9

42)

4.2

47)

5.4

53

6.0

53

6.1

on the temperature and has been determined to be a_hex

3.3 nm at 258C.

The question arises, how these molecules with a tetrahedral

central core could organize into columns. Typically, thermo-

tropic hexagonal columnar phases are formed by anisometric

disclike molecules^[23]or by amphiphilic or polymeric taper-

shaped molecules.^[24±26]However, no flat disclike molecular

shape or taper shape is provided by the tetrahedral central

core of the pentaerythritol tetrabenzoates. Rather, these

molecules can adapt different conformations with the alkyl

chains more or less randomly distributed around the central

tetrahedral linking unit. The CPK models of two selected

conformations of the pentaerythritol tetrabenzoate 1d are

shown in Figure 2. A conformer with a tetrahedral shape is

shown in Figure 2a. A rather flat arrangement of the 3,4-

dialkoxybenzoyl units is also possible as shown in Figure 2b,

but it is impossible to arrange all four 3,4-dialkoxybenzoyl

units in such a way that they form a really over-all flat disc.

Furthermore, energy is necessary to force the molecules into

the flat conformation and, additionally, any restriction of the

number of conformations would be entropically disfavored.

This situation is different from molecules with a flat and rigid

core in which the disclike shape is inherently given.

More detailed inspection of the molecular models reveals

that in the center of the molecules the polar building blocks

( COO , phenyl, O ) are concentrated, thus creating

distinct polar regions. In these polar regions a large part of

the cohesive energy is provided by polar forces, whereas the

cohesive forces in the periphery result exclusively from the

dispersion forces between the alkyl chains. Therefore, the

polar regions of neighboring molecules should preferably

interact with each other, rather than be distributed between

the aliphatic chains. This leads to the aggregation of the polar

groups with formation of segregated regions. During the

process of self-organization the average conformation of the

individual molecules is influenced. Conformers with a rather

flat shape, similar to that one shown in Figure 2b should be

favored in respect to other conformers, because they enable

the most efficient interaction of their polar regions with those

of neighboring molecules (induced fit). Thus, the central polar

units can aggregate with formation of extended cylinders.

´

±

241.9

The appearance of mesomorphic properties, however,

strongly depends on the length of the alkyl chains. The hexyl

derivative 1a was obtained as an oily liquid that can be

supercooled to 308C without a phase transition. Crystal-

lization sets in after storage for several months at room

temperature (m.p. 458C). The mesophase stability continu-

ously rises with elongation of the chains and then decreases

again. The melting temperatures increase at first (maximum

at compounds 1b and 1c), then they decrease (minimum at

compound 1e) and finally strongly rise again. This leads to

enantiotropic mesophases for compounds 1e and 1 f. Re-

markably, the long-chain compounds 1e ± 1g crystallize much

more rapidly than the short-chain compounds 1a ± 1d. While

the liquid-crystalline samples of compounds 1a ± 1d can be

stored for several days at room temperature without crystal-

lization, the crystalline state of the hexadecylderivative 1g can

only be supercooled to 468C by rapid cooling. Above this

temperature no mesophase was detected. Therefore, we con-

clude that a maximum of mesophase stability (538C) is reached

for compounds 1e and 1 f, and that the clearing temperatures

decrease on further elongation of the alkyl chains.

The didecyloxybenzoate 1d was investigated in more detail.

The DSC (differential scanning calorimetry) heating and

cooling traces of this compound are shown in Figure 1.

Though its liquid-crystalline phase is monotropic (metasta-

ble), the crystalline state can easily be supercooled down to

308C without crystallization (see cooling curve). Slow

crystallization occurs only after prolonged storage at room

temperature.

The X-ray diffraction pattern of its mesophase is charac-

terized by a diffuse scattering in the wide-angle region cor-

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Micro Segregation

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The diameter of the molecule 1d in the disclike conforma-

tion as shown in Figure 2b with all-trans-conformations of the

alkyl chains amounts to D 4.2 nm. Taking into account the

molten disordered state of the alkyl chains and the possibility

of interdigitation of the alkyl chains of neighboring molecules

in the liquid-crystalline state, the hexagonal lattice parameter

(a_hex 3.3 nm) corresponds very well (a_hex/D 0.79) with the

proposed arrangement of the molecules.

a)

Thus, the thermotropic liquid-crystalline properties of these

molecules are not caused by a well-defined anisometric

molecular shape, instead their mesogenity is mainly driven

by micro segregation of distinct incompatible molecular

parts.^[27]In this respect the molecules described here can be

regarded as (starlike) block molecules, that is, as low-

molecular-weight analogues of block-copolymers.^[28]

As in block copolymers, the incompatibility of different

molecular parts gives rise to the segregation of chemically

slightly different segments into well-organized different

microdomains. In AB-diblock copolymers, consisting of two

different polymer chains A and B, the micro segregation is

determined by the size of the blocks (number of statistical

segments in the blocks N N_A N_B) and the degree of

chemical and structural difference between the blocks. The

latter is described by the segment interaction parameter

b)

c_AB,

^{[29, 30]}which is related to the difference of cohesive energy

in the different blocks and can be estimated according to

c_AB V_R(d_Ad_B)²/RT from the solubility parameter d_Aand

d_B. The morphology of the micro-segregated regions is

influenced by the volume fractions of the blocks (f) and the

difference in conformational properties of the two blocks (e).

Since c depends on temperature, micro segregation is temper-

ature dependent and occurs below a certain order± disorder

transition temperature.

Figure 2. CPK models of possible conformations of compound 1d: a) con-

former with a tetrahedral preorganization of the 3,4-didecyloxyphenyl

groups; b) conformer with most flat, disclike arrangement of the 3,4-

didecyloxyphenyl units.

In analogy to block-copolymers the stability of the meso-

phases of the molecules under discussion (measured as their

clearing temperatures) should depend on the size of the

distinct regions and on the degree of difference between them.

Thus the mesophases should be stabilised either by enlarging

the molecules, that is, on increasing the number of segments

covalently bound to each other, and/or by increasing the

intramolecular polarity contrast, that is, by enhancing the

polarity in the polar region. At first we changed the intra-

molecular polarity contrast by structural variations in the

central linking unit.

Furthermore, in these conformers the alkyl chains are radially

preorganized around the central cores; this additionally

favors their organization in cylinders. As shown in Figure 3

Molecules incorporating amide groups: In order to evaluate

the importance of the polarity of the central regions, we at

first replaced one of the carboxyl groups of the tetraester 1d

by an amide group (Table 2), which is more polar and

provides additional cohesive forces by hydrogen bonding.

The amide 2 and also compound 3,^[8c]which has the amide

group directly attached to the central quaternary carbon

atom, have enantiotropic liquid-crystalline phases. The meso-

phases of both compounds have the same spherulitic texture

as the ester compounds 1. However, only one (compound 2)

or two (compound 3) equidistant reflections (see Table 3)

were detected in the small-angle region of the X-ray

diffraction pattern beside a diffuse scattering in the wide-

angle range. These reflections do not allow an assignment of a

Figure 3. Core-shell model of the organization of the compounds 1 in their

hexagonal columnar mesophases.^[8]

these cylinders are surrounded by the liquidlike aliphatic

chains and organize into a hexagonal 2D-lattice, which allows

the most efficient space filling.

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Table 2. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of compounds 1d, 2 and 3.

Table 4. Comparison of the phase transition temperatures (T [8C]) of the

pentaerythritol derivatives 1d, 4, 5b, 6 and 7 (italics refer to the transition

enthalpies DH [kJmol ¹]).

X¹

X²

X³

X⁴

K

´

Col

(´

I

´

X

K

´

Col

(´

I

´

1d

4

COO

OOC

54

102.3

7

10.6

10

34.5

11

59.7

14

47)

5.4

32

5.1

24

5.0

23

6.1

21

6.8

1d

2

COOCH₂

54

47)

5.4

72

5.9

66

7.6

COO

CH₂O

COO

CH₂O

OOC

OCH₂

´

102.3

[a]

CONHCH₂

CONH

´

±

´

5b

6

3

47

29.5

7

[a] Crystallization has not yet been observed.

54.1

Table 3. Scattering vectors (d₁d₃[nm]) and hexagonal lattice parameter

(a_hex) of the mesophases of selected compounds; a_hexvalues in square brackets

are calculated from the (10) reflection assuming a hexagonal lattice.

polarized-light optical microscopic textures of their meso-

phases are again spherulitic textures as observed for the other

tetrahedral molecules. As a typical example, the texture of 4 is

shown in Figure 4. X-Ray diffraction proved the hexagonal

d [nm]

T [8C]

(10)

(11)

(20)

a_hex[nm]

1d

2

3

25

40

2.89

2.88

2.82

2.89

2.98

diffuse

2.84

2.81

2.88

1.65

1.43

1.47

3.33

[3.33]

[3.24]

3.40

4

1.70

1.77

1.46

1.53

5b

17

18

25

26

3.53

[3.35]

[3.24]

[3.32]

columnar mesophase from the X-ray results, but it should be

emphasized that the 3^0.5reflection is often not observed in the

scattering diagrams because of its low intensity. Therefore, on

the basis of the observed textures and because of the complete

miscibility of the mesophases of 2 and 3 with the Col_hphase of

compound 1d, we assume that the mesophases of the amides 2

and 3 are hexagonal columnar mesophases.

Both amides 2 and 3 show enhanced stabilities of their

liquid-crystalline phases in comparison with the tetrabenzoate

1d; this is in accordance with the proposed model. It shows

that the mesophases of the pentaerythritol tetrabenzoates can

indeed be stabilized by enhancing the intramolecular polarity

contrast. However, in these amides intermolecular hydrogen

bonding also contributes to the mesophase stabilization.

Therefore we did not synthesize other molecules of this type

with a further increased number of amide groups. Instead we

asked what would happen, if we decrease the polarity in the

central region.

Figure 4. Optical texture of the hexagonal columnar mesophase of

compound 4 as obtained by cooling from the isotropic melt (crossed

polarizers) at 308C.

columnar structure (see Table 3) of the mesophases of

compounds 4 and 5b.

Replacement of only one carboxyl group of the tetraben-

zoate 1d by a CH₂O group lowers the mesophase stability

considerably. The effect of the second ether group is less

pronounced (compound 5b). The diether 5b and the triether 6

have nearly the same clearing temperature as the tetraether 7,

in which all ester group are replaced by the less-polar ether

groups. The more-polar ester groups clearly stabilize the

mesophases, but they are not necessary for mesogenity.

Obviously, the intramolecular polarity contrast provided by

the aromatic units, together with the ether oxygens (both

benzyl ethers and phenyl ethers) is sufficient to enable micro

Tetrahedral molecules incorporating ether groups: In order to

achieve this the carboxyl groups of the tetrabenzoate 1d were

replaced step by step by less polar CH₂O groups. Compounds

4 ± 7 (see Table 4) are all liquid-crystalline materials. The

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Chem. Eur. J. 1999, 5, No. 5

Micro Segregation

1643±1660

segregation for these molecules. Though the observed de-

pendence of the mesophase stability on the polarity of the

central core unit is in line with the proposed model based on

micro segregation, we have to take into account that also

other molecular parameter are changed by these structural

variations that can also influence the mesomorphic properties.

This is discussed in the next section.

petes with the mesophase destabilizing effect of the increased

rigidity. Thus, polarity and rigidity compete with each other in

these molecules. The decreased mesophase stability of the

amide 3 in comparison with the amide 2 is probably a result of

the increased rigidity of the CONH connecting unit

(compound 2) in comparison with the CONHCH₂unit of

3. It is also possible that the plateau like behavior of the

clearing temperatures of the ether compounds 4 ± 7 could be

the result of a competition between rigidity (and other

molecular parameter) and micro segregation. In any case,

segregation tendency and rigidity act in different directions in

these pentaerythritol derivatives.

In contrast to these molecules with tetrahedral cores, in

classical disclike mesogens increased rigidity of the disc-

shaped central units favors mesophase formation. There are

also some cases of mesogens with a rather flexible central core

forming columnar mesophases. One example is provided by

the mesogenic azacrown derivatives.^[32]Acylated azacrowns

form columnar mesophases, whereas the related alkyl deriv-

atives do not. Here, rigidification of the molecules by the

amide groups is assumed to stabilize disclike conformers and

thus stabilizes columnar mesophases. However, not only the

rigidity, but also the polarity contrast is much larger in the

acylated azacrowns (amides) than in the alkylated azacrowns

(amines), and therefore micro segregation should also con-

tribute to mesophase formation. Here, both effects act in the

same direction and therefore no decision can be made

concerning the importance of micro segregation in these

molecules. However, in the tetrahedral molecules described

herein, both effects are in competition to each other,

uncovering the importance of micro segregation for their

mesophase formation.

The interplay of polarity and rigidity: In order to evaluate the

cohesive energy provided by the distinct molecular parts we

have estimated the solubility parameter of the central units by

using the group contributions and equations proposed by Hoy

for amorphous polymers (Table 5).^[31]The solubility parame-

ter d_trepresents the square root of the total cohesive energy

Table 5. Solubility parameter d_tand their polar (d_p), hydrogen bonding

(d_h) and dispersion (d_d) components of the central building blocks of the

compounds 1d, 2 and 4 ± 7 as calculated according to the method of Hoy

[J^0.5cm ^1.5].^[31]

central unit

d_t

d_p

d_h

d_d

CONHCH₂C(CH₂OOC )₃

C(CH₂OOC )₄

CH₂OCH₂C(CH₂OOC )₃

( CH₂OCH₂)₂C(CH₂OOC )₂

( CH₂OCH₂)₃CCH₂OOC

26.6

24.2

23.5

22.9

22.2

21.5

15.7

14.3

13.3

12.2

10.9

9.4

16.6

13.7

13.2

13.8

14.6

15.1

15.8

±

C(CH₂OCH₂

)

4

density, whereas d_d, d_p, and d_hrepresent the dispersion, polar,

and hydrogen bonding components, respectively. Clearly the

cohesive forces between the alkyl chains are exclusively

dispersion forces, whereas dispersion and polar forces are

found in the region of the benzoate groups. Because the 3,4-

didecyloxyphenyl groups are identical constituents of the

molecules 1d, 2, and 4 ± 7, their contribution should be

constant. Therefore, we have considered only the central

C(CH₂X)₄units (X OOC, NHCO, OCH₂) without the

aromatic rings. The d_pvalues of the central units decrease in

the same way as the stability of their liquid-crystalline phases

decreases; this is in agreement with the proposed model. The

especially strong increase of mesophase stability by introduc-

tion of the amide group should largely be caused by the

additional hydrogen bonding.

As mentioned above, by means of structure variations it is

impossible to change one parameter exclusively. Also other

molecular parameters, such as bond angles, bond lengths, the

rotational barriers, and the conformational energies, are

changed. Therefore these effects can additionally contribute

to the total effect. The rigidity of the connecting units between

the central tetrahedral core and the aromatic rings, for

example, should increase in the order CH₂OCH₂<

COOCH₂< CONHCH₂< CONH. In this order tetrahedral

shaped conformers that inhibit mesophase formation (Fig-

ure 2a) should be favored, whereas deformation of the

molecules to give a more disclike shape becomes increasingly

more difficult. Because the adaptation of a disclike shape

facilitates molecular self-organization in columns, columnar

mesophases should be stabilized by reducing the rigidity of

the connecting units. Since the polarity of the connecting units

rises in the same direction as the rigidity increases, the

mesophase stabilization gained by increased polarity com-

Tetrahedral biphenyl derivatives: We have tried to further

evaluate the influence of rigidity on mesophase formation.

