Tailoring thermotropic cubic mesophases: Amphiphilic polyhydroxy derivatives

J O U R N A L O F

Tailoring thermotropic cubic mesophases: amphiphilic polyhydroxy

derivatives†

Konstanze Borisch,a Siegmar Diele,b Petra Go¨ring,b Horst Kresseb and Carsten Tschierske*a

aInstitut fur Organische Chemie, Martin-L uther-Universitat Halle-W ittenberg, Kurt-Mothes Str.

¨

2, D-06120 Halle, Germany

¨

C H E M I S T R Y

bInstitut fur Physikalische Chemie, Martin-L uther-Universitat Halle-W ittenberg, Muhlpforte 1,

¨

D-06108 Halle, Germany

¨

Novel amphiphilic polyhydroxy compounds [N-(3,4-dialkoxybenzoyl)-1-amino-1-deoxy--glucitols (glucamides), N-(3,4-

dialkoxybenzoyl)-1-deoxy-1-methylamino--glucitols, N-(3,4,5-trialkoxybenzoyl)-1-deoxy-1-methylamino--glucitols (N-

methylgucamides), 1-benzoylaminopropane-2,3-diols, 2-benzoylaminopropane-1,3-diols, 2-(3,4,5-tridodecyloxybenzoylamino)-2-

(hydroxymethyl)propane-1,3-diol and (3,4,5-tridodecyloxybenzoyl)bis(2,3-dihydroxypropyl)amine] have been synthesized. Their

thermotropic liquid crystalline phases were investigated by means of polarizing microscopy, diﬀerential scanning calorimetry and

X-ray diﬀraction. Depending on the chain length, and the size of the hydrophilic polyhydroxy units, diﬀerent mesophases have

been found: smectic A phases (S ), inverted bicontinuous cubic phases (Cub , Ia3d), hexagonal columnar phases (Col ) and

A

I2

V2

H2

micellar cubic mesophases (Cub , Pn3m or P43n). In strong analogy to lyotropic systems, the type of thermotropic mesophase

depends on the ratio between the volume of the lipophilic moiety and the surface area of the hydrophilic moiety at the

hydrophilic–lipophilic interface. The crossing from zero interface curvature (S phase) to the ﬁnite negative curvature of the

inverted cylindrical aggregates of the columnar mesophase takes place via bicontinuous cubic mesophases. The cylindrical

A

aggregates of the columnar mesophase are stable over a rather broad range of variation of the structural parameter. At a certain

degree of the size of the lipophilic moiety in respect to the surface area of the hydrophilic group, however, the transition from the

hexagonal columnar to a micellar cubic mesophase takes place. On the basis of proton conductivity measurements and from

packing considerations we propose that this cubic lattice is built up by eight closed micelles per unit cell which have a rod-like

shape and represent small segments of extended columns. Therefrom we can propose a model for the transformations between

these diﬀerent thermotropic mesophases.

Cubic mesophases represent ordered supermolecular arrange-

ments which are optically isotropic. They are common in

surfactant–solvent and lipid–solvent systems1 and have

attracted considerable interest due to their application in the

pharmaceutical industry, their potential use in drug release

systems and as templates for the preparation of mesoporous

silicates and also because of their biological signiﬁcance.2 Well-

deﬁned cubic structures can also be found in amphiphilic block

copolymers3 and polyelectrolytes.4

As shown in Fig. 1 several diﬀerent cubic phases can be

observed in lyotropic systems when the concentration of the

surfactant is changed. They can either occur as intermediate

phases between lamellar and hexagonal columnar phases

(bicontinuous cubic phases, V-phases), or between the hexag-

onal columnar phases and the micellar solutions (discontinuous

cubic phases, I-phases).5,6 The ﬁrst type can be regarded as

interwoven networks of branched columns, the second one has

a diﬀerent microstructure. It is assumed to consist of a cubic

arrangement of closed spherical or nonspherical micelles. The

value of the interface curvature between hydrophilic regions

and lipophilic regions was recognized as the key factor

determining the morphology of the polymolecular aggregates

forming the mesophase (layers, columns, closed micelles),7

whereas the sign of the interface curvature distinguishes

between normal (type 1, the interface curvature is directed

away from the regions with stronger cohesive interactions) and

inverted phase types (type 2, the interface curvature is directed

toward the regions with stronger cohesive forces). From a

crystallographic point of view one can distinguish between

diﬀerent cubic lattices: primitive (Pn3m/Q224, Pm3n/Q223), body

centred (Ia3d/Q230, Im3m/Q229) and face centred (Fm3m/Q225,

Fd3m/Q227). The diﬀerent types of cubic lattices found up to

now in the diﬀerent regions of the lyotropic phase sequence

are collected in the principal phase diagram given in Fig. 1.1,8–10

It has to be mentioned that additional intermediate mesophases

(ribbon-phases, rhombohedral, tetragonal and ortorhombic

phases11,12 and isotropic hexagonal phases13) can be found

between the lamellar phase and the normal and inverted

columnar phases.