Therefore the ester compound 8 (Figure 5), in which the

phenyl rings of the tetrabenzoate 1d are replaced by rodlike

biphenyl units, was synthesized.^[33]This compound displays a

monotropic mesophase with a nonspecific texture. It occurs

on cooling at 728C and immediately crystallizes. Due to the

rapid crystallization no X-ray studies could be performed. In

the contact region with the hexagonal columnar phase of the

pentaerythritol tetrabenzoate 1d, a broad isotropic region

occurs. This indicates the incompatibility of the hexagonal

columnar phase of 1d with the unknown phase of 8.

The tetraphenylmethane derivative 9, in which the rather

flexible CH₂OOC groups of 1d are formally replaced by rigid

1,4-phenylene units, is only

a crystalline solid (m.p.

748C).^{[34, 35]}The isotropic melt can be supercooled to 428C

without formation of a mesophase.

Additionally we have synthesized compound 10, in which

the tetrahedral central unit is directly connected to the phenyl

rings. For preparative reasons a tetrahedral tin atom instead of

a tetrahedral carbon was used. This compound is also

nonmesogenic. Another example of a rigid tetrahedral

molecule is provided by the zinc acetylacetonate 11. Here,

rigidity is combined with a polar center, but this compound is

also only a crystalline solid. It seems, that indeed no

mesophases can be obtained in rigid tetrahedral molecules.^[36]

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to clarify this we have changed the number of alky chains

attached to the polar central regions. Grafting additional alkyl

chains to the phenyl benzoate moieties of the pentaerythritol

tetrabenzoates 1 decreases the mesophase stability (Table 6).

Compound 12b with twelve lipophilic decyloxy chains has a

Table 6. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of the pentaerythritol tetrabenzoates 12 ± 14.

R¹

R²

K

Col

I

12a

12b

OC₆H₁₃

OC₁₀H₂₁

OC₆H₁₃

OC₁₀H₂₁

´

< 20

41

121.9

50

236.1

42

72.7

72

±

(´

±

´

8)

5.9

±

12c

13a

13b

14

OC₁₆H₃₃

OC₁₀H₂₁

OC₁₆H₃₃

H

OC₁₆H₃₃

H

´

±

(´

´

±

H

180.1

35

OC₁₀H₂₁

7)

96.3

9.3

considerably lower mesophase stability than 1d bearing only

eight of these chains. Obviously the space required by the

twelve alkyl chains is larger than necessary for the efficient

surrounding of the polar cylindrical regions. Thus, the polar

interactions between the central regions of neighboring

molecules are disturbed for steric reasons. This shows, that

the molecules must be able to interact efficiently through both

of their incompatible parts in order to form liquid-crystalline

phases.

Also the 4-alkoxybenzoates 13, which carry only four

instead of eight alkoxy chains, are not mesomorphic (13a can

be supercooled to 258C, 13b to 258C). Interestingly, no

smectic phases were found as could be expected from the

nearly equivalent space filling of polar and lipophilic regions

in these molecules. Probably the tetrahedral preorganization

of the substituents around the pentaerythritol central units

disfavors the formation of layer structures and instead

mesomorphic properties get lost.

In the following we have combined different building

blocks. In the series 5a ± c the length of four alkyl chains was

changed keeping the other four chains constant. Compound

5a which combines hexyl and decyl chains has a significantly

lower mesophase stability than compound 5b with eight decyl

chains (Table 7). Again, the hexadecyl substituted compound

5c is a rather high-melting crystalline solid which cannot be

supercooled.

Figure 5. Phase transition temperatures (T [8C]) of the tetrahedral

compounds 8 ± 11.

Influence of the number and position of the chains: As

mentioned above, the mesomorphic properties of the pen-

taerythritol tetrakis(2,3-dialkoxybenzoates) occur at a certain

length of the alkyl chains. The reason may be that in short-

chain compounds the number of repeat units (CH₂) in the

lipophilic regions is not large enough for micro segregation,

but additionally space filling effects are responsible. In order

In compound 15 two double chain and two triple chain units

are combined, whereas in compound 16 double chain and

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Micro Segregation

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Table 7. Phase transition temperatures (T/8C) and transition enthalpies

DH/ kJmol ¹(italics) of the desymmetrized compounds 5, 15 and 16.

R¹

R²

R³

H

K

´

Col

´

I

´

[a]

5a

5b

5c

15

16

C₆H₁₃O

±

5

3.2

10

34.5

42

112.2

8

12.6

1

C₁₀H₂₁O

C₁₆H₃₃O

C₁₀H₂₁O

C₁₆H₃₃O

C₁₀H₂₁O

H

´

24

5.0

±

´

Figure 6. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of the erythritol and d-threitol tetrabenzoates 17

and 18.

H

±

´

C₁₀H₂₁O

H

14

7.6

3

2.9

phases. The clearing points are slightly decreased in compar-

ison with the pentaerythritol derivative 1d.

´

26.9

In the X-ray diffraction pattern of the mesophases of both

compounds a diffuse scattering in the wide-angle region

indicates the liquidlike organization of the alkyl chains. Only

one reflection corresponding to a d value of 2.84 nm is found

in the small-angle region of the diffraction pattern of the

threitol derivative 18 (see Table 3). Therefore the assignment

of the mesophase is based on the spherulitic texture and the

uninterrupted miscibility with the pentaerythritol tetraben-

zoate 1d; these both point to a hexagonal columnar meso-

phase. In the case of the erythritol tetrabenzoate 17, only a

diffuse scattering is found in the small-angle region. Its

position corresponds to that found in the small-angle scatter-

ing of the diastereomer 18. Though this diffraction pattern is

reminiscent of nematic phases, this can be excluded from the

observed spherulithic texture. Additionally, there is an unin-

terrupted miscibility with the columnar phase of the proven

hexagonal columnar mesophase of the pentaerythritol tetra-

benzoate 1d. Probably, the unusual X-ray pattern of this

compound can be explained by a partial loss of long-range

positional order of the columns due to the slightly elongated

shape of the molecules.^[38]

[a] Crystallization has not yet been observed.

single chain units are connected. In both cases the mesophase

stability is lower than that one of the compound 5b with four

3,4-didecyloxyphenyl groups. It seems, that in this class of

compounds a number of eight alkyl chains grafted to the

central core represents an optimum for mesophase formation.

Interestingly, the optimal number of alkyl chains can also be

realized very simply by mixing two pentaerythritol derivatives

that have a different number of alkyl chains. In the contact

region between the 3,4,5-tridecyloxybenzoate 12b and the

nonmesogenic 4-decyloxybenzoate 13a the columnar meso-

phase of 12b is slightly stabilized (T_cl,max 128C). This means

that in the contact region the optimal conditions for meso-

phase formation is realized. This behavior is reminiscent of

lyotropic systems and of thermotropic phases of mixed

systems of amphiphilic polyhydroxy compounds.^[25]

These results show that an appropriate number and length

of the aliphatic chains is important for mesophase formation

in this class of compounds. However, the position of the

alkoxy chains is also of importance. The 3,5-didecyloxyben-

zoate 14, which is an isomer of the 3,4-didecyloxybenzoate 1d

that differs exclusively in the position of the alkyl chains to

each other, has a clearing temperature similar to the 3,4,5-

trisubstituted compound 12b. One explanation could be that

the space required by the two chains in 3,5-position is

approximately the same as that required by the three chains

of the trialkoxy benzoates. On the other hand, it is often

observed that 3,5-dialkoxybenzoates have lower mesophase

stabilities than the corresponding 3,4-dialkoxybenzoates.^{[25c, 37]}

Tribenzoates: In a next step we asked, what would happen if

the number of 3,4-dialkoxybenzoyl groups connected with

each other is changed. In compound 19 one of the 3,4-

dialkoxybenzoyl units of the pentaerythritol tetrabenzoate 1d

is removed. The tribenzoate of tris(hydroxymethyl)methane

is a rather high melting solid without mesomorphic properties

(supercooled to 558C). Also on cooling the glycerol ester 20 to

308C no liquid crystalline phases were found (see Table 8). It

seems, that in this class of compounds a minimum number of

at least four 3,4-dialkoxybenzoyl groups must be connected

with each other to observe liquid-crystalline properties.

Interestingly, the replacement of one carboxyl group of the

glycerol ester 20 by an amide group (increased polarity and

additional hydrogen bonding) can produce liquid crystallinity

(compound 21, see Table 8).^[8c]However, only the amide 21

can be supercooled to sufficiently low temperatures that

allows the observation of the mesophase.

Linear tetrabenzoates: In a next step we investigated the

influence of the topology of connection of the 3,4-dialkoxy-

benzoate units. For this purpose the tetrahedral pentaery-

thritol linking unit was replaced by central units that allow the

3,4-dialkoxybenzoate groups to be fixed in a more linear

fashion. The tetrakis(3,4-didecyloxybenzoates) of erythritol

17 and d-threitol 18^[8c](Figure 6) form monotropic meso-

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Table 8. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of tris(3,4-didecyloxybenzoates) 19 ± 22.

X

Y

O

K

´

Col

±

I

´

19

20

21

22

OCH₂

75

95.4

98

103.9

97

±

O

´

±

(´

±

´

O

NH

O

64)

2.6

±

85.6

94

NH

87.7

Pentabenzoates and hexabenzoates: The adonitol derivative

23, the d-mannitol derivative 24,^[8c]and the dipentaerythritol

derivative 26 are molecules in which five or six 3,4-didecyloxy-

benzoate units are connected (Figure 7). All three compounds

exhibit liquid crystalline properties. The highest mesophase

stability is found for compounds 24 and 26 with the largest

number of phenyl benzoate units. The increased clearing

temperature of the d-mannitol derivative 24 in comparison

with the d-threitol derivative 18 indicates, that the meso-

phases can be stabilized by increasing the number of 3,4-

dialkoxybenzoyl groups connected with each other (i.e., by

increasing the number of nonmesogenic repeat units). An

especially high clearing temperature was found for the

dipentaerythritol derivative 26. Compound 26 was investigat-

ed by X-ray diffraction. As in the cases of other polybenzoates

with nontetrahedral central linking units its X-ray diffraction

pattern is characterized by a diffuse scattering in the wide-

angle range and only two equidistant reflections in the small-

angle region. Again, the optical textures (spherulitic textures)

of the mesophases of compounds 23, 24, and 26 and the

uninterrupted miscibility of the mesophases of these com-

pounds with the Col_hphase of the pentaerythritol tetraben-

zoate 1d suggest that the mesophases of these compounds are

also hexagonal columnar phases.

Figure 7. Phase transition temperatures (T [8C]) and transition enthalpies

DH [kJmol ¹] (italics) of the compounds 23 ± 26.

As expected, replacing one carboxyl group of the mannitol

hexabenzoate 24 by an amide group (compound 25) signifi-

cantly stabilizes the liquid crystalline phase.

different segments into well-organized different microdo-

mains. The micro segregation can be observed below a certain

order± disorder temperature, the clearing temperature, and

depends on the size of the incompatible segments and on the

degree of incompatibility between them. For example, the

ethyl 3,4-didecyloxybenzoate 27 (see Figure 8), which repre-

sents a monomeric segment of the liquid crystalline com-

pound 1d, is a nonmesomorphic compound. If the ester group

of 27 is replaced by more polar groups, such as a polyhydroxy

group^{[24a±d, 25]}in the pentaerythritol ether V (an intermediate

in the synthesis of compound 4) a stronger amphiphilicity is

generated and columnar liquid-crystalline properties can be

found for this small but strongly amphiphilic tapered mole-

cule (Figure 8). Another way to reinforce micro segregation

Conclusion

The compounds described herein belong to a novel class of

thermotropic liquid-crystalline compounds forming columnar

mesophases. Their mesogenic properties are neither caused

by a specific anisometric shape of these molecules as known

from classical disc-shaped mesogens nor by a strong amphi-

philicity as known from ionic amphiphiles and polyhydroxy

amphiphiles. Instead their mesogenity is mainly driven by

micro segregation of incompatible molecular parts.^[27]As in

block copolymers^[28]the incompatibility of different molecular

parts gives rise to the segregation of the chemically slightly

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Micro Segregation

1643±1660

gap between classical amphiphilic mesogens, several non-

conventional dendritic and oligomeric liquid crystals, and

mesomorphic block copolymers. Most importantly, they

provide a novel designing principle for liquid crystals that

could lead to interesting new materials in the near future.

Experimental Section

General: ¹H, ¹³C, and ¹¹⁹Sn NMR spectra were obtained on Varian

Gemini 200, Varian Unity 400, and Varian Unity 500 spectrometers. Mass

spectra were recorded on an AMD 402 Intectra (70 eV) instrument and on

a Hewlett ± Packard LD-TOF-system G2025A. Microanalyses were per-

formed with a CHNF-932 (Leco) elemental analyzer. Infrared spectro-

scopy was performed with a Perkin-Elmer Spektrum 1000 spectrometer.

Thin-layer chromatography was performed on aluminium TLC plates

(silica gel 60 F₂₅₄) from Merck. For the preparative centrifugal thin-layer

chromatography a Chromatotron from Harrison Research Europe (Mut-

tenz) was used. Transition temperatures were measured by the use of a

Mettler FP 82 HT hot stage and control unit in conjunction with a Nikon

Optiphot 2 polarizing microscope, and these were confirmed from differ-

ential scanning calorimetry (Perkin Elmer DSC-7). Tetrahydrofuran,

diethyl ether, and benzene were distilled from sodium/benzophenone

ketyl; dichlormethane was distilled from P₄O₁₀; DMF was distilled from

CaH₂; ethanol and glyme were used as obtained. Adonitol (Acros),

1-amino-1-deoxy-d-sorbitol (Aldrich), 2-amino-1,3-propanediol (Aldrich),

1-amino-2,3-propanediol (Merck), ethyl 4-bromobenzoate (Aldrich), N-

cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl-p-toluenesulfon-

ate (CMC, Fluka), 4-(dimethylamino)pyridine (Merck), dipentaerythritol

(Aldrich), meso-erythritol (Acros), glycerol (Ferak Berlin), 2-(hydroxy-

methyl)-1,3-propanediol (Aldrich), d-mannitol, pentaerythritol (Merck),

phosphorus tribromide (Merck), pyridinium 4-toluenesulfonate (Merck),

4-toluene sulfonic acid (Chemapol), d-threitol (Fluka), trifluoro acetic acid

(Merck), and tris(hydroxymethyl)aminomethane (Serva) were used with-

out further purification. Sodium hydride (80% suspension in paraffin) was

washed three times with dry hexane under an argon atmosphere and dried

under a stream of argon. Substituted benzoic acids^[25c], 3,4-didecyloxybenz-

aldehyde,^[41]3,4-didecyloxybenzyl bromide,^[15]3,4-didecyloxyphenylboron-

ic acid,^[20]4-(hydroxymethyl)-1-methyl-2,6,7-trioxabicyclo[2.2.2]octane,^[12]

tetrakis(4-bromophenyl)methane,^[19]3,4-didecyloxybromobenzene,^{[20, 42]}1,3-

bis(3,4-didecyloxyphenyl)-1,3-propanedione,^[22]and Pd(PPh₃)₄^[43]were syn-

thesized according to literature procedures.

Figure 8. Structural variations at the nonmesogenic dialkoxybenzoate 27

which could lead to mesomorphic properties (Cub cubic mesophase).

consists in the enlargement of the antagonistic molecular

parts by linking them together covalently. This is realized in

the compounds described herein. In this way the phenyl

benzoate units become preorganized; this enables them to

interact cooperatively forming a polar region that is able to

segregate from the regions of the lipophilic alkyl chains. The

relative space filling of the segregated regions and the

preorganization of the lipophilic chains around the central

linking units favor columnar aggregates.

The compounds reported in this paper are related to other

nonconventional mesogens reported recently, such as open

chain oligoamides^{[2, 3, 4]}, some DOBOB-esters of 2-hydroxy-

methyl-2-nitro-1,3-propanediol^[39]and pentaerythritol,^[40]and

diabolo mesogens.^[7]Cone-shaped dendritic 3,4,5-tris-(3,4,5-

trialkoxybenzyloxy)benzene derivatives and related dendrons

of higher generation also can self-organize to columnar and

cubic mesophases and provide an alternative approach to

reinforce micro segregation (see Figure 8).^[5]Here the polar

regions are enlarged by dendritic branching. Also higher

generation dendrimers consisting of branched oligoamine

polar regions, peripherally surrounded by 3,4-dialkoxyben-

zoate groups, have recently been reported.^[4]

Acylation of polyhydroxy compounds and amino alkoholsÐgeneral

procedure: At 208C

a suspension of the appropriate polyhydroxy

compound or amino alcohol was stirred in dry CH₂Cl₂(70 mL per mmol).

Two equivalents of the appropriately substituted benzoic acid, 2.4 equiv-

alents of CMC per XH group to be acylated, and a catalytic amount of

DMAP (20 mg) were added, and the mixture was stirred for 72 hours at

208C. The reaction mixture was washed once with water (70 mL). The

aqueous phase was extracted with CHCl₃(20 mL), and the organic layer

was dried over Na₂SO₄. The solvent was removed in vacuo to give the crude

product, which was purified by preparative centrifugal thin-layer chroma-

tography (Chromatotron). The complete acylation was proved by infrared

spectroscopy of the final products (absence of nÄ_{O H}).

1,3-Bis(3,4-dihexyloxybenzoyloxy)-2,2-bis(3,4-dihexyloxybenzoyloxymethyl)-

propane (1a): Synthesized from pentaerythritol (0.136 g, 1 mmol) and 3,4-

dihexyloxybenzoic acid (2.6 g, 8 mmol). Purified twice by chromatography

with petroleum ether/ethyl acetate (10:1.5 ± 2). Yield: 0.27 g (20% ); m.p.

458C; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 ± 0.90 (m, 24H;

CH₃), 1.31 ± 1.36 (m, 32H; CH₂), 1.43 ± 1.47 (m, 16H; O(CH₂)₂CH₂), 1.76 ±

1.84 (m, 16H; OCH₂CH₂), 3.98 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.00 (t,

³J(H,H) 6.6 Hz, 8H; OCH₂), 4.60 (s, 8H; CCH₂), 6.77 (d, ³J(H,H)

8.5 Hz, 4H; Ar H), 7.47 (d, ⁴J(H,H) 2.0 Hz, 4H; Ar H), 7.56 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 4H; Ar H); MS (MALDI-TOF,

DHB): m/z: 1375.5 [MNa] , 1392.1 [MK] ; C₈₁H₁₂₄O₁₆(1353.7): calcd

C 71.87, H 9.22; found C 71.91, H 9.33.

In summary, the molecules described herein can be

regarded as the most simple starlike low-aspect-ratio block

molecules that form liquid-crystalline phases. They bridge the

1,3-Bis(3,4-dioctyloxybenzoyloxy)-2,2-bis(3,4-dioctyloxybenzoyloxymethyl)-

propane (1b): Synthesized from pentaerythritol (0.136 g, 1 mmol) and 3,4-

dioctyloxybenzoic acid (3.1 g, 8 mmol). Purified twice by chromatography

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with petroleum ether/ethyl acetate (10:1.5). Yield: 0.46 g (29%); K 558C

Col 318C I; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t,

1.86 (m, 16H; OCH₂CH₂), 3.98 (t, ³J(H,H) 6.4 Hz, 8H; CH₂), 4.01 (t,

³J(H,H) 6.6 Hz, 8H; OCH₂), 4.61 (s, 8H; CCH₂), 6.78 (d, ³J(H,H)

8.6 Hz, 4H; Ar H), 7.48 (d, ⁴J(H,H) 2.0 Hz, 4H; Ar H), 7.57 (dd,

³J(H,H) 8.6 Hz, ⁴J(H,H) 2.0 Hz, 4H; Ar H); MS (MALDI-TOF,

3

³J(H,H) 7.0 Hz, 12H; CH₃), 0.87 (t, J(H,H) 7.0 Hz, 12H; CH₃), 1.26 ±

1.34 (m, 64H; CH₂), 1.42 ± 1.48 (m, 16H; O(CH₂)₂CH₂), 1.76 ± 1.84 (m,

16H; OCH₂CH₂), 3.97 (t, ³J(H,H) 7.0 Hz, 8H; OCH₂), 4.00 (t, ³J(H,H)

7.0 Hz, 8H; OCH₂), 4.60 (s, 8H; CCH₂), 6.77 (d, ³J(H,H) 8.6 Hz, 4H;

DHB): m/z: 2475.7 [MH] , 2496.3 [MNa] , 2512.8 [MK] ;

C₁₆₁H₂₈₄O₁₆(2475.7) calcd C 78.10, H 11.55; found C 77.75, H 11.35.

4

3

Ar H), 7.47 (d, J(H,H) 2.1 Hz, 4H; Ar H), 7.55 (dd, J(H,H) 8.6 Hz,

⁴J(H,H) 2.1 Hz, 4H; Ar H); MS (MALDI-TOF, DHB): m/z: 1579.3

1,3-Bis(3,4,5-trihexyloxybenzoyloxy)-2,2-bis(3,4,5-trihexyloxybenzoyloxy-

methyl)propane (12a): Synthesized from pentaerythritol (0.136 g, 1 mmol)

and 3,4,5-trihexyloxybenzoic acid (3.4 g, 8 mmol). Purified twice by

chromatography with petroleum ether/ethyl acetate (10:1). Yield: 0.55 g

(31%); m.p. < 208C; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d

0.85 ± 0.89 (m, 36H; CH₃), 1.27 ± 1.35 (m, 48H; CH₂), 1.42 ± 1.48 (m, 24H;

O(CH₂)₂CH₂), 1.68 ± 1.80 (m, 24H; OCH₂CH₂), 3.94 (t, ³J(H,H) 6.6 Hz,

16H; OCH₂), 3.98 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.58 (s, 8H; CCH₂),

7.19 (s, 8H; Ar H); ¹³C NMR (50 MHz, CDCl₃): d 13.84, 22.48, 22.54,

25.59, 25.67, 29.24 29.59, 30.21, 31.50, 43.39 (CCH₂), 63.02 (CCH₂), 69.27,

[MH] , 1602.2 [MNa] , 1618.7 [MK] ; C₉₇H₁₅₆O₁₆(1578.1): calcd C

73.83, H 9.95; found C 73.81, H 9.96.

1,3-Bis(3,4-dinonyloxybenzoyloxy)-2,2-bis(3,4-dinonyloxybenzoyloxymethyl)-

propane (1c): Synthesized from pentaerythritol (0.136 g, 1 mmol) and 3,4-

dinonyloxybenzoic acid (3.2 g, 8 mmol). Purified twice by chromatography

with petroleum ether/ethyl acetate (10:1.5). Yield: 0.39 g (23%); K 558C

Col 428C I; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t,

³J(H,H) 7.1 Hz, 12H; CH₃), 0.87 (t, ³J(H,H) 6.8 Hz, 12H; CH₃),

1.25 ± 1.34 (m, 80H; CH₂), 1.42 ± 1.47 (m, 16H; O(CH₂)₂CH₂), 1.76 ± 1.84

(m, 16H; OCH₂CH₂), 3.97 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.00 (t,

³J(H,H) 6.6 Hz, 8H; CH₂), 4.60 (s, 8H; CCH₂), 6.76 (d, ³J(H,H) 8.6 Hz,

4H; Ar H), 7.47 (d, ⁴J(H,H) 2.0 Hz, 4H; Ar H), 7.55 (dd, ³J(H,H)

8.6 Hz, ⁴J(H,H) 2.0 Hz, 4H; Ar H); MS (MALDI-TOF, CHC): m/z:

73.52, 108.33, 123.99, 143.18, 153.11, 165.98 (C O); MS (MALDI-TOF,

DHB): m/z: 1755.0 [M] , 1777.1 [MNa] , 1794.1 [MK] ; C₁₀₅H₁₇₂O₂₀

(1754.3).

1,3-Bis(3,4,5-tridecyloxybenzoyloxy)-2,2-bis(3,4,5-tridecyloxybenzoyloxy-

methyl)propane (12b): Synthesized from pentaerythritol (0.136 g, 1 mmol)

and 3,4,5-tridecyloxybenzoic acid (4.7 g, 8 mmol). Purified twice by

chromatography with petroleum ether/ethyl acetate (10:0.7). Yield:

0.43 g (18%); K 418C Col 88C I; ¹H NMR (500 MHz, CDCl₃, 258C,

1712.0 [MNa] , 1728.2 [MK] ; C₁₀₅H₁₇₂O₁₆(1690.3): calcd C 74.61, H

10.25; found C 74.42, H 10.20.

1,3-Bis(3,4-didecyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzoyloxymethyl)-

propane (1d): Synthesized from pentaerythritol (0.136 g, 1 mmol) and 3,4-

didecyloxybenzoic acid (3.5 g, 8 mmol). Purified twice by chromatography

with petroleum ether/ethyl acetate (10:0.7 ± 1.5). Yield: 0.41 g (22%); K

548C Col 478C I; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.85 ± 0.87

(m, 24H; CH₃), 1.25 ± 1.34 (m, 96H; CH₂), 1.42 ± 1.48 (m, 16H;

O(CH₂)₂CH₂), 1.76 ± 1.83 (m, 16H; OCH₂CH₂), 3.97 (t, ³J(H,H) 6.6 Hz,

8H; OCH₂), 4.00 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.60 (s, 8H; CCH₂),

6.77 (d, ³J(H,H) 8.5 Hz, 4H; Ar H), 7.48 (d, ⁴J(H,H) 1.9 Hz, 4H;

Ar H), 7.57 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 1.9 Hz, 4H; Ar H);

¹³C NMR (125 MHz, CDCl₃): d 14.07, 22.67, 25.99, 26.05, 29.11, 29.25,

29.34, 29.35, 29.40, 29.45, 29.56, 29.59, 29.61, 29.64, 31.91, 43.23 (CCH₂),

3

TMS): d 0.86 (t, J(H,H) 7.1 Hz, 24H; CH₃), 0.87 (t, J(H,H) 7.1 Hz,

12H; CH₃), 1.25 ± 1.33 (m, 144H; CH₂), 1.42 ± 1.48 (m, 24H; O(CH₂)₂CH₂),

1.68 ± 1.79 (m, 24H; OCH₂CH₂), 3.93 (t, ³J(H,H) 6.4 Hz, 16H; OCH₂),

3.97 (t, ³J(H,H) 6.4 Hz, 8H; OCH₂), 4.58 (s, 8H; CCH₂), 7.18 (s, 8H;

Ar H); MS (MALDI-TOF, CHC): m/z: 2449.0 [MNa] , 2465.7 [MK] ;

C

₁₅₃H₂₆₈O₂₀(2427.5): calcd C 75.70, H 11.12; found C 75.93, H 11.18.

1,3-Bis(3,4,5-trihexadecyloxybenzoyloxy)-2,2-bis(3,4,5-trihexadecyloxy-

benzoyloxymethyl)propane (12c): Synthesized from pentaerythritol

(0.068 g, 0.5 mmol) and 3,4,5-trihexadecyloxybenzoic acid (3.7 g, 4 mmol).

Purified twice by chromatography with CHCl₃/petroleum ether (6:10 ± 0)

and recrystallization from ethyl acetate. Yield: 0.47 g (27%); m.p. 508C;

¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t, ³J(H,H) 6.8 Hz,

36H; CH₃), 1.24 ± 1.31 (m, 288H; CH₂), 1.41 ± 1.50 (m, 24H; O(CH₂)₂CH₂),

1.68 ± 1.79 (m, 24H; OCH₂CH₂), 3.93 (t, ³J(H,H) 6.6 Hz, 16H; OCH₂),

3.97 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.57 (s, 8H; CCH₂), 7.18 (s, 8H;

63.34 (CCH₂), 69.08, 69.35, 112.06, 114.44, 121.75, 123.68, 148.73, 153.58,

1

165.94 (C O); IR (Nujol): nÄ 1721 cm (C O); MS (MALDI-TOF,

DHB): m/z: 1803.5 [MH] , 1826.3 [MNa] , 1843.2 [MK] ; C₁₁₃H₁₈₈O₁₆

(1802.5): calcd C 75.30, H 10.50; found C 75.19, H 10.41.

Ar H); MS (MALDI-TOF, DHB): m/z: 3457.6 [MNa] ; C₂₂₅H₄₁₂O₂₀

1,3-Bis(3,4-diundecyloxybenzoyloxy)-2,2-bis(3,4-diundecyloxybenzoyloxy-

methyl)propane (1e): Synthesized from pentaerythritol (0.136 g, 1 mmol)

and 3,4-diundecyloxybenzoic acid (3.7 g, 8 mmol). Purified twice by

chromatography with petroleum ether/CHCl₃(1:1 ± 2). Yield: 0.59 g

(31%); K 148C Col 538C I; ¹H NMR (400 MHz, CDCl₃, 258C, TMS):

d 0.87 (t, ³J(H,H) 7.1 Hz, 12H; CH₃), 0.88 (t, ³J(H,H) 7.3 Hz, 12H;

CH₃), 1.26 ± 1.33 (m, 112H; CH₂), 1.42 ± 1.48 (m, 16H; O(CH₂)₂CH₂), 1.77 ±

1.86 (m, 16H; OCH₂CH₂), 3.99 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.02 (t,

³J(H,H) 6.6 Hz, 8H; OCH₂), 4.62 (s, 8H; CCH₂), 6.78 (d, ³J(H,H)

8.5 Hz, 4H; Ar H), 7.48 (d, ⁴J(H,H) 1.9 Hz, 4H; Ar H), 7.57 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 1.9 Hz, 4H; Ar H); MS (MALDI-TOF,

(3437.3): calcd C 78.62, H 12.07; found C 78.72, H 12.24.

1,3-Bis(4-decyloxybenzoyloxy)-2,2-bis(4-decyloxybenzoyloxymethyl)pro-

pane (13a): Synthesized from pentaerythritol (0.204 g, 1.5 mmol) and

4-decyloxybenzoic acid (3.4 g, 12 mmol). Purified twice by chromatography

with petroleum ether/ethyl acetate (10:0.2 ± 1). Yield: 0.31 g (18%); m.p.

428C; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t, ³J(H,H)

6.8 Hz, 12H; CH₃), 1.26 ± 1.40 (m, 48H; CH₂), 1.42 ± 1.46 (m, 8H;

O(CH₂)₂CH₂), 1.74 ± 1.80 (m, 8H; OCH₂CH₂), 3.96 (t, ³J(H,H) 6.4 Hz,

8H; OCH₂), 4.62 (s, 8H; CCH₂), 6.82 (d, ³J(H,H) 8.8 Hz, 8H; Ar H),

7.91 (d, ³J(H,H) 8.8 Hz, 8H; Ar H); MS (MALDI-TOF, CHC): m/z:

DHB): m/z: 1914.5 [MH] , 1936.1 [MNa] , 1952.7 [MK] ; C₁₂₁

-

1199.5 [MNa] , 1216.2 [MK] ; C₇₃H₁₀₈O₁₂(1177.5): calcd C 74.46, H

H₂₀₄O₁₆(1914.7): calcd C 75.90, H 10.73; found C 75.96, H 10.85.