In contrast to lyotropic cubic systems relatively few thermo-

tropic compounds with cubic phases are known. They have

been found for nitro- and cyano-substituted biphenyl car-

boxylic acids,14,15 dibenzoylhydrazides,16 strontium soaps,17

polycatenar compounds,18–21 discotic molecules,22,23 silver

complexes,24,25 a spherical compound,26 a few calamitic com-

pounds27,28 and polypeptides.29 In most cases, bicontinuous

structures with a body centred lattice (Ia3d, Im3m) have been

found for these cubic phases.18,15 More recently diﬀerent types

of thermotropic cubic phases have been observed for amphi-

philic oligoethylene imines,30 diols31,32 and carbohydrate

derivatives.33–36 In the case of double chain carbohydrates

body centred cubic phases (Ia3d) were usually found whereas

cubic phases with primitive cubic lattices (Pm3n or P43n) have

only recently been detected for the thermotropic phases of

some triple chain amphiphilic carbohydrates36 and diol com-

pounds32 and also for some dendrimers.37 From packing

considerations it was concluded that the cubic phases of

these compounds should represent inverted micellar cubic

mesophases.

† Presented at the Third International Conference on Materials

Chemistry, MC3, University of Exeter, Exeter, 21–25 July, 1997.

* E-mail: coqfx@mlucom.urz.uni-halle.de

J. Mater. Chem., 1998, 8(3), 529–543

529

N-methylglucamides, 2,3-dihydroxypropylamides and some

related acylated amino alcohols with diﬀerent numbers of alkyl

chains and hydroxy groups.39,40 The results of the investigation

of these compounds are summarized in this report.

Results and Discussion

Syntheses

The

homologous

N-benzoyl-1-amino-1-deoxy--glucitol

derivatives 1, N-benzoyl-1-deoxy-1-methylamino--glucitols 2

and 3 were synthesized according to the procedure given for

the hexyl and dodecyl derivatives.36 The other materials were

synthesized by aminolysis of substituted benzoyl chlorides with

an excess of 1-aminopropane-2,3-diol (compounds 5–7)

(Scheme 1), 2-aminopropane-1,3-diol (compounds 8 and 9)

and 2-amino-2-(hydroxymethyl)propane-1,3-diol (compound

10) respectively. The tetraol 11 was obtained by aminolysis of

3,4,5-tridodecyloxybenzoyl chloride with diallylamine, followed

by OsO -catalyzed dihydroxylation of the oleﬁnic double

bonds. The ﬁnal compounds were puriﬁed by column chroma-

4

tography and repeated crystallization. Details are given in the

Experimental part.

Amphiphilic carbohydrate derivatives

Optically isotropic mesophases of double chain carbo-

hydrates—bicontinuous cubic phases. At ﬁrst we investigated

the homologues series of the double chain glucamides 1 and

the analogous N-methylglucamides 2 (Tables 1 and 2). In both

series of compounds optically isotropic mesophases were found

for one or two compounds with a medium chain length.

In the case of the glucamides 1 the pentyloxy derivative 1/5

and the hexyloxy derivative 1/6 have optically isotropic meso-

phases. The isotropic mesophase of 1/6 has recently been

investigated and it was found that this phase is a cubic

Fig. 1 Schematic representation of the major lyotropic liquid crystal-

line phase types occurring in detergen–solvent and lipid–solvent

systems depending on the solvent concentration (refs. 1,8); abbrevi-

ations: L =lamellar a-phase, V=bicontinuous cubic mesophase, H=

a

hexagonal columnar phase, I=discontinuous (micellar) cubic phase;

subscripts: 1=normal phase (type 1, the interface curvature is directed

away from the regions with stronger cohesive interactions), 2=

inverted phases (type 2, the interface curvature is directed toward the

regions with stronger cohesive forces). The positions of the known

types of lyotropic cubic phases in the ideal phase diagram are shown

together with their space-groups and space-group numbers. Curiously,

some inverse systems exhibit phase sequences which are not in accord

with this ﬁgure. It is unknown why in some systems the sequences

H –V or V –L occur on increasing the surfactant concentration

mesophase with a body centred lattice (Ia3d; a =8.31 nm

cub

at 175 °C).36 The lower homologues (compounds 1/4 and 1/5)

display smectic A phases (beside an isotropic mesophase in

the case of 1/5) and the higher homologue 1/7 with two

2

a

(ref. 1). The ‘rod-like’ versions of the bicontinuous cubic phases are

shown. They can also be regarded as bilayers draped on the underlying

minimal surfaces (refs. 1,41). Additional to the shown cubic phases a

chiral cubic phase with the space group P4 32 (Q212) was found in a

ternary lipid–protein–water system (ref. 9). Recently, a novel variant

3

of the cubic phases with the space group Im3 has been found in a

ternary lyotropic system between

phase (ref. 10).