9.24; found C 74.10, H 9.14.

1,3-Bis(3,4-didodecyloxybenzoyloxy)-2,2-bis(3,4-didodecyloxybenzoyloxy-

methyl)propane (1 f): Synthesized from pentaerythritol (0.102 g,

0.75 mmol) and 3,4-didodecyloxybenzoic acid 2.9 g (6 mmol). Purified

twice by chromatography with petroleum ether/ethyl acetate (10:0.7 ± 1.5).

Yield: 0.18 g (12%); K 248C Col 538C I; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.84 ± 0.87 (m, 24H; CH₃), 1.24 ± 1.33 (m, 128H; CH₂),

1.42 ± 1.47 (m, 16H; O(CH₂)₂CH₂), 1.76 ± 1.83 (m, 16H; OCH₂CH₂), 3.97 (t,

1,3-Bis(4-hexadecyloxybenzoyloxy)-2,2-bis(4-hexadecyloxybenzoyloxy-

methyl)propane (13b): Synthesized from pentaerythritol (0.136 g, 1 mmol)

and 4-hexadecyloxybenzoic acid (2.9 g, 8 mmol). Purified by chromatog-

raphy with petroleum ether/ethyl acetate (10:1) and recrystallization from

ethyl acetate. Yield: 0.33 g (22%); m.p. 728C; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.86 (t, ³J(H,H) 6.9 Hz, 12H; CH₃), 1.24 ± 1.40 (m, 96H;

CH₂), 1.42 ± 1.46 (m, 8H; O(CH₂)₂CH₂), 1.74 ± 1.80 (m, 8H; OCH₂CH₂),

3.96 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.62 (s, 8H; CCH₂), 6.83 (d,

3

³J(H,H) 6.6 Hz, 8H; OCH₂), 4.00 (t, J(H,H) 6.6 Hz, 8H; OCH₂), 4.60

(s, 8H; CCH₂), 6.76 (d, ³J(H,H) 8.6 Hz, 4H; Ar H), 7.46 (d, ⁴J(H,H)

2.0 Hz, 4H; Ar H), 7.55 (dd, ³J(H,H) 8.6 Hz, ⁴J(H,H) 2.0 Hz, 4H;

3

³J(H,H) 8.8 Hz, 8H; Ar H), 7.91 (d, J(H,H) 8.8 Hz, 8H; Ar H); MS

(MALDI-TOF, DHB): m/z: 1536.0 [MNa] , 1552.9 [MK] ; C₉₇H₁₅₆O₁₂

Ar H); MS (MALDI-TOF, DHB): m/z: 2049.7 [MNa] , 2066.5 [MK] ;

(1514.1): calcd C 76.94, H 10.37; found C 76.74, H 10.20.

C

₁₂₉H₂₂₀O₁₆(2026.9): calcd C 76.44, H 10.93; found C 76.15, H 10.94.

1,3-Bis(3,5-didecyloxybenzoyloxy)-2,2-bis(3,5-didecyloxybenzoyloxymethyl)-

propane (14): Synthesized from pentaerythritol (0.136 g, 1 mmol) and 3,5-

didecyloxybenzoic acid (3.5 g, 8 mmol). Purified twice by chromatography

with petroleum ether/ethyl acetate (10:0.4 ± 0.6). Yield: 0.74 g (41%); K

358C Col 78C I; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t,

³J(H;H) 7.1 Hz, 24H; CH₃), 1.24 ± 1.38 (m, 96H; CH₂), 1.40 ± 1.43 (m,

16H; O(CH₂)₂CH₂), 1.71 ± 1.76 (m, 16H; OCH₂CH₂), 3.89 (t, ³J(H,H)

1,3-Bis(3,4-dihexadecyloxybenzoyloxy)-2,2-bis(3,4-dihexadecyloxybenzoyl-

oxymethyl)propane (1g): Synthesized from pentaerythritol (0.102 g,

0.75 mmol) and 3,4-dihexadecyloxybenzoic acid (3.6 g, 6 mmol). Purified

by chromatography with CHCl₃and recrystallization from ethyl acetate.

1

Yield: 0.15 g (8%); m.p. 588C; H NMR (400 MHz, CDCl₃, 258C, TMS):

d 0.87 (t, ³J(H,H) 6.8 Hz, 24H; CH₃), 1.21 ± 1.46 (m, 208H; CH₂), 1.76 ±

1654

ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

0947-6539/99/0505-1654 $ 17.50+.50/0

Chem. Eur. J. 1999, 5, No. 5

Micro Segregation

1643±1660

6.4 Hz, 16H; OCH₂), 4.60 (s, 8H; CCH₂), 6.58 (t, ⁴J(H,H) 2.2 Hz, 4H;

Ar H), 7.06 (d, ⁴J(H,H) 2.2 Hz, 8H; Ar H); MS (MALDI-TOF, DHB):

¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t, ³J(H,H) 6.8 Hz,

18H; CH₃), 1.25 ± 1.33 (m, 72H; CH₂), 1.40 ± 1.45 (m, 12H; O(CH₂)₂CH₂),

1.74 ± 1.84 (m, 12H; OCH₂CH₂), 3.95 (t, ³J(H,H) 6.6 Hz, 2H; OCH₂), 3.96

(t, ³J(H,H) 6.8 Hz, 4H; OCH₂), 3.99, 4.02 (m, 6H; OCH₂), 4.57 (dd,

²J(H,H) 11.7 Hz, ³J(H,H) 6.1 Hz, 2H; CHCH_AH_B), 4.67 (dd,

²J(H,H) 11.7 Hz, ³J(H,H) 4.6 Hz, 2H; CHCH_AH_B), 5.71 ± 5.76 (m,

1H; CH), 6.81 (d, ³J(H,H) 8.5 Hz, 3H; Ar H), 7.49 (d, ⁴J(H,H)

2.0 Hz, 2H; Ar H), 7.50 (d, ⁴J(H,H) 2.2 Hz, 1H; Ar H), 7.60 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.62 (dd, ³J(H,H)

8.5 Hz, ⁴J(H,H) 2.2 Hz, 1H; Ar H); MS (MALDI-TOF, DHB): m/z:

m/z: 1801.9 [M] , 1824.2 [MNa] , 1840.6 [MK] ; C₁₁₃H₁₈₈O₁₆(1802.5):

calcd C 75.30, H 10.50; found C 75.24, H 10.63.

2-(3,4-Didecyloxybenzoylamino)-1,3-bis(3,4-didecyloxybenzoyloxy)-2-(3,4-

didecyloxybenzoyloxymethyl)propane (3): Synthesized from tris(hydroxy-

methyl)aminomethane (0.121 g, 1 mmol) and 3,4-didecyloxybenzoic acid

(3.5 g, 8 mmol). Purified twice by chromatography with CHCl₃/methanol

1

(10:0 ± 0.5). Yield: 0.3 g (17%); K 478C Col 668C I; H NMR (500 MHz,

3

CDCl₃, 258C, TMS): d 0.86 (t, J(H,H) 6.8 Hz, 24H; CH₃), 1.26 ± 1.40

1363.8 [MNa] , 1380.4 [MK] ; C₈₄H₁₄₀O₁₂(1341.8): calcd C 75.19, H

(m, 96H; CH₂), 1.42 ± 1.45 (m, 16H; O(CH₂)₂CH₂), 1.73 ± 1.82 (m, 16H;

OCH₂CH₂), 3.91 (t, ³J(H,H) 6.4 Hz, 6H; OCH₂), 3.98 ± 4.02 (m, 10H;

OCH₂), 4.94 (s, 6H; CCH₂), 6.76 (d, ³J(H,H) 8.5 Hz, 3H; Ar H), 6.83 (d,

³J(H,H) 8.6 Hz, 1H; Ar H), 7.31 (dd, ³J(H,H) 8.6 Hz, ⁴J(H,H)

2.2 Hz, 1H; Ar H), 7.36 (s, 1H; NH), 7.38 (d, ⁴J(H,H) 2.2 Hz, 1H;

10.51; found C 75.19, H 10.52.

3-(3,4-Didecyloxybenzoylamino)-1,2-bis(3,4-didecyloxybenzoyloxy)pro-

pane (21): Synthesized from 3-amino-1,2-propanediol (0.136 g, 1.5 mmol)

and 3,4-didecyloxybenzoic acid (3.9 g, 9 mmol). Purified twice by chroma-

tography with CHCl₃/methanol (10:0 ± 0.05) and recrystallization from

ethyl acetate. Yield: 0.22 g (11%); K 978C M 658C I; ¹H NMR (500 MHz,

[D₆]acetone, 258C, TMS): d 0.85 ± 0.88 (m, 18H; CH₃), 1.28 ± 1.36 (m,

72H; CH₂), 1.45 ± 1.53 (m, 12H; O(CH₂)₂CH₂), 1.71 ± 1.82 (m, 12H;

OCH₂CH₂), 3.82 ± 3.99 (m, 8H; OCH₂, CH₂NH), 4.01 ± 4.06 (m, 6H;

OCH₂), 4.48 (dd, ²J(H,H) 12.0 Hz, ³J(H,H) 6.6 Hz, 1H; CHCH_AH_B),

4.71 (dd, ²J(H,H) 12.0 Hz, ³J(H,H) 3.7 Hz, 1H; CHCH_AH_B), 5.55 ± 5.60

(m, 1H; CH), 6.93 (d, ³J(H,H) 9.0 Hz, 1H; Ar H), 6.96 (d, ³J(H,H)

8.5 Hz, 1H; Ar H), 6.98 (d, ³J(H,H) 8.5 Hz, 1H; Ar H), 7.44 (d,

⁴J(H,H) 2 Hz, 1H; Ar H), 7.44 (dd, ³J(H,H) 9.0 Hz, ⁴J(H,H) 2 Hz,

1H; Ar H), 7.47 (d, ⁴J(H,H) 2.0 Hz, 1H; Ar H), 7.51 (d, ⁴J(H,H)

2.0 Hz, 1H; Ar H), 7.58 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 1H;

4

3

Ar H), 7.46 (d, J(H,H) 2.0 Hz, 3H; Ar H), 7.56 (dd, J(H,H) 8.5 Hz,

⁴J(H,H) 2.0 Hz, 3H; Ar H); ¹³C NMR (200 MHz, CDCl₃): d 14.08,

22.67, 25.97, 26.07, 29.08, 29.22, 29.37, 29.48, 29.57, 29. 62, 31.91, 59.94

(CCH₂), 63.94 (CCH₂), 69.05, 69.20, 111.93, 112.29, 114.30, 119.76, 121.52,

123.80, 126.53, 148.64, 148.98, 152.09, 153.63, 166.51 (COO), 167.17

1

(CONH); IR (Nujol): nÄ (N H), 1714 (C O), 1667 (C O), 1513 cm

(N H); MS (MALDI-TOF, DHAP): m/z: 1788.7 [MH] ; C₁₁₂H₁₈₇NO₁₅

(1787.5): calcd C 75.26, H 10.53, N 0.78; found C 75.30, H 10.70, N 0.76.

Tetrakis-O-(3,4-didecyloxybenzoyl)erythritol (17): Synthesized from meso-

erythritol (0.122 g, 1 mmol) and 3,4-didecyloxybenzoic acid (3.5 g, 8 mmol).

Purified twice by chromatography with CHCl₃/petroleum ether (1:1 ± 0).

Yield: 0.42 g (24%); K 578C Col 398C I; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.83 ± 0.88 (m, 24H; CH₃), 1.26 ± 1.34 (m, 96H; CH₂),

1.40 ± 1.47 (m, 16H; O(CH₂)₂CH₂), 1.74 ± 1.84 (m, 16H; OCH₂CH₂), 3.91 ±

3.96 (m, 8H; OCH₂), 3.97 ± 4.02 (m, 8H; OCH₂), 4.52 (dd, ²J(H,H)

12.1 Hz, ³J(H,H) 5.8 Hz, 2H; CHCH_AH_B), 4.82 (dd, ²J(H,H) 11.8 Hz,

³J(H,H) 2.9 Hz, 2H; CHCH_AH_B), 5.85 ± 5.87 (m, 2H; CH), 6.79 (d,

³J(H,H) 8.5 Hz, 2H; Ar H), 6.80 (d, ³J(H,H) 8.5 Hz, 2H; Ar H), 7.46

(d, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.47 (d, ⁴J(H,H) 2.0 Hz, 2H; Ar H),

7.58 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.60 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H); MS (MALDI-TOF,

4

Ar H), 7.62 (dd, ³J(H,H) 8.5 Hz, J(H,H) 2.0 Hz, 1H; Ar H), 7.97 (t,

³J(H,H) 6.1 Hz, 1H; N H); MS (MALDI-TOF, DHAP): m/z: 1340.8

[M] ; C₈₄H₁₄₁NO₁₁(1340.9): calcd C 75.24, H 10.59, N 1.04; found C 75.45,

H 10.58, N 0.95.

2-(3,4-Didecyloxybenzoylamino)-1,3-bis(3,4-didecyloxybenzoyloxy)pro-

pane (22): Synthesized from 2-amino-1,3-propanediol (0.136 g, 1.5 mmol)

and 3,4-didecyloxybenzoic acid (3.9 g, 9 mmol). Purified twice by chroma-

tography with CHCl₃/methanol (10:0 ± 0.05) and recrystallization from

ethyl acetate. Yield: 0.47 g (23%); m.p. 948C; ¹H NMR (500 MHz,

3

[D₆]acetone, 258C, TMS): d 0.88 (t, J(H,H) 6.4 Hz, 18H; CH₃), 1.30 ±

DHB): m/z: 1789.4 [MH] , 1812.0 [MNa] , 1828.3 [MK] ;

₁₁₂H₁₈₆O₁₆(1788.5): calcd C 75.21, H 10.47; found C 75.48, H 10.43.

1.41 (m, 72H; CH₂), 1.47 ± 1.51 (m, 12H; O(CH₂)₂CH₂), 1.73 ± 1.83 (m,

12H; OCH₂CH₂), 3.95 ± 3.98 (m, 6H; OCH₂), 4.04 (t, ³J(H,H) 6.4 Hz,

2H; OCH₂), 4.07 (t, ³J(H,H) 6.3 Hz, 4H; OCH₂), 4.55 (dd, ²J(H,H)

11.2 Hz, ³J(H,H) 6.6 Hz, 2H; CHCH_AH_B), 4.62 (dd, ²J(H,H) 11.4 Hz,

³J(H,H) 5.6 Hz, 2H; CHCH_AH_B), 4.91 ± 4.92 (m, 1H; CH), 6.95 (d,

³J(H,H) 8.8 Hz, 1H; Ar H), 6.97 (d, ³J(H,H) 8.5 Hz, 2H; Ar H), 7.46

(s, 1H; Ar H), 7.47 (d, ³J(H,H) 2 Hz, 1H; N H), 7.54 (d, ⁴J(H,H)

2.0 Hz, 2H; Ar H), 7.62 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H;

Ar H), 7.68 (d, ³J(H,H) 8.8 Hz, 1H; Ar H); MS (MALDI-TOF, DHB):

C

Tetrakis-O-(3,4-didecyloxybenzoyl)-d-threitol (18): Synthesized from d-

threitol (0.122 g, 1 mmol) and 3,4-didecyloxybenzoic acid (3.5 g, 8 mmol).

Purified twice by chromatography with CHCl₃/petroleum ether (1:1 ± 0).