a rectangular and a lamellar

It seems that the mesophases of the pure carbohydrate- and

polyhydroxy-amphiphiles represent thermotropic analogues of

the diﬀerent lyotropic mesophases occurring in detergent–

solvent systems. In order to conﬁrm this analogy, we have

initiated a systematic study of the inﬂuence of slight variations

of the lipophilic and the polar regions of amphiphilic polyhy-

droxy compounds on the appearance of the diﬀerent types of

thermotropic cubic mesophases.‡ For this purpose we have

synthesized novel double chain and triple chain glucamides,

‡ In a related study the inﬂuence of the alkyl chain size on the

lyotropic mesophase structure of 1-alkanoyl-1-deoxy-1-methylamino-

-glucitols has been investigated (ref. 38).

Scheme 1 Reagents and condition: i, RBr, K CO , cyclohexanone; ii,

KOH, H O, EtOH; iii, H O, H+; iv, SOCl ; v, DMF, DMAP, 2,3-

2

3

2

dihydroxypropylamine

530

J. Mater. Chem., 1998, 8(3), 529–543

Table 1 Transition temperatures and associated enthalpy values (lower

lines; in italics) of the N-(3,4-dialkoxybenzoyl)-1-amino-1-deoxy--

glucitols 1a

T /°C

compound

1/4

R

DH/kJ mol−1

K 174 (S 156) Iso

C H

4

9

11

A

66.3

K 172 (M 162 S 168) Iso

0.7

1/5

C H

5

A

68.7

0.5

K 172 Cub 185 (Col 185) Iso

1/6b,c

1/7

C H

6

13

V2 H2

Fig. 2 Optical photomicrograph (crossed polarizers) of the isotropic

mesophase of compound 1/6 growing from the hexagonal columnar

mesophase at 184 °C

73.5

0.7

K 169 Col 203 Iso

C H

7

15

H2

72.9

1.1

K 166 Col 239 Iso

1/9

C H

9

19

H2

94.8

K 162 Col 254 Iso

2.6

1/12b

C

H

head groups. They are connected three-by-three and separated

by a gyroid minimal surface41 within the lipophilic continuum

of the alkyl chains (see Fig. 1).

12 25

H2

91.2

0.9

aAbbreviations: K=crystalline solid, S =smectic A phase, Col

=

A

H2

More detailed investigation of the cubic to liquid phase

transition has been done. On heating, a direct transition from

the cubic phase to the liquid state occurs at 185 °C. On fast

cooling from the liquid however, a spherulitic texture occurs

at the same temperature. This texture is typical for hexagonal

columnar phases and is identical with the optical texture of

the hexagonal columnar mesophases of the glucamides

1/7–1/12. Immediately after this phase transition took place

the cubic phase appear as highly viscous isotropic domains

with cornered boundaries (see Fig. 2). These domains grow

rapidly and coalesce to a homogeneous area. On re-heating a

direct transition from the highly viscous cubic phase to the

ﬂuid liquid was found at 185 °C. The spherulitic texture cannot

be found on very slow cooling (<2 K min−1). Obviously the

formation of the cubic phase can be supercooled and therefore

a columnar phase is observed ﬁrst as a metastable (monotropic)

phase. Interestingly the clearing temperature of the columnar

mesophase and the transition temperature of the cubic phase

to the liquid state seem to be identical (DT <1 K).

inverted hexagonal columnar mesophase, Cub =inverted bicontinu-

V2

ous cubic mesophase, M=optically isotropic (probably cubic) meso-

phase of unknown structure, Iso=isotropic liquid; values in

parentheses refer to metastable (monotropic) mesophases. In the

compound numbering X/Y, X represents the compound type, and Y

the length of the alkyl chain. bRef. 36. cThe texture of a columnar

mesophase is only detected on cooling (see text).

Table 2 Transition temperatures, associated enthalpy values (lower

lines) and lattice parameter of the smectic phase (d ) and of the

lam

hexagonal columnar mesophases (a ) at the measurement tempera-

hex

tures (lower lines in brackets) of the N-(3,4-dialkoxybenzoyl)-1-deoxy-

1-methylamino--glucitols 2a

T /°C

d

/nm

a

/nm

The lower homologue 1/5 displays an enantiotropic smectic

A phase which turns into an isotropic mesophase on cooling

below 162 °C. This phase transition can also be supercooled

lam

hex

compound

2/6b

R

DH/kJ mol−1

K 93 S 130 Iso

(T /°C)

C H

3.19

(120)

—

6

13

A

(down to 158 °C); however this S phase is a thermo-

29.5

K 96 M 118 (S 118) Iso

0.7

A

dynamically stable (enantiotropic) phase in the temperature

2/7c

C H

—

7

15

A

range between 162 and 168 °C. Remarkably, the appearance

of the isotropic domains is diﬀerent from that of the Cub

phase of compound 1/6. They appear as circular domains (the

27.5

K 87 Col 155 Iso

0.4

2/8

C H

—

4.27

(80)

8

17

H2

V2

18.5

K 68 Col 174 Iso

0.1

2/9

C H

4.46

(80)

4.88

(120)

—

same texture as shown in Fig. 3). Due to rapid crystallization

of this compound no X-ray investigation of its isotropic

mesophase can be carried out to conﬁrm a cubic structure.

No transition to an optically isotropic mesophase was found

9

19

H2

K 54 Col 194 Iso

18.0

0.2

2/12b

2/16

C

H

12 25

H2

K 82 Col 194 Iso

22.5

0.9

H

16 33

H2

on cooling the S phase of the dibutoxy derivative 1/4 down

45.7

1.2

A

to 146 °C. At this temperature rapid crystallization sets in.

Also the N-methylglucamide 2/7 has an optically isotropic

mesophase. This mesophase again occurs intermediate between

a smectic A phase (compound 2/6) and a hexagonal columnar

phase (compound 2/8). Comparing the homologous series of

the glucamides 1 with the N-methylglucamides 2 indicates that

in the series of the N-methylglucamides 2 the isotropic meso-

phase occurs at a longer chain length. Therefore, one can

conclude that the N-methylglucamide group is slightly larger

than the glucamide group. However, it has to be considered

that the transition temperatures of the glucamides are signiﬁ-

cantly higher than those of the corresponding N-methylgluca-

mides (due to the additional hydrogen bonding of the NMH

group) and therefore their alkyl chains have an increased

aAbbreviations as in Table 1. bRef. 36. cThe fan-like texture of a S

A

phase is only detected on cooling (see text). The value of the transitions

to the isotropic liquid was found by microscopic investigations. In the

DSC heating cycle an endotherm was detected at 125 °C.

heptyloxy chains has a hexagonal columnar mesophase. Thus,

with respect to the chain length, the cubic phase occurs as an

intermediate phase between the S phase and the inverted

A

hexagonal columnar phase. In analogy to lyotropic systems it

can therefore be concluded that this cubic phase should be an

inverted bicontinuous cubic phase (V -phase). It should consist

of two interwoven yet non-connected networks of cylinders

containing the hydrogen bonding networks of the carbohydrate

2

J. Mater. Chem., 1998, 8(3), 529–543

531

phase type also changes. In analogy to lyotropic systems

(Fig. 1), an inverted hexagonal columnar phase (Col ) can be

H2

found between the isotropic mesophase of compound 2/7 and

the inverted micellar cubic phase (Cub ) of compound 3/12.

Thus, the same type of binary phase diagram as for compound

I2

1/6 (forming a Cub phase) with 3/12 was found.36 Therefore,

we conclude that this isotropic mesophase should represent an

V2

inverted bicontinuous network structure (Cub ). However,

due to the low number and intensity of scatterings in the

V2

SAXRS we were not yet able to determine the type of cubic

lattice.

Micellar cubic mesophases of triple chain carbohydrate amphi-

philes. Now let us turn to triple chain compounds, which have

an increased size of the lipophilic moiety and should form

strongly curved aggregates. The phase transition temperatures

of the triple chain N-methylglucamides 3 are summarized

in Table 3.

Fig. 3 Optical photomicrograph (crossed polarizers) of the optically

isotropic mesophase of compound 2/7 growing from the S phase

at 90 °C

A

In contrast to the analogous double chain compounds 2, in

this homologous series the compounds with a short and

medium chain length (3/6 and 3/8) have a hexagonal columnar

mesophase and an optically isotropic mesophase occurs on

elongation of the alkyl chains, i.e. on increasing the interface

curvature between polar and lipophilic regions. Therefore it

can be concluded that this phase represents a cubic phase

consisting of a cubic arrangement of closed inverted micelles.