Yield: 0.35 g (20%); K 448C Col 408C I; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.86 (t, ³J(H,H) 6.1 Hz, 24H; CH₃), 1.25 ± 1.33 (m, 96H;

CH₂), 1.40 ± 1.45 (m, 16H; O(CH₂)₂CH₂), 1.73 ± 1.83 (m, 16H; OCH₂CH₂),

3.93 (t, ³J(H,H) 7.1 Hz, 4H; OCH₂), 3.95 (t, ³J(H,H) 6.4 Hz, 4H;

OCH₂), 3.99 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.59 (dd, ²J(H,H) 12.0 Hz,

³J(H,H) 6.1 Hz, 2H; CHCH_AH_B), 4.68 (dd, ²J(H,H) 11.8 Hz,

³J(H,H) 3.9 Hz, 2H; CHCH_AH_B), 5.84 ± 5.88 (m, 2H; CH), 6.78 (d,

³J(H,H) 8.5 Hz, 2H; Ar H), 6.79 (d, ³J(H,H) 8.5 Hz, 2H; Ar H), 7.45

(d, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.49 (d, ⁴J(H,H) 2.0 Hz, 2H; Ar H),

7.56 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.61 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H); MS (MALDI-TOF,

m/z: 1343.3 [MH] , 1364.9 [MNa] , 1381.3 [MK] ; C₈₄H₁₄₁NO₁₁

(1340.9): calcd C 75.24, H 10.59, N 1.04; found C 75.24, H 10.58, N 0.89.

Pentakis-O-(3,4-didecyloxybenzoyl)adonitol (23): Synthesized from ado-

nitol (0.076 g, 0.5 mmol) and 3,4-didecyloxybenzoic acid (2.2 g, 5 mmol);

Purified twice by chromatography with CHCl₃/petroleum ether (1:1 ± 0).

Yield: 0.09 g (8%); K 548C Col 368C I; ¹H NMR (500 MHz, CDCl₃, 258C,

TMS, 258C, TMS): d 0.82 ± 0.88 (m, 30H; CH₃), 1.24 ± 1.38 (m, 120H;

CH₂), 1.42 ± 1.44 (m, 20H; O(CH₂)₂CH₂), 1.71 ± 1.83 (m, 20H; OCH₂CH₂),

3.89 ± 3.93 (m, 10H; OCH₂), 3.95 ± 4.02 (m, 10H; OCH₂), 4.49 (dd,

²J(H,H) 12.0 Hz, ³J(H,H) 6.6 Hz, 2H; CHCH_AH_B), 4.85 (dd,

²J(H,H) 12.1 Hz, ³J(H,H) 3.9 Hz, 2H; CHCH_AH_B), 5.91 ± 5.94 (m,

2H; CHCHCH), 6.04 (t, ³J(H,H) 5.4 Hz, 1H; CHCHCH), 6.72 (d,

³J(H,H) 8.5 Hz, 2H; Ar H), 6.79 (d, ³J(H,H) 8.5 Hz, 1H; Ar H), 6.80

(d, ³J(H,H) 8.5 Hz, 2H; Ar H), 7.43 (d, ⁴J(H,H) 2.0 Hz, 2H; Ar H),

7.46 (d, ⁴J(H,H) 2.0 Hz, 1H; Ar H), 7.47 (d, ⁴J(H,H) 2.0 Hz, 2H;

Ar H), 7.53 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.59 (dd,

³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 1H; Ar H), 7.61 (dd, ³J(H,H)

8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H); MS (MALDI-TOF, DHB): m/z:

DHB): m/z: 1790.9 [MH] , 1812.9 [MNa] , 1829.5 [MK] ;

C₁₁₂H₁₈₆O₁₆(1788.5): calcd C 75.21, H 10.47; found C 75.05, H 10.31.

1,3-Bis(3,4-didecyloxybenzoyloxy)-2-(3,4-didecyloxybenzoyloxymethyl)-

propane (19): Synthesized from 2-(hydroxymethyl)-1,3-propanediol

(0.16 g, 1.5 mmol) and 3,4-didecyloxybenzoic acid (3.9 g, 9 mmol). Purified

twice by chromatography with CHCl₃/petroleum ether (1:1 ± 0). Yield:

0.56 g (28%); m.p. 768C; ¹H NMR (400 MHz, CDCl₃, 258C, TMS): d

0.84 ± 0.87 (m, 18H; CH₃), 1.25 ± 1.41 (m, 72H; CH₂), 1.43 ± 1.46 (m, 12H;

O(CH₂)₂CH₂), 1.76 ± 1.85 (m, 12H; OCH₂CH₂), 2.80 (t, ³J(H,H) 5.7 Hz,

1H; CH), 3.97 ± 4.03 (m, 12H; OCH₂), 4.51 (d, ³J(H,H) 5.8 Hz, 6H;

CCH₂), 6.80 (d, ³J(H,H) 8.6 Hz, 3H; Ar H), 7.50 (d, ⁴J(H,H) 2.0 Hz,

3H; Ar H), 7.59 (dd, ³J(H,H) 8.6 Hz, ⁴J(H,H) 2.0 Hz, 3H; Ar H); MS

2234.9 [M] , 2257.7 [MNa] , 2273.0 [MK] ; C₁₄₀H₂₃₂O₂₀(2235.1): calcd

(MALDI-TOF, DHB): m/z: 1356.5 [M] , 1379.7 [MNa] ; C₈₅H₁₄₂O₁₂

C 75.23, H 10.45; found C 75.31, H 10.44.

(1355.9): calcd C 75.29, H 10.54; found C 75.31, H 10.49.

Hexakis-O-(3,4-didecyloxybenzoyl)-d-mannitol (24): Synthesized from d-

mannitol (0.091 g, 0.5 mmol) and 3,4-didecyloxybenzoic acid (2.6 g,

6 mmol). Purified twice by chromatography with CHCl₃/petroleum ether

(1,5:1). Yield: 0.35 g (26%); K ? Col 558C I; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.84 ± 0.88 (m, 36H; CH₃), 1.25 ± 1.48 (m, 168H; CH₂),

1,2,3-Tris(3,4-didecyloxybenzoyloxy)propane (20): Synthesized from dry

glycerol (freshly destilled, 0.138 g, 1.5 mmol) and 3,4-didecyloxybenzoic

acid (3.9 g, 9 mmol). Purified twice by chromatography with CHCl₃and

crystallized once from ethyl acetate. Yield: 0.55 g (27%); m.p. 988C;

Chem. Eur. J. 1999, 5, No. 5

ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

0947-6539/99/0505-1655 $ 17.50+.50/0

1655

C. Tschierske et al.

FULL PAPER

1.67 ± 1.83 (m, 24H; OCH₂CH₂), 3.82 ± 3.93 (m, 20H; OCH₂), 3.98 (t,

³J(H,H) 6.6 Hz, 4H; OCH₂), 4.45 (dd, ²J(H,H) 12.3 Hz, ³J(H,H)

5.7 Hz, 2H; CHCH_AH_B), 4.86 (dd, ²J(H,H) 12.2 Hz, ³J(H,H) 3.4 Hz,

2H; CHCH_AH_B), 5.75 ± 5.77 (m, 2H; CHCHCHCH), 6.10 (virtual brd, 2H;

11.9 Hz, 2H; CH 4,6_ax), 3.98 (d, ²J(H,H) 11.9 Hz, 2H; CH 4,6_eq),

4.01 ± 4.08 (m, 8H; OCH₂), 4.50 (t, ³J(H,H) 5.1 Hz, 1H; CH), 4.77 (s,

2H; CH₂OOC), 6.86 (d, ³J(H,H) 8.4 Hz, 1H; Ar H), 6.89 (d, ³J(H,H)

8.4 Hz, 1H; Ar H), 7.24 (t, ³J(H,H) 6.4 Hz, 1H; N H), 7.37 (dd,

³J(H,H) 8.4 Hz, ⁴J(H,H) 2.2 Hz, 1H; Ar H), 7.47 (d, ⁴J(H,H)

2.2 Hz, 1H; Ar H), 7.56 (d, ⁴J(H,H) 2.0 Hz, 1H; Ar H), 7.69 (dd,

³J(H,H) 8.4 Hz, ⁴J(H,H) 2.0 Hz, 1H; Ar H); MS: m/z (%): 1105 (8)

3

CHCHCHCH), 6.59 (d, J(H,H) 8.5 Hz, 2H; Ar H), 6.60 (d, J(H,H)

8.5 Hz, 2H; Ar H), 6.73 (d, ³J(H,H) 8.5 Hz, 2H; Ar H), 7.38 (d,

4

⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.42 (d, J(H,H) 2.0 Hz, 4H; Ar H), 7.45

(dd, ³J(H,H) 8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.49 (dd, ³J(H,H)

8.5 Hz, ⁴J(H,H) 2.0 Hz, 2H; Ar H), 7.56 (dd, ³J(H,H) 8.5 Hz,

⁴J(H,H) 2.0 Hz, 2H; Ar H); MS (MALDI-TOF, DHB): m/z: 2682.2

[M] , 487 (25), 447 (17), 434 (25), 417 (100), 277 (43), 154 (47), 137 (30), 71

(17), 57 (37); C₆₉H₁₁₉NO₉(1106.5): calcd C 74.89, H 10.82, N 1.26; found C

74.75, H 10.52, N 1.25.

[M] , 2705.2 [MNa] ; C₁₆₈H₂₇₈O₂₄(2681.7): calcd C 75.24, H 10.44; found

The obtained 5-(3,4-didecyloxybenzoylaminomethyl)-5-(3,4-didecyloxy-

benzoyloxymethyl)-2-nonyl-1,3-dioxane (1.24 g, 1.12 mmol) was dissolved

in ethanol (70 mL). After addition of water (1 mL) and a catalytic amount

of PPTS (20 mg) the solution was heated at reflux temperature for 5 h. The

solution cooled to 0 ± 58C and the white precipitat formed was removed

and recrystallisized twice from methanol. Yield: 0.84 g (77%); K 728C Col

978C I; ¹H NMR (400 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.88 (m, 12H;

CH₃), 1.25 ± 1.34 (m, 48H; CH₂), 1.42 ± 1.46 (m, 8H; O(CH₂)₂CH₂), 1.79 ±

1.86 (m, 8H; OCH₂CH₂), 3.48 (d, ³J(H,H) 6.4 Hz, 2H; CH₂NH), 3.53 (s,

4H; CH₂OH), 4.00 ± 4.06 (m, 8H; OCH₂), 4.23 (s, 2H; CH₂OOC), 6.85 (d,

³J(H,H) 8.5 Hz, 1H; Ar H), 6.88 (d, ³J(H,H) 8.5 Hz, 1H; Ar H), 7.14

(brt, ³J(H,H) 6.4 Hz, 1H; N H), 7.35 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H)

2.1 Hz, 1H; Ar H), 7.44 (d, ⁴J(H,H) 2.1 Hz, 1H; Ar H), 7.52 (d,

⁴J(H,H) 2.1 Hz, 1H; Ar H), 7.64 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H)

2.1 Hz, 1H; Ar H); ¹³C NMR (100 MHz, CDCl₃): d 13.95, 22.55, 25.85,

25.90, 28.94, 29.01, 29.12, 29.22, 29.24, 29.28, 29.31, 29.47, 29.52, 31.81, 38.09

(CCH₂), 46.62 (CH₂NH), 62.24 (CH₂OH), 62.70 (CH₂OOC), 69.08, 69.17,

69.35, 69.43, 112.06, 112.47, 112.87, 114.58, 120.04, 121.30, 124.20, 125.40,

C 74.86, H 10.21.

1-(3,4-Didecyloxybenzoylamino)-1-deoxypentakis-O-(3,4-didecyloxyben-

zoyl)-d-sorbitol (25): Synthesized from 1-amino-1-deoxy-d-sorbitol

(0.135 g, 0.75 mmol) and 3,4-didecyloxybenzoic acid (3.9 g, 9 mmol).

Purified twice by chromatography with CHCl₃/petroleum ether (1,5:1).

1

Yield: 0.71 g (35%); K ? Col 788C I; H NMR (500 MHz, CDCl₃, 258C,

TMS): d 0.86 ± 0.89 (m, 36H; CH₃), 1.27 ± 1.53 (m, 168H; CH₂), 1.70 ± 1.86

(m, 24H; OCH₂CH₂), 3.63 ± 3.66 (m, 1H; CH_AH_BNH), 3.84 ± 4.02 (m, 24H;

OCH₂), 4.16 ± 4.23 (m, 1H; CH_AH_BNH), 4.42 (dd, ²J(H,H) 12.2 Hz,

³J(H,H) 5.6 Hz, 1H; CH_AH_BCH), 4.78 (dd, ²J(H,H) 12.1 Hz,

³J(H,H) 3.5 Hz, 1H; CH_AH_BCH), 5.62 ± 5.64 (m, 1H; CH), 5.74 ± 5.78

(m, 1H; CH), 5.96 (dd, ²J(H,H) 5.3 Hz, ³J(H,H) 3.9 Hz, 1H; CH), 6.18

(dd, ²J(H,H) 6.9 Hz, ³J(H,H) 3.7 Hz, 1H; CH), 6.52 (d, ³J(H,H)

3

8.6 Hz, 1H; Ar H), 6.60 (d, J(H,H) 8.6 Hz, 1H; Ar H), 6.71 ± 6.77 (m,

5H; Ar H), 7.16 ± 7.19 (m, 1H; NH), 7.37 ± 7.60 (m, 11H; Ar H); MS

(MALDI-TOF, DHB): m/z: 2683.5 [M] ; 2705.3 [MNa] ; C₁₆₈H₂₇₉NO₂₃

(2680.7): calcd C 75.27, H 10.48, N 0.52; found C 75.15, H 10.50, N 0.50.

148.91, 149.26, 152.73, 154.17, 167.95 (COO), 169.30 (CONH); IR (Nujol):

Bis[3-(3,4-didecyloxybenzoyloxy)-2,2-(3,4-didecyloxybenzoyloxymethyl)-

propyl]ether (26): Synthesized from dipentaerythritol (0.19 g, 0.75 mmol)

and 3,4-didecyloxybenzoic acid (3.9 g, 9 mmol). Purified twice by chroma-

tography with CHCl₃/petroleum ether (1:1 ± 0). Yield: 0.27 g (13%); K ?

Col 798C I; ¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.86 (t,

1

nÄ 3389 cm (OH, NH), 1698 (C O), 1575 cm ¹(NH); MS: m/z (%): 967

(12) [M] , 840 (32), 533 (31), 434 (45), 417 (88), 294 (28), 277 (42), 154

(100), 137 (34), 57 (29); C₅₉H₁₀₁NO₉(968.3).