The nonyloxy derivative 3/9 and the decyloxy derivative

3/10 display a columnar–cubic dimorphism. In contrast to the

double chain carbohydrates, the triple chain glucamides have

the cubic phases as high temperature mesophases above the

hexagonal columnar phase. The X-ray pattern of these cubic

phases can be indexed on the basis of primitive cubic lattices

mobility which gives rise to a larger eﬀective volume of their

lipophilic region.

Also for the N-methylglucamide 2/7 a direct transition from

the isotropic mesophase to the liquid state can only be found

in the heating cycles. On cooling from the liquid state a fan-

like texture with homeotropic regions and oily streaks can be

observed and not a spherulitic texture as found in the case of

the glucamide 1/6. These textural features are typical for a

smectic A phase. Immediately after the appearance of the S

phase small circular and optically isotropic domains occur (see

A

Fig. 3), which rapidly grow and coalesce with formation of a

uniform optically isotropic area. The viscosity of these circular

domains is signiﬁcantly larger than that of the surrounding

(e.g. a =7.93 nm at 121 °C for compound 3/9). The space

group can be either Pm3n or P43n. Interestingly, the cubic

cub

S

phase. Thus, it can easily be distinguished from the homeo-

tropically aligned regions of the S phase. On re-heating only

A

lattice parameter amounts to approximately twice the hexag-

onal lattice parameter of the hexagonal columnar phase below

A

a direct transition to the ﬂuid isotropic phase was found at

118 °C and no S phase occurs. Obviously, the formation of

the isotropic mesophase is again kinetically hindered. This

(e.g. a =4.08 nm at 90 °C for 3/9). The same relationship

between the hexagonal and cubic lattice parameter is found

for other triple chain amphiphiles and will be discussed below.

A

hex

kinetic eﬀect points to a three dimensional structure of this

mesophase.

This and the high viscosity of the isotropic mesophase

represent typical features of cubic mesophases.

The inverted bicontinuous structure of the isotropic meso-

phase of compound 1/6 can be conﬁrmed by miscibility

experiments. The binary phase diagram of the system 2/7–3/12

is shown in Fig. 4.

N-(3,5-Didodecyloxybenzoyl)-1-amino-1-deoxy-D-glucitol

4/12. The 3,5-disubstituted glucamide 4/12 shows exclusively

a hexagonal columnar mesophase.

Because the structural parameter continuously changes in

the contact region between these two compounds, the meso-

If one compares this compound with the related 3,4-disubsti-

tuted double chain compound 1/12 and the triple chain

carbohydrates 3/12, a signiﬁcantly lower mesophase stability

is found for 4/12. The absence of a cubic mesophase leads to

the assumption that this 3,5-disubstitution pattern gives rise

to behaviour more similar to the 3,4-disubstituted compound

than to the triple chain compound 3/12.

The columnar mesophases of the double and triple chain

glucamides. The hexagonal columnar phases of the amphiphilic

polyhydroxy compounds consist of extended aggregates of

hydrogen bonding networks surrounded by the molten alkyl

chains. Comparison of the hexagonal lattice parameter of the

double chain compound 2/8 (a =4.27 nm at T =80 °C) and

hex

the triple chain compound 3/8 (a =3.83 nm at T =80 °C)

hex

Fig. 4 Binary phase diagram of the system 2/7–3/12

which have both the same chain length and the same molecular

532

J. Mater. Chem., 1998, 8(3), 529–543

Table 3 Transition temperatures, associated enthalpy values (lower lines) and lattice parameter of the hexagonal columnar mesophases (a ) and

the cubic mesophases (a ) at the measurement temperatures (lower lines in brackets) of the N-(3,4,5-trialkoxybenzoyl)-1-deoxyl-1-methylamino-

hex

cub

-glucitols 3a

T /°C

a

/nm

a

/nm

hex

cub

compound

3/6b

R

DH/kJ mol−1

K 94 Col 145 Iso

(T /°C)

C H

3.49

(100)

3.83

(80)

4.08

(52)

—

6

13

H2

40.2

K 75 Col 147 Iso

1.3

3/8

C H

—

8

17

H2

48.8

K 50 Col 102 Cub 143 Iso

0.7

3/9

C H

7.93

(121)

—

9

19

H2 I2

62.1

1.1

0.8

3/10

C

H

K 59 Col 89c Cub 158 Iso

10 21

H2 I2

55.2

0.3

K 75 Cub 185 Iso

0.6

3/12b

H

—

8.55

(90)

12 25

I2

112.3

1.2

aAbbreviations: Cub =inverted micellar cubic mesophase, other abbreviations as in Table 1. bRef. 36. cThis phase transition refers to the heating

I2

cycle. On cooling the cubic–columnar transition occurs is at 56 °C.

length (L =2.55 nm as estimated from CPK models) indicates

that the (average) diameter of the columns of the double chain

compound is signiﬁcantly larger then the diameter of the

columns of the triple chain compound. Further examples are

collected in Table 4. Assuming a density of r=1 g cm−3 the

number n of molecules arranged side by side in a single slice

of the columns with a thickness (h) of 0.45 nm was estimated

according to eq. (1).

n=(a2/2)√3h(N /M)r

(1)

A

The parameter a is the hexagonal lattice parameter, N the

Avogadro constant and M the molecular mass. The estimated

A

Fig. 5 Cross section of the columnar mesophases of (a) the triple chain

amphiphiles and (b) the double chaing amphiphiles

values of n amount to about 5 for the triple chain compounds

3/6–3/8. This value corresponds to those values found

in columnar phases of other tapered polyhydroxy

compounds.42–45

Obviously, the three alkoxy chains can eﬀectively surround

the polar regions of the hydrogen bonding networks and a

nearly circular shape of the columns can be assumed.

In contrast, in the columnar mesophases of all investigated

double chain compounds (1/8–1/12) a much larger number,

about eight molecules per slice, was observed. This number is

larger than found for other wedge shaped polyhydroxy amphi-

philes. Probably the columns of these double chain compounds

are non-circular (see Fig. 5). Taking into account the fact that

the orientation of the deformations can change along the axis

of the columns and/or that they are arranged randomly

oriented in the hexagonal lattice, the cross sections of these

aggregates should be circular on average, giving rise to the

typical scattering pattern of hexagonal columnar phases.46

Amphiphilic diols, triols and tetraols

Single chain, double chain and triple chain 1-benzamidopro-

pane-2,3-diol derivatives. In a next step we decided to investigate

the inﬂuence of the structure of the hydrophilic parts of the

amphiphilic molecules on their mesophase behaviour. At ﬁrst

we synthesized and investigated single chain, double chain and

triple chain 1-benzamidopropane-2,3-diol derivatives (com-

pounds 5–7 in Table 5). These compounds are structurally

related to the glucamides 1–3, but they have only two instead

of ﬁve hydroxy groups. In this way the number of attractive

hydrogen bonds is decreased and consequently the phase

transition temperatures are shifted to lower values.

Table 4 Comparison of the hexagonal lattice parameter (a ), the

molecular length (L ) (as determined from CPK models assuming an

hex

all trans-conformation of the chains) and the number of molecules (n)

arranged in each slice of the columnar mesophases (with a high of

0.45 nm) of the double chain and triple chain amphiphiles with the

same length of the alkyl chains

As in the case of related -glucamides,35 three diﬀerent types

of mesophases were found for the 1-benzamidopropane-2,3-

diol derivatives depending on the number of alkyl chains.

Compound 5/12 with only one dodecyloxy chain forms a

triple chain

amphiphile

double chain

amphiphile

a

/nm

a

/nm

smectic A phase, a hexagonal columnar phase (Col ) is found

for the double chain compound 6/12 and a cubic phase was

hex

L /nm Comp. (T /°C)

hex

Comp. (T /°C)

R

n

H2

detected for compound 7/12 with three dodecyloxy chains

(Table 5).

The inverted micellar structure of the cubic phase of com-

pound 7/12 was at ﬁrst proven by means of miscibility

experiments. The optical microscopic picture of the contact

region between the smectic phase of 5/12 and the cubic phase

C H

O

2.55

2.7

3/8

3/9

7/6

3.83

(80)

4.08

(52)

3.13

(75)

5.0

5.4

4.7

2/8

2/9

6/6

4.27

(80)

4.46

(80)

3.48

(84)

7.7

8.0

7.2

8

17

19

13

C H

9

C H

1.9

6

J. Mater. Chem., 1998, 8(3), 529–543

533

Table 5 Transition temperatures, associated enthalpy values (lower lines) and lattice parameter of the smectic phase (d), of the hexagonal

columnar mesophases (a ) and the cubic mesophases (a ) at the measurement temperatures (lower lines in brackets) of the 1-benzoyl-

hex

aminopropane-2,3-diols 5–7a

cub

T /°C

d/nm

(T/°C)

a

/nm

a

/nm

hex

cub

compound

5/12

6/6

R1

R2

R3

DH/kJ mol−1

80 K 89 S 132 Iso

(T/°C)