2-(3,4-Didecyloxybenzoylaminomethyl)-1,3-bis(3,4-didecyloxybenzoyl-

oxy)-2-(3,4-didecyloxybenzoyloxymethyl)propane (2): Synthesized from

III (0.29 g, 0.3 mmol) and 3,4-didecyloxybenzoic acid (0.52 g, 1.2 mmol)

according to the general procedure. Purified by chromatography with

CHCl₃/methanol (10:0 ± 0.1). Yield: 0.46 g (85%); K ? Col 728C I; ¹H NMR

(400 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.88 (m, 24H; CH₃), 1.25 ± 1.46

(m, 112H; CH₂), 1.75 ± 1.84 (m, 16H; OCH₂CH₂), 3.70 (d, ³J(H,H)

6.4 Hz, 2H; CH₂NH), 3.97 ± 4.03 (m, 16H; OCH₂), 4.54 (s, 6H; CH₂O),

6.78 (d, ³J(H,H) 8.7 Hz, 3H; Ar H), 6.84 (d, ³J(H,H) 8.5 Hz, 1H;

Ar H), 7.23 (t, ³J(H,H) 6.4 Hz, 1H; N H), 7.35 (dd, ³J(H,H) 8.5 Hz,

3

³J(H,H) 7.0 Hz, 18H; CH₃), 0.87 (t, J(H,H) 7.3 Hz, 18H; CH₃), 1.25 ±

1.34 (m, 144H; CH₂), 1.40 ± 1.47 (m, 24H; O(CH₂)₂CH₂), 1.74 ± 1.82 (m,

24H; OCH₂CH₂), 3.67 (s, 4H; CH₂OCH₂), 3.94 (t, ³J(H,H) 6.7 Hz, 12H;

3

OCH₂), 3.95 (t, J(H,H) 6.5 Hz, 12H; OCH₂), 4.50 (s, 12H; CCH₂), 6.68

(d, ³J(H,H) 8.6 Hz, 6H; Ar H), 7.42 (d, ⁴J(H,H) 2.1 Hz, 6H; Ar H),

7.46 (dd, ³J(H,H) 8.6 Hz, ⁴J(H,H) 2.1 Hz, 6H; Ar H); MS (MALDI-

TOF, DHB): m/z: 2776.8 [MNa] , 2791.7 [MK] ; C₁₇₂H₂₈₆O₂₅(2753.8):

calcd C 75.02, H 10.46; found C 75.07, H 10.59.

Synthesis of 2

4

⁴J(H,H) 2.3 Hz, 1H; Ar H), 7.45 (d, J(H,H) 2.3 Hz, 1H; Ar H), 7.51

5-Aminomethyl-5-hydroxymethyl-2-nonyl-1,3-dioxane (II): A solution of

(d, ⁴J(H,H) 1.9 Hz, 3H; Ar H), 7.60 (dd, ³J(H,H) 8.5 Hz, ⁴J(H,H)

I

^[11](6.2 g, 20 mmol) in dry diethyl ether (50 mL) was slowly added at 208C

1.9 Hz, 3H; Ar H); MS (MALDI-TOF, DHAP): m/z: 1801.6 [M] ;

under an argon atmosphere to a stirred suspension of LiAlH₄(0.9 g,

23.6 mmol) in dry diethyl ether (30 mL). The mixture was stirred for 4 h at

this temperature. Afterwards water (30 mL) was slowly added drop by drop

at 0 ± 58C (CAUTION, exothermic reaction). The white precipitate formed

was removed and washed with diethyl ether (30 mL). The combined

organic phases were dried over Na₂SO₄. The solvent was removed in vacuo

and the residue was recrystallisized from ethyl acetate/petroleum ether

(10:1). Yield: 3.2 g (51%); m.p. 1488C; ¹H NMR (500 MHz, CDCl₃, 258C,

C₁₁₃H₁₈₉NO₁₅(1801.2): calcd C 75.35, H 10.55, N 0.78; found C 75.25, H

10.47, N 0.79.

Synthesis of 4

2-(3,4-Didecyloxybenzyloxymethyl)-2-hydroxymethyl-1,3-propanediol

(V): A suspension of IV^[12](1.12 g, 7 mmol) and NaH (0.19 g, 7.9 mmol) in

dry DMF (30 mL) was stirred for 2 h at 208C. 3,4-Didecyloxybenzyl

bromide [crude product as obtained from 3,4-didecyloxybenzyl alkohol

(4.2 g, 10 mmol) by treatment with PBr₃in dry benzene^[15]] dissolved in dry

DMF (70 mL) was added dropwise. The mixture was stirred for 5 h at 508C

and for 12 h at 208C and then poured into ice water (100 mL). The mixture

was extracted three times with diethyl ether (70 mL), and the organic

extracts were washed with water (40 mL) and brine (40 mL). The solvent

was removed in vacuo, and the residue was dissolved in ethanol (100 mL).

After addition of hydrochloric acid (0.01m; 20 mL) the solution was stirred

for 1 h at 208C. Then NaHCO₃(0.7 g) was added, and the mixture was

stirred for an additional 1 h at 208C. The solvent was removed in vacuo and

the residue was purified by chromatography with CHCl₃/methanol

3

TMS): d 0.86 (t, J(H,H) 7.0 Hz, 3H; CH₃), 1.24 ± 1.37 (m, 14H; CH₂),

1.56 ± 1.60 (m, 2H; CH₂CH), 3.24 (s, 2H; CH₂NH₂), 3.46 (s, 2H; CH₂OH),

3.47 (d, ²J(H,H) 11.9 Hz, 2H; CH 4,6_ax), 3.93 (d, ²J(H,H) 11.9 Hz, 2H;

CH 4,6_eq), 4.42 (t, ³J(H,H) 5.1 Hz, 1H; CH); ¹³C NMR (100 MHz,

CDCl₃): d 13.90, 22.53, 23.80, 29.18, 29.04, 29.43, 31.78, 34.78, 36.99

(CCH₂), 44.47 (CH₂NH₂), 67.67 (CH₂OH), 70.81 (CHOCH₂), 103.08 (CH);

1

IR (Nujol): nÄ 3371 (OH), 3134 cm (NH); MS: m/z (%): 273 (6) [M] ,

230 (40), 146 (56), 115 (37), 100 (30), 88 (44), 82 (46), 70 (78), 57 (100);

C₁₅H₃₁NO₃(273.3).

2-(3,4-Didecyloxybenzoylaminomethyl)-2-(3,4-didecyloxybenzoyloxy-

methyl)-1,3-propanediol (III): 5-(3,4-Didecyloxybenzoylaminomethyl)-5-

(3,4-didecyloxybenzoyloxymethyl)-2-nonyl-1,3-dioxane was synthesized

from II (0.82 g, 3 mmol) and 3,4-didecyloxybenzoic acid (5.2 g, 12 mmol)

according to the general procedure. Purified by chromatography with

CHCl₃/methanol (10:0.5). Yield: 1.54 g (46%); m.p. 158C; ¹H NMR

(400 MHz, CDCl₃, 258C, TMS): d 0.86 ± 0.89 (m, 15H; CH₃), 1.27 ± 1.49

(m, 70H; CH₂), 1.62 ± 1.68 (m, 2H; CH₂CH), 1.79 ± 1.88 (m, 8H;

OCH₂CH₂), 3.15 (d, ³J(H,H) 6.4 Hz, 2H; CH₂NH), 3.73 (d, ²J(H,H)

1

(10:0.2 ± 50). Yield: 0.3 g (8%); K 648C Col 798C I; H NMR (400 MHz,

CDCl₃, 258C, TMS): d 0.86 (t, ³J(H,H) 6.8 Hz, 6H; CH₃), 1.25 ± 1.44

(m, 28H; CH₂), 1.75 ± 1.82 (m, 4H; OCH₂CH₂), 3.46 (s, 2H; CH₂OCH₂Ph),

3

3.70 (s, 6H; CH₂OH), 3.96 (t, J(H,H) 6.5 Hz, 4H; OCH₂), 4.40 (s, 2H;

CH₂Ph), 6.77 ± 6.83 (m, 3H; Ar H); IR (Nujol): nÄ 3345 cm ¹(OH); MS:

m/z (%): 538 (100) [M] , 419 (33), 404 (12), 279 (64), 263 (13), 139 (37), 123

(53), 111 (10), 83 (16), 71 (14 ), 57 (26); C₃₂H₅₈O₆(538.7): calcd C 71.34, H

10.84; found C 71.13, H 10.82.

1656

ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

0947-6539/99/0505-1656 $ 17.50+.50/0

Chem. Eur. J. 1999, 5, No. 5

Micro Segregation

1643±1660

1,3-Bis(3,4-didecyloxybenzoyloxy)-2-(3,4-didecyloxybenzoyloxymethyl)-2-

(3,4-didecyloxybenzyloxymethyl)propane (4): Synthesized from V (0.134 g,

0.25 mmol) and 3,4-didecyloxybenzoic acid (0.65 g, 1.5 mmol) according to

the general procedure. Purified by chromatography with CHCl₃/petroleum

ether (1:1 ± 0). Yield: 0.165 g (37%); K 78C Col 328C I; ¹H NMR

(400 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.87 (m, 24H; CH₃), 1.25 ± 1.44

(m, 112H; CH₂), 1.70 ± 1.84 (m, 16H; OCH₂CH₂), 3.64 (s, 2H;

CH₂OCH₂Ph), 3.84 (t, ³J(H,H) 6.6 Hz, 2H; CH₂OPhCH₂), 3.85 (t,

³J(H,H) 6.5 Hz, 2H; CH₂OPhCH₂), 3.96 (t, ³J(H,H) 6.4 Hz, 6H;

CH₂OPhCOO), 4.00 (t, ³J(H,H) 6.6 Hz, 6H; CH₂OPhCOO), 4.40 (s,

2H; PhCH₂), 4.51 (s, 6H; CH₂OOC), 6.67 (d, ³J(H,H) 8.0 Hz, 1H;

Ar H), 6.73 ± 6.77 (m, 5H; Ar H), 7.45 (d, ⁴J(H,H) 2.0 Hz, 3H; Ar H),

7.49 (dd, ³J(H,H) 8.6 Hz, ⁴J(H,H) 2.0 Hz, 3H; Ar H); ¹³C NMR

(100 MHz, CDCl₃): d 13.94, 22.57, 25.91, 25.96, 29.05, 29.17, 29.24, 29.26,

29.32, 29.37, 29.41, 29.48, 29.50, 29.52, 29.55, 29.58, 31.83, 43.65 (CCH₂),

63.58 (CCH₂OOC), 68.65 (CCH₂OCH₂), 69.06, 69.16, 69.33, 69.40, 73.62,

6.75 (dd, ³J(H,H) 8.1 Hz, ⁴J(H,H) 1.7 Hz, 2H; Ar H), 6.78 (d,

³J(H,H) 8.3 Hz, 2H; Ar H), 6.79 (d, ⁴J(H,H) 1.7 Hz, 2H; Ar H),

7.45 (dd, ³J(H,H) 8.3 Hz, ⁴J(H,H) 2.1 Hz, 2H; Ar H), 7.47 (d,

⁴J(H,H) 2.1 Hz, 2H; Ar H); MS (MALDI-TOF, DHB): m/z: 1571.7

[MNa] , 1588.3 [MK] ; C₉₇H₁₆₀O₁₄(1550.1): calcd C 75.16, H 10.39;

found C 74.84, H 10.37.

1,3-Bis(3,4-didecyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)-

propane (5b): Synthesized from VII (0.282 g, 0.3 mmol) and 3,4-didecyloxy-

benzoic acid (0.52 g, 1.2 mmol) according to the general procedure.

Purified twice by chromatography with CHCl₃/methanol (10:0 ± 0.2). Yield

0.42 g (79%); K 108C Col 248C I; ¹H NMR (400 MHz, CDCl₃, 258C,

3

TMS): d 0.87 (t, J(H,H) 6.4 Hz, 12H; CH₃), 0.88 (t, J(H,H) 7.1 Hz,

12H; CH₃), 1.27 ± 1.49 (m, 112H; CH₂), 1.70 ± 1.86 (m, 16H; OCH₂CH₂),

3.61 (s, 4H; CH₂OCH₂Ph), 3.88 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCH₂),

3.89 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCH₂), 3.97 (t, ³J(H,H) 6.6 Hz, 4H;

CH₂OPhCOO), 4.02 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCOO), 4.40 (s, 4H;

PhCH₂), 4.45 (s, 4H; CH₂OOC), 6.71 (d, ³J(H,H) 8.2 Hz, 2H; Ar H),

6.75 (dd, ³J(H,H) 8.2 Hz, ⁴J(H,H) 1.6 Hz, 2H; Ar H), 6.77 (d,

³J(H,H) 8.4 Hz, 2H; Ar H), 6.79 (d, ⁴J(H,H) 1.6 Hz, 2H; Ar H),

7.44 (dd, ³J(H,H) 8.4 Hz, ⁴J(H,H) 1.8 Hz, 2H; Ar H), 7.47 (d,

⁴J(H,H) 1.8 Hz, 2H; Ar H); ¹³C NMR (100 MHz, CDCl₃): d 13.94,

22.56, 25.93, 25.96, 26.00, 29.08, 29.17, 29.26, 29.34, 29.38, 29.40, 29.42, 29.49,

29.52, 29.53, 29.57, 31.83, 44.20 (CCH₂), 63.85 (CCH₂OOC), 68.91

(CCH₂OCH₂), 69.04, 69.18, 69.30, 69.41, 73.50, 112.11, 113.63, 113.91,

112.13, 113.65, 113.90, 114.53, 120.40, 122.18, 123.66, 130.62, 148.83, 148.97,

1

149.47, 153.60, 166.20 (C O); IR (Nujol): nÄ 1714 cm (C O); MS

(MALDI-TOF, CHC): m/z: 1810.8 [MNa] , 1827.4 [MK] ; C₁₁₃H₁₉₀O₁₅

(1788.5): calcd C 75.88, H 10.69; found C 75.79, H 10.76.

Synthesis of the pentaerythritol ethers 5, 6, 7, 15, and 16

3,9-Bis(3,4-didecyloxyphenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (VI): A

mixture of pentaerythritol (1.36 g, 0.01 mol), 3,4-didecyloxybenzaldehyde

(8.4 g, 0.02 mol) and a catalytic amount of PPTS (20 mg) was refluxed in

benzene (80 mL) for 20 h with a water separator. The solution was cooled

to 208C and was washed with saturated aqueous solution of NaHCO₃

(30 mL). The organic phase was dried over Na₂SO₄, and the solvent was

removed in vacuo. The residue was recrystallisized from acetone. Yield:

6.5 g (69%); K 408C S_A488C I; ¹H NMR (200 MHz, CDCl₃, 258C, TMS):

d 0.86 (t, ³J(H,H) 6.4 Hz, 12H; CH₃), 1.25 ± 1.43 (m, 56H; CH₂), 1.70 ±

114.52, 120.27, 122.50, 123.55, 131.04, 148.77, 148.87, 149.42, 153.46, 166.26

1

(C O); IR (Nujol): nÄ 1714 cm (C O); MS (MALDI-TOF, DHB): m/z:

1797.0 [MNa] , 1813.7 [MK] ; C₁₁₃H₁₉₂O₁₄(1774.5): calcd C 76.48, H

10.89; found C 76.33, H 10.82.