OC

H

K

4.03

(85)

—

12 25

1

2

A

11.6 36.6

K 79 Col 87 Iso

0.8

OC H

3.48

(84)

4.2

—

6

13

6

13

H2

22.0

0.3

K 98 Col 148 Iso

6/12

7/6

OC

H

OC

H

—

12 25

H2

K 49 Col 91 Iso

(105)

3.13

(75)

3.16

(45)

3.33

(50)

—

60.4

1.4

OC H

—

6

13

15

6

13

15

6

13

15

17

19

H2

23.6

K 46 Col 92 Iso

1.4

7/7

OC H

—

7

H2

25.7

1.5

7/8

OC H

K 59 Col 74b Cub 85c Iso

6.89

(75)

7.06

(65)

7.94

(45)

8

17

8

17

8

H2 I2

38.6

0.6

0.4

7/9

OC H

K 49 Cub 104d Iso

9

19

9

19

9

I2

45 K 69 Cub 126 Iso

24.4

0.3

I2

7/12

OC

H

OC

H

OC

H

K

—

12 25

1

2

36.0 11.5

0.7

aAbbreviations as in Tables 1–3. bThis phase transition refers to the cooling cycle. On heating the columnar–cubic phase transition is observed

at 79 °C due to the ‘overheating’ of this phase transition. cOn cooling the cubic phase appears at 77 °C. dThis value was found by microscopic

investigations. In the DSC–heating cycle an endotherm was detected at 107 °C.

of compound 7/12 between crossed polarizers is shown in

Fig. 6. In the contact region between the cubic phase of the

triple chain diol 7/12 and the smectic phase of the single chain

diol 5/12 a hexagonal columnar phase is induced (large

spherulites in the centre of Fig. 6). The detailed phase diagram

of the system 5/12–7/12, obtained by investigation of binary

mixtures, is shown in Fig. 7.

The induction of a columnar mesophase in the contact

region of these two compounds is an important piece of

evidence for the proposed inverse micellar structure of the

cubic mesophase of the triple chain diol 7/12. The X-ray

diﬀraction pattern of this cubic phase can be indexed on the

basis of a primitive cubic lattice (Pm3n or P43n) with a lattice

parameter a =7.45 nm at T =90 °C.

The dependence of the mesophase type on the chain length

(see Table 5) was investigated for the triple chain diols 7. The

cub

Fig. 7 Binary phase diagram of the system 5/12–7/12

short chain diols 7/6 and 7/7 have columnar mesophases; a

columnar/cubic dimorphism was found for the octyloxy deriva-

tive 7/8. Fig. 8 shows the transition from the hexagonal

columnar phase to the cubic mesophase as it can be seen on

heating compound 7/8 between crossed polarizers.

The higher homologues 7/9 and 7/12 have exclusively cubic

mesophases. The cubic phases of 7/8 and 7/12 have the same

kind of primitive cubic lattice (Pm3n or P43n). As an example

the diﬀraction pattern of the cubic phase of compound 7/12

is shown in Fig. 9.

The DSC heating and cooling traces of compound 7/8 are

Fig. 6 Optical photomicrograph (crossed polarizers) of the Col

phase developing in the contact region between the micellar cubic

H2

shown in Fig. 10. It indicates that the crystalline state can be

strongly supercooled. Even after prolonged storage only partial

crystallization takes place. Therefore any heating cycle after

Cub phase of compound 7/12 (optical isotropic region at the right-

hand side) and the S phase of compound 5/12 (left-hand side) at 95 °C

I2

A

534

J. Mater. Chem., 1998, 8(3), 529–543

Fig. 9 X-Ray pattern of the micellar cubic mesophase of compound

7/12 at 70 °C

Fig. 10 DSC heating and cooling trace of 7/8 (10 K min−1)

dimensional structure (cubic phase) to the columnar mesophase

occur without supercooling eﬀects. Therefore, the values for

this transition were taken from the cooling cycles. All other

reported values correspond to the heating cycles.

There is another interesting point concerning the transition

from the optically isotropic mesophases to the ﬂuid liquid

state. This transition can be detected microscopically by the

sudden increase of the ﬂuidity. In many cases however (e.g.

compound 7/9) the corresponding endotherm in the DSC

heating curve is detected at higher temperatures then observed

by microscopy. The reason for this behaviour is not clear.

However, related phenomena were reported for several other

compounds with transitions from three-dimensional ordered

mesophases to isotropic liquids47 (cubic phases of long chain

nitro-biphenyl carboxylic acids, TGB-phases and blue phases

of chiral liquid crystals).