1,3-Bis(3,4-dihexadecyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzyloxy-

methyl)propane (5c): Synthesized from VII (0.312 g; 0.33 mmol) and 3,4-

dihexadecyloxybenzoic acid (0.8 g, 1.33 mmol) according to the general

procedure. Purified twice by chromatography with CHCl₃/petroleum ether

(1:1 ± 0). Yield: 0.37 g (53%); m.p. 428C; ¹H NMR (500 MHz, CDCl₃,

258C, TMS): d 0.85 ± 0.88 (m, 24H; CH₃), 1.24 ± 1.47 (m, 160H; CH₂),

1.70 ± 1.83 (m, 16H; OCH₂CH₂), 3.59 (s, 4H; CH₂OCH₂Ph), 3.86 (t,

³J(H,H) 6.7 Hz, 4H; CH₂OPhCH₂), 3.88 (t, ³J(H,H) 6.7 Hz, 4H;

CH₂OPhCH₂), 3.95 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCOO), 4.00 (t,

³J(H,H) 6.6 Hz, 4H; CH₂OPhCOO), 4.38 (s, 4H; PhCH₂), 4.43 (s, 4H;

CH₂OOC), 6.70 (d, ³J(H,H) 8.3 Hz, 2H; Ar H), 6.73 (dd, ³J(H,H)

8.3 Hz, ⁴J(H,H) 1.8 Hz, 2H; Ar H), 6.75 (d, ³J(H,H) 8.6 Hz, 2H;

1.83 (m, 8H; OCH₂CH₂), 3.61 (d, ²J(H,H) 11.5 Hz, 2H; CH 5_ax

,

CH 11_ax), 3.78 (brd, ²J(H,H) 11.5 Hz, 2H; CH 5_eq, CH 11_eq), 3.80 (d,

²J(H,H) 11.7 Hz, 2H; CH 1_ax, CH 7_ax), 3.96 (t, ³J(H,H) 6.8 Hz, 4H;

OCH₂), 3.98 (t, ³J(H,H) 6.6 Hz, 4H; OCH₂), 4.84 (brd, ²J(H,H)

10.2 Hz, 2H; CH 1_eq, CH 7_eq), 5.37 (s, 2H; Ph CH), 6.84 (d, ³J(H,H)

8.2 Hz, 2H; Ar H), 6.98 (dd, ³J(H,H) 8.2 Hz, ⁴J(H,H) 1.8 Hz, 2H;

Ar H), 7.01 (d, ⁴J(H,H) 1.8 Hz, 2H; Ar H); MS: m/z (%): 936 [M]

(100), 796 (10), 138 (15), 85 (16), 71 (18), 57 (38); C₅₉H₁₀₀O₈(937.3): calcd C

75.60, H 10.74; found C 75.68, H 10.51.

2,2-Bis(3,4-didecyloxybenzyloxymethyl)-1,3-propanediol (VII): Com-

pound VI (4.7 g, 5mmol) was dissolved in dry THF (100 mL) and cooled

to 58C. NaBH₄(2 g, 52 mmol) was added and a solution of trifluoro acetic

acid (40 mL, 52 mmol) in dry THF (50 mL) was added dropwise with

stirring over 1.5 h at this temperature. The mixture was allowed to warm to

208C within 4 h while stirring and then it was poured into 10% aqueous

KOH (300 mL). The solution was extracted three times with diethyl ether

(100 mL). The organic extracts were washed with brine (50 mL) und dried

over Na₂SO₄. The solvent was removed in vacuo, and the residue was

purified by recrystallization from ethanol and chromatography with CHCl₃/

methanol (10:0.1). Yield: 3,7 g (79%); K 408C Col 518C I; ¹H NMR

4

3

Ar H), 6.77 (d, J(H,H) 1.8 Hz, 2H; Ar H), 7.43 (dd, J(H,H) 8.6 Hz,

⁴J(H,H) 1.8 Hz, 2H; Ar H), 7.45 (d, J(H,H) 1.8 Hz, 2H; Ar H); MS

4

(MALDI-TOF, DHB): m/z: 2132.1 [MNa] , 2149.1 [MK] ; C₁₃₇H₂₄₀O₁₄

(2111.1): calcd C 77.94, H 11.45; found C 77.92, H 11.42.

1,3-Bis(3,4,5-tridecyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)-

propane (15): Synthesized from VII (0.29 g, 0.31 mmol) and 3,4,5-

tridecyloxybenzoic acid (0.73 g, 1.24 mmol) according to the general

procedure. Purified twice by chromatography with CHCl₃/petroleum ether

(1:2 ± 0). Yield: 0.56 g (87%); K 88C Col 148C I; ¹H NMR (400 MHz,

CDCl₃, 258C, TMS): d 0.84 ± 0.87 (m, 30H; CH₃), 1.25 ± 1.43 (m, 140H;

CH₂), 1.68 ± 1.79 (m, 20H; OCH₂CH₂), 3.59 (s, 4H; CH₂OCH₂Ph), 3.84 ±

3.91 (m, 16H; CH₂OPhCOO, CH₂OPhCH₂), 3.97 (t, ³J(H,H) 6.6 Hz, 4H;

CH₂OPhCOO), 4.38 (s, 4H; PhCH₂), 4.45 (s, 4H; CH₂OOC), 6.69 (d,

³J(H,H) 8.2 Hz, 2H; Ar H), 6.72 (dd, ³J(H,H) 8.2 Hz, ⁴J(H,H)

1.6 Hz, 2H; Ar H), 6.76 (d, ⁴J(H,H) 1.6 Hz, 2H; Ar H), 7.15 (s, 4H;

3

(400 MHz, CDCl₃, 258C, TMS): d 0.86 (t, J(H,H) 6.8 Hz, 12H; CH₃),

1.25 ± 1.29 (m, 48H; CH₂), 1.40 ± 1.45 (m, 8H; O(CH₂)₂CH₂), 1.75 ± 1.82 (m,

8H; OCH₂CH₂), 3.49 (s, 4H; CCH₂), 3.64 (s, 4H; CH₂OH), 3.95 (t,

³J(H,H) 6.6 Hz, 8H; OCH₂), 4.38 (s, 4H; OCH₂Ph), 6.76 (dd, ³J(H,H)

8.2 Hz, ⁴J(H,H) 1.8 Hz, 2H; Ar H), 6.79 (d, ⁴J(H,H) 1.8 Hz, 2H;

Ar H), 6.80 (d, ³J(H,H) 8.2 Hz, 2H; Ar H); ¹³C NMR (100 MHz,

CDCl₃): d 14.08, 22.67, 26.06, 26.08, 29.35, 29.38, 29.44, 29.46, 29.58, 29.64,

31.91, 44.84 (CCH₂), 65.08 (CH₂OH), 69.38, 69.41, 71.84 (CCH₂OCH₂),

73.68 (CCH₂OCH₂), 113.66, 113.80, 120.41, 130.49, 148.98, 149.30; IR

Ar H); MS (MALDI-TOF, DHB): m/z: 2108.8 [MNa] , 2125.5 [MK] ;

₁₁₃H₂₃₂O₁₆(2087.0): calcd C 76.54, H 11.19; found C 76.56, H 11.34.

C

1,3-Bis(4-decyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)-

propane (16): Synthesized from VII (0.376 g, 0.4 mmol) and 4-decyloxy-

benzoic acid (0.45 g, 1.6 mmol) according to the general procedure.

Purified twice by chromatography with CHCl₃/petroleum ether(1:1 ± 0).

Yield: 0.36 g (62%); K 18C Col 38C I; ¹H NMR (500 MHz, CDCl₃, 258C,

TMS): d 0.85 ± 0.88 (m, 18H; CH₃), 1.25 ± 1.47 (m, 84H; CH₂), 1.69 ± 1.80

(m, 12H; OCH₂CH₂), 3.58 (s, 4H; CH₂OCH₂Ph), 3.86 (t, ³J(H,H) 6.5 Hz,

4H; CH₂OPhCH₂), 3.88 (t, ³J(H,H) 6.7 Hz, 4H; CH₂OPhCH₂), 3.96 (t,

³J(H,H) 6.5 Hz, 2H; CH₂OPhCOO), 4.38 (s, 4H; PhCH₂), 4.43 (s, 4H;

CH₂OOC), 6.69 (d, ³J(H,H) 8.3 Hz, 2H; Ar H), 6.74 (dd, ³J(H,H)

8.3 Hz, ⁴J(H,H) 1.8 Hz, 2H; Ar H), 6.77 (d, ⁴J(H,H) 1.8 Hz, 2H;

Ar H), 6.81 (d, ³J(H,H) 8.8 Hz, 4H; Ar H), 7.81 (d, ³J(H,H) 8.8 Hz,

1

(Nujol): nÄ 3362 cm (OH); MS: m/z (%): 940 (6) [M] , 537 (100), 419

(47), 279 (37), 263 (18), 139 (25), 123 (38), 83 (17), 57 (27).

1,3-Bis(3,4-dihexyloxybenzoyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)-

propane (5a): Synthesized from VII (0.376 g, 0.4 mmol) and 3,4-dihexyloxy-

benzoic acid (0.52 g, 1.61 mmol) according to the general procedure.

Purified twice by chromatography with CHCl₃. Yield: 0.29 g (46%); K ?

Col 58C I; ¹H NMR (400 MHz, CDCl₃, 258C, TMS): d 0.86 ± 0.92 (m,

24H; CH₃), 1.26 ± 1.49 (m, 80H; CH₂), 1.70 ± 1.87 (m, 16H; OCH₂CH₂),

3.61 (s, 4H; CH₂OCH₂Ph), 3.88 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCH₂),

3.90 (t, ³J(H,H) 6.8 Hz, 4H; CH₂OPhCH₂), 3.97 (t, ³J(H,H) 6.6 Hz, 4H;

CH₂OPhCOO), 4.02 (t, ³J(H,H) 6.6 Hz, 4H; CH₂OPhCOO), 4.40 (s, 4H;

PhCH₂), 4.45 (s, 4H; CH₂OOC), 6.72 (d, ³J(H,H) 8.1 Hz, 2H; Ar H),

4H; Ar H); MS (MALDI-TOF, DHB): m/z: 1484.1 [MNa] , 1500.8

Chem. Eur. J. 1999, 5, No. 5

ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

0947-6539/99/0505-1657 $ 17.50+.50/0

1657

C. Tschierske et al.

FULL PAPER

[MK] ; C₉₃H₁₅₂O₁₂(1462.0): calcd C 76.40, H 10.47; found C 76.22, H

1.28 ± 1.52 (m, 31H; CH₂, OCH₂CH₃), 1.81 ± 1.88 (m, 4H; OCH₂CH₂),

4.01 ± 4.11 (m, 4H; OCH₂CH₂), 4.40 (q, 2H; OCH₂CH₃), 6.96 (d,

³J(H,H) 8.8 Hz, 1H; Ar H), 7.15 ± 7.19 (m, 2H; Ar H), 7.61 (d,

10.44.

3-(3,4-Didecyloxybenzyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)pro-

panol (VIII): A suspension of VII (0.94 g, 1 mmol) and NaH (53 mg,

2.2 mmol) in dry DMF (15 mL) was stirred 2 h at 208C under an argon

atmosphere. 3,4-Didecyloxybenzyl bromide [crude product as obtained

from 3,4-didecyloxybenzyl alkohol (1.3 g, 3 mmol) by treatment with PBr₃

in dry benzene^[15]] dissolved in dry DMF (40 mL) was added drop by drop.

The mixture was stirred for 5 h at 508C and 12 h by 208C and then poured

into ice water (50 mL). The solution was extracted three times with diethyl

ether (30 mL), and the organic extracts were washed with water (30 mL)

and brine (30 mL), and dried over Na₂SO₄. The solvent was removed in

vacuo and the purification of the residue by chromatography with CHCl₃

gave the crude products VIII and 7. VIII was further purified by

chromatography with CHCl₃/petroleum ether (1:1.0); Yield: 0.33 g

(24%); K 118C Col 298C I; ¹H NMR (400 MHz, CDCl₃, 258C, TMS):

d 0.84 ± 0.87 (m, 18H; CH₃), 1.25 ± 1.40 (m, 72H; CH₂), 1.42 ± 1.45 (m,

12H; O(CH₂)₂CH₂), 1.73 ± 1.81 (m, 12H; OCH₂CH₂), 3.50 (s, 6H;

CH₂OCH₂Ph), 3.72 (s, 2H; CH₂OH), 3.93 (t, ³J(H,H) 6.6 Hz, 4H;

OCH₂), 3.94 (t, ³J(H,H) 6.6 Hz, 4H; OCH₂), 4.36 (s, 6H; CH₂Ph), 6.75

(dd, ³J(H,H) 8.2 Hz, ⁴J(H,H) 1.6 Hz, 3H; Ar H), 6.78 (d, ³J(H,H)

8.2 Hz, 3H; Ar H), 6.79 (d, ⁴J(H,H) 1.6 Hz, 3H; Ar H); ¹³C NMR

(100 MHz, CDCl₃): d 13.94, 22.56, 25.97, 26.00, 29.24, 29.25, 29.31, 29.36,

29.38, 29.50, 29.49, 29.54, 31.82, 44.96 (CCH₂), 66.19 (CCH₂OH), 69.34,

69.44, 70.84 (CCH₂OCH₂), 73.50 (CCH₂OCH₂), 113.71, 113.95, 120.27,

131.21, 148.94, 149.39; IR (Nujol): nÄ 3454 cm ¹(OH).

1-(3,4-Didecyloxybenzoyloxy)-3-(3,4-didecyloxybenzyloxy)-2,2-bis(3,4-di-

decyloxybenzyloxymethyl)propane (6): Synthesized from VIII (0.208 g,

0.155 mmol) and 3,4-didecyloxybenzoic acid (0.13 g, 0.31 mmol) according

to the general procedure. Purified by chromatography with CHCl₃/

petroleum ether (10:2 ± 0). Yield: 0.198 g (75%); K 108C Col 238C I;

¹H NMR (400 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.87 (m, 24H; CH₃),

1.25 ± 1.42 (m, 112H; CH₂), 1.70 ± 1.85 (m, 16H; OCH₂CH₂), 3.54 (s, 6H;

CH₂OCH₂Ph), 3.88 (t, ³J(H,H) 6.6 Hz, 6H; CH₂OPhCH₂), 3.90 (t,

³J(H,H) 6.6 Hz, 6H; CH₂OPhCH₂), 3.95 (t, ³J(H,H) 6.6 Hz, 2H;

CH₂OPhCOO), 4.00 (t, ³J(H,H) 6.6 Hz, 2H; CH₂OPhCOO), 4.36 (s,

8H; CH₂OOC, PhCH₂), 6.71 ± 6.78 (m, 10H; Ar H), 7.36 (dd, ³J(H,H)

8.4 Hz, ⁴J(H,H) 1.9 Hz, 1H; Ar H), 7.45 (d, ⁴J(H,H) 1.9 Hz, 1H;

Ar H); ¹³C NMR (100 MHz, CDCl₃): d 13.97, 22.58, 25.98, 26.01, 29.10,

29.17, 29.27, 29.33, 29.37, 29.40, 29.42, 29.52, 29.58, 31.84, 44.84 (CCH₂),

64.13 (CCH₂OCH₂), 68.99 (CCH₂OCH₂), 69.18, 69.39, 73.38, 111.98, 113.53,

3

³J(H,H) 8.6 Hz, 2H; Ar H), 8.08 (d, J(H,H) 8.6 Hz, 2H; Ar H); IR

1

(Nujol): nÄ 1706 cm (C O); MS: m/z (%): 538 (58) [M] , 398 (15), 258

(60), 213 (10), 57 (20), 43 (100); C₃₅H₅₄O₄(538.7): calcd C 78.03, H 10.09;

found C 78.15, H 10.29.

A suspension of ethyl 4-(3,4-didecyloxyphenyl)benzoate (3.0 g, 5.5 mmol)

and KOH (0.7 g, 11 mmol) in ethanol (100 mL) was heated at reflux for 3 h,

during which the mixture became clear. After acidification of the hot

solution with hydrochloric acid (2m; 15 mL), the mixture was cooled to 0 ±

58C. The white precipitat was removed and recrystallisized twice from

acetone. Yield: 2.6 g (93%); M.p 1538C; ¹H NMR (400 MHz, CDCl₃,

258C, TMS): d 0.87 ± 0.90 (m, 6H; CH₃), 1.28 ± 1.37 (m, 24H; CH₂), 1.46 ±

1.51 (m, 4H; O(CH₂)₂CH₂), 1.81 ± 1.89 (m, 4H; OCH₂CH₂), 4.05 (t,

3

³J(H,H) 6.6 Hz, 2H; OCH₂), 4.08 (t, J(H,H) 6.6 Hz, 2H; OCH₂), 6.97

(d, ³J(H,H) 8.2 Hz, 1H; Ar H), 7.16 ± 7.20 (m, 2H; Ar H), 7.65 (d,

3

³J(H,H) 8.4 Hz, 2H; Ar H), 8.14 (d, J(H,H) 8.4 Hz, 2H; Ar H); IR

1

(Nujol): nÄ 3250 (OH), 1841 cm (C O); MS: m/z (%): 510 (63) [M] ,

370 (18), 230 (100), 71 (15), 57 (40), 43 (68); C₃₃H₅₀O₄(510.7): calcd C 77.61,

H 9.86; found C 77.80, H 10.00.

1,3-Bis[4-(3,4-didecyloxyphenyl)benzoyloxy]-2,2-bis[4-(3,4-didecyloxy-

phenyl)benzoyloxymethyl]propane (8): Synthesized from pentaerythritol

(0.068 g, 0.5 mmol) and 4-(3,4-didecyloxyphenyl)benzoic acid (2.04 g,

4 mmol) according to the general procedure. Purified by chromatography

with CHCl₃/methanol (1:0 ± 0.05). Yield: 0.52 g (49%); K 928C M 728C I;

¹H NMR (400 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.88 (m, 24H; CH₃),

1.25 ± 1.34 (m, 96H; CH₂), 1.42 ± 1.48 (m, 16H; O(CH₂)₂CH₂), 1.77 ± 1.85

(m, 16H; OCH₂CH₂), 4.00 (t, ³J(H,H) 6.6 Hz, 8H; OCH₂), 4.01 (t,

³J(H,H) 6.6 Hz, 2H; OCH₂), 4.74 (s, 8H; CCH₂), 6.89 (d, ³J(H,H)

8.2 Hz, 4H; Ar H), 7.06 ± 7.09 (m, 8H; Ar H), 7.54 (d, ³J(H,H) 8.4 Hz,

8H; Ar H), 8.02 (d, ³J(H,H) 8.4 Hz, 8H; Ar H); MS (MALDI-TOF,

DHB): m/z: 2108.5 [MH] ; C₁₃₇H₂₀₄O₁₆(2106.9): calcd C 78.10, H 9.75;

found C 78.13, H 9.87.

Tetrakis[4-(3,4-didecyloxyphenyl)phenyl]methane (9): Tetrakis(4-bromo-

phenyl)methane^[19](0.16 g, 0.25 mmol) was dissolved at 208C in Glyme

(20 mL). After addition of Pd(PPh₃)₄(35 mg, 0.03 mmol) the mixture was

stirred for 15 min. 3,4-Didecyloxyphenylboronic acid^[20](0.6 g, 1.38 mmol)

dissolved in glyme (30 mL) and saturated aqueous solution of NaHCO₃

(5 mL) were added while stirring was continued. The reaction mixture was

heated at reflux under an argon atmosphere for 8 h. The solvent was

removed in vacuo and CHCl₃(50 mL) was added. The organic phase was

separated, washed with water (20 mL), dried over Na₂SO₄, and concen-

trated by rotary evaporation. The residue was purified by chromatography

with petroleum ether/CHCl₃(2:0.5 ± 2); Yield: 0.04 g (8%); m.p. 748C;

¹H NMR (500 MHz, CDCl₃, 258C, TMS): d 0.84 ± 0.88 (m, 24H; CH₃),

1.25 ± 1.34 (m, 96H; CH₂), 1.43 ± 1.47 (m, 16H; O(CH₂)₂CH₂), 1.78 ± 1.84

(m, 16H; OCH₂CH₂), 4.01 (t, ³J(H,H) 6.8 Hz, 8H; OCH₂), 4.02 (t,

³J(H,H) 6.8 Hz, 8H; OCH₂), 6.91 (d, ³J(H,H) 8.3 Hz, 4H; Ar H),

113.82, 114.40, 120.12, 122.74, 123.42, 131.38, 148.64, 148.72, 149.29, 153.26,

1

166.28 (C O); IR (Nujol): nÄ 1713 cm (C O); MS (MALDI-TOF,

DHB): m/z: 1782.4 [MNa] , 1798.7 [MK] ; C₁₁₃H₁₉₄O₁₃(1760.5): calcd

C 77.09, H 11.10; found C 76.98, H 11.03.

1,3-Bis(3,4-didecyloxybenzyloxy)-2,2-bis(3,4-didecyloxybenzyloxymethyl)-

propane (7): Purified by chromatography with petroleum ether/ethyl

acetate (10:0.05); Yield: 90 mg (5%); K 148C Col 218C I; ¹H NMR

(400 MHz, C₆D₆, 258C, TMS): d 0.91 ± 0.96 (m, 24H; CH₃), 1.29 ± 1.34 (m,

96H; CH₂), 1.44 ± 1.48 (m, 16H; O(CH₂)₂CH₂), 1.71 ± 1.78 (m, 16H;

OCH₂CH₂), 3.84 (t, ³J(H,H) 6.4 Hz, 8H; OCH₂), 3.87 (t, ³J(H,H)

6.4 Hz, 8H; OCH₂), 3.97 (s, 8H; CCH₂), 4.54 (s, 8H; CH₂Ph), 6.81 (d,

³J(H; H) 8.2 Hz, 4H; Ar H), 6.98 (dd, ³J(H; H) 8.2 Hz, ⁴J(H; H)

1.8 Hz, 4H; Ar H), 7.03 (d, ⁴J(H; H) 1.8 Hz, 4H; Ar H); ¹³C NMR

(100 MHz, C₆D₆): d 14.11, 22.89, 26.42, 26.45, 29.61, 29.64, 29.73, 29.76,

29.84, 29.87, 29.89, 29.93, 29.96, 32.14, 32.16, 46.26 (CCH₂), 69.17, 69.27,

69.90 (CCH₂), 73.72, 114.04, 114.26, 120.45, 132.22, 149.54, 150.15; MS

3

7.10 ± 7.12 (m, 8H; Ar H), 7.33 (d, J(H,H) 8.5 Hz, 8H; Ar H), 7.46 (d,

³J(H,H) 8.5 Hz, 8H; Ar H); ¹³C NMR (100 MHz, CDCl₃): d 14.11,

22.68, 26.04, 27.00, 29.31, 29.34, 29.43, 29.58, 29.63, 30.94, 31.90, 41.94, 69.37,

69.43, 112.92, 114.05, 119.44, 125.78, 131.42, 133.64, 138.44, 145.32, 148.72,

149.22; MS (MALDI-TOF, DHB): m/z: 1873.3 [M] ; 1897.0 [MNa]

;

C₁₂₉H₁₉₆O₈(1874.7).

Tetrakis(3,4-didecyloxyphenyl)stannane (10): 3,4-Didecyloxybromoben-

zene (5.2 g, 11 mmol) was dissolved in dry diethyl ether (100 mL) and

cooled to 208C. Under an argon atmosphere butyllithium (6.8 mL of a

1.6 molar solution in n-hexane, 11 mmol) was added slowly with stirring.

The mixture was stirred at this temperature for 2 h. A solution of SnCl₄

(0.3 mL, 2.5 mmol) in dry benzene (20 mL) was added slowly. When

addition was complete the mixture was allowed to warm to 208C, while

stirring was continued. Afterwards the mixture was heated at reflux for 5 h.

After cooling to 08C a saturated aqueous solution of NH₄Cl (50 mL) was

added at 0 ± 58C. The organic layer was washed with brine and dried over

Na₂SO₄. The solvent was removed in vacuo to give the crude product,

which was purified by chromatography with petroleum ether/ethyl acetate

(10:1.5) and recrystallization from acetone. Yield: 170 mg (4%); m.p.

538C; ¹H NMR (400 MHz, C₆D₆, 258C, TMS): d 0.91 (t, ³J(H,H)

6.8 Hz, 12H; CH₃), 0.92 (t, ³J(H,H) 7.0 Hz, 12H; CH₃), 1.27 ± 1.44 (m,

112H; CH₂), 1.64 ± 1.74 (m, 16H; OCH₂CH₂), 3.82 (t, ³J(H,H) 6.4 Hz,

(MALDI-TOF, DHAP): m/z: 1745.8 [M] ; C₁₁₃H₁₉₆O₁₂(1746.6): calcd C

77.71, H 11.30; found C 77.60, H 11.22.

Synthesis of 8

4-(3,4-Didecyloxyphenyl)benzoic acid: Ethyl 4-bromobenzoate (2.5 g,

11.5 mmol) was dissolved in glyme (25 mL) at 208C. After addition of

Pd(PPh₃)₄(0.4 g, 35 mmol) the mixture was stirred for 15 min. 3,4-

Didecyloxyphenylboronic acid (4.0 g, 9.2 mmol) dissolved in glyme

(100 mL) and saturated aqueous solution of NaHCO₃(35 mL) was added,

while stirring was continued. The reaction mixture was heated at reflux

temperature under an argon atmosphere for 8 h and then it was cooled to

0 ± 58C. The ethyl 4-(3,4-didecyloxyphenyl)benzoate precipitated and was

removed and recrystallisized twice from methanol. Yield: 3.2 g (65%); m.p.

63 ± 658C; ¹H NMR (200 MHz, CDCl₃): d 0.85 ± 0.92 (m, 6H; CH₃),

1658

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Micro Segregation

1643±1660

8H; OCH₂), 3.86 (t, ³J(H,H) 6.2 Hz, 8H; OCH₂), 6.98 (d, ³J(H,H)

7.6 Hz, 4H; Ar H), 7.60 (d, ³J(H,H) 7.6 Hz, 4H; Ar H), 7.65 (s, 4H;

Ar H); ¹³C NMR (100 MHz, C₆D₆): d 14.47, 23.22, 26.67, 29.96, 30.04,

30.16, 32.45, 69.06, 69.41, 114.94, 122.70, 130.04, 131.10, 150.80, 151.42; ¹¹⁹Sn

NMR (149 MHz, C₆D₆): d 108.12; MS (MALDI-TOF, DHAP): m/z:

[18] a) N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun. 1981, 11, 513;

b) M. Hird, G. W. Gray, K. J. Toyne, Mol. Cryst. Liq. Cryst. 1991,

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[19] C. M. Wilson, A. C. Griffin, J. Mater. Chem. 1993, 3, 991.

[20] C. Sauer, S. Diele, N. Lindner, C. Tschierske, Liq. Cryst. 1998, 25, 109.

[21] H. Gilmann, L. A. Gist, J. Org. Chem. 1957, 22, 368.

[22] K. Ohta, H. Ema, H. Muroki, I. Yamamoto, K. Matsuzaki, Mol. Cryst.

Liq. Cryst. 1987, 147, 61.

1677.8 [M] ; C₁₀₄H₁₈₀O₈Sn (1677.0): calcd C 74.48, H 10.81; found C 74.42, H

10.57.

Zinc bis[1,3-bis(3,4-didecyloxyphenyl)-1,3-propanedionate] (11): A solu-

tion of sodium hydride (0.28 mg, 80 per cent dispersion in mineral oil,

0.0118 mmol) in dimethoxyethane (1 mL) was added dropwise to an

solution of 1,3-bis(3,4-didecyloxyphenyl)-1,3-propanedione^[22](10.0 mg,

0.0118 mmol) and ZnCl₂(0.81 mg, 0.0059 mmol) in dimethoxyethane

(5 mL). The mixture was refluxed for 6 h, during which a white precipitate

was formed. The precipitate was filtered off and washed with cold

dimethoxyethane. Column chromatography (chloroform/ethanol 10:0.3 ±

1) afforded a white solid in 19% yield (2 mg). M.p. 1188C; ¹H NMR

[23] A. N. Cammidge, R. J. Bushby, in Handbook of Liquid Crystals,

Vol. 2B (Eds.: D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess, V. Vill),

Wiley-VCH, Weinheim, 1998, 693.

[24] a) A. Eckert, B. Kohne, K. Praefcke, Z. Naturforsch B 1988, 43, 878;

b) K. Praefcke, B. Kohne, A. Eckert, J. Hempel, Z. Naturforsch. B

1990, 45, 1084; c) K. Praefcke, P. Marquardt, B. Kohne, W. Stephan, J.

Carbohydr. Chem. 1991, 10, 539; d) G. Lattermann, G. Staufer, Liq.

Cryst. 1989, 4, 347; e) V. Percec, J. Heck, G. Johansson, D. Tomazos, M.

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1031; f) V. Percec, G. Johannson, J. Heck, G. Ungar, S. V. Batty, J.

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[25] a) K. Borisch, S. Diele, P. Göring, C. Tschierske, Chem. Commun.

1996, 237; b) K. Borisch, S. Diele, P. Göring, H. Müller, C. Tschierske,

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3

(400 MHz, CDCl₃, 258C, TMS): d 0.86 (t, J(H,H) 6.9 Hz, 24H; CH₃),

1.49 ± 1.25 (m, 112H; CH₂), 1.84 ± 1.77 (m, 16H; OCH₂CH₂), 3.44 (s, 2H;

CH), 4.03 (2t, 16H; OCH₂), 6.87 (d, ³J(H,H) 8.5 Hz, 4H; Ar H), 7.56 (d,

3

4

⁴J(H,H) 2 Hz, 4H; Ar H), 7.69 (dd, J(H,H) 8.5, J(H,H) 2 Hz, 4H;

Ar H).

[26] There are several other classes of compounds in which columnar

mesophases have been found, for example, rectangular, oblique and

sometimes also hexagonal columnar thermomesophases can be found

in polycatenar molecules (J. Malthete, H. T. Nguyen, C. Destrade, Liq.

Cryst. 1993, 13, 171.), in anhydrous soaps (A. Skoulios, V. Luzzati,

Acta Crystallogr. 1961, 14, 278), in rod-coil molecules (M. Lee, N.-K.

Oh, W.-C. Zin, Chem. Commun. 1996, 1787), in calamitic molecules

with lateral polar groups (F. Hildebrandt, J. A. Schröter, C.

Tschierske, R. Festag, M. Wittenberg, J. H. Wendorff, Adv. Mater,

1997, 9, 564), and rectangular and oblique columnar phases were

found as modulated smectic phases of polar calamitic compounds (F.

Hardouin, A. M. Levelut, M. F. Achart, G. Sigaud, J. Chim. Phys.

1983, 80, 53). Also rodlike polymers, such as polyglutamates can form

columnar mesophases (R. Sakamoto, A. Osawa, Mol. Cryst. Liq.

Cryst. 1987, 153, 385).

Acknowledgments

This work was supported by the Kultusministerium des Landes Sachsen

Anhalt.

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Chem. Eur. J. 1999, 5, No. 5

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C. Tschierske et al.

FULL PAPER

Vorländer group: H. Voigt, PhD thesis, Universität Halle, 1924. These

Schiff-base derivatives with terminal methoxy groups have no liquid-

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[36] In contrast, related acetylacetonates of Fe, Co, and Ni that have

octahedral geometry are mesomorphic.^[6]It seems that additional

interactions between the metal centers could be responsible for

mesophase formation in the octahedral metallomesogens.

[37] G. Staufer, Dissertation, Bayreuth 1990, 47.

[42] J. W. Goodby, M. Hird, K. J. Toyne, T. Watson, J. Chem. Soc. Chem.

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[43] D. R. Coulson, L. C. Satek, S. O. Grim, Inorg. Synth. 1973, 13, 121.

Received: December 7, 1998 [F1368]

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Chem. Eur. J. 1999, 5, No. 5

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The importance of micro segregation for mesophase formation: Thermotropic columnar mesophases of tetrahedral and other low-aspect-ratio organic materials

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