Comparing the homologous series of the triple diols 7 with

that of the corresponding triple chain N-methylglucamides 3

reveals that the same phase sequence is found in both series

of compounds; however the transition from the columnar to

the cubic phase occurs in the series of compounds 7 which

already have a chain length of eight instead of nine or ten

carbon atoms. This means, that the eﬀective size of the 1-

amidopropane-2,3-diol unit at the hydrophilic–lipophilic

interface should be slightly smaller than that of the 1-methyl-

amidoglucitol group. This is also evident from the comparison

of the double chain compounds 2/6 and 6/6. The N-methylglu-

camide 2/6 is a smectic liquid crystal whereas the diol 6/6

forms a columnar mesophase.

Fig. 8 Optical photomicrographs (crossed polarizers) of the Cub

phase developing on heating the Col phase of compound 7/8.

I2

H2

(a) Col phase at 74 °C; Cub phase (black regions) growing into the

H2

I2

Col phase at (b) 78 and (c) 79 °C (the reduced sharpness of this

picture is due to the rapid growing of the cubic domains during the

time of exposition).

H2

the ﬁrst one gives signiﬁcantly lower melting enthalpies and

sometimes also diﬀerent melting temperatures. All melting

temperatures and enthalpies given in Tables 1–3, 4, 6 and 8

refer to the ﬁrst heating cycles.

Due to the three dimensional structure of the cubic phases

the formation of these isotropic phases can be kinetically

hindered. On cooling, the transition from the liquid to the

cubic phase is often supercooled and on heating the transition

from the columnar to the cubic phase can be overheated.

Therefore diﬀerent values can result for the heating and cooling

cycles depending on the heating–cooling rates (see for example

Fig. 10). If the cubic phase represents the high temperature

mesophase, only on cooling does the transition from the three-

2-Benzamidopropane-1,3-diols. In the next step, two selected

examples of 2-benzamidopropane-1,3-diols (compounds 8/6

and 9/12, Table 6) have been synthesized. These compounds

J. Mater. Chem., 1998, 8(3), 529–543

535

Table 6 Transition temperatures and associated enthalpy values (lower lines) of the 2-benzoylaminopropane-1,3-diol 8/6 and 9/12a

T /°C

compound

8/6

R1

R2

R3

DH/kJ mol−1

K 64 K 108 [Cub 50 (Col 50)] Iso

OC H

H

6

13

6

13

1

2

V2

H2

4.5

31.6

9/12

OC

H

OC

H

OC

H

K 67 (Col 62b) Cub 104c Iso

12 25

H2 I2

39.3

2.1

0.4

aAbbreviations as in Tables 1–3. bThis phase transition refers to the cooling cycle. On heating the columnar–cubic phase transition is observed

at 72 °C due to the ‘overheating’ of this phase transition. cFound by microscopic investigations. In DSC heating cycles the phase transition

occurs at 108 °C.

diﬀer from the 1-benzamidopropane-2,3-diols 6/6 and 7/12

only in the position of their hydroxy groups to each other.

Interestingly, the triple chain 1,3-diol 9/12 displays a

columnar/cubic dimorphism, whereas the corresponding 1,2-

diol 7/12 with the same number and length of the chains forms

a micellar cubic phase exclusively. This means that the 1,3-

diol unit represents a signiﬁcantly larger hydrophilic group

than the corresponding 1,2-diol unit. This is in accordance

with the diﬀerent molecular areas found in the densely packed

monomolecular layers of 1,2-diols (0.21 nm2 per molecule)48

and 1,3-diols (0.24 nm2 per molecule)49 at the air–water

interface. The double chain compound 8/6 has only mono-

tropic liquid crystalline properties. On rapid cooling from the

isotropic melt, at ﬁrst the typical texture of a hexagonal

columnar phase appears, which at 50 °C immediately turns

into an isotropic phase. On heating, a direct transition into

the isotropic liquid takes place and no columnar phase can be

detected. This behaviour is analogous to that found for the

double chain glucamide 1/6 and therefore it is very likely that

the optically isotropic mesophase of this compound represents

Fig. 11 Plot of the speciﬁc conductivity k of (&) 7/8 and (+) 9/12

versus the reciprocal absolute temperature 1/T

a bicontinuous cubic phase (Cub phase). Due to the mono-

tropic character and the rapid crystallization, no X-ray investi-

gations were possible to conﬁrm the proposed cubic structure

of this phase.

V2

imental ﬁnding strongly supports the inverted micellar struc-

ture of the cubic phases of the triple chain amphiphiles under

investigation.

Because the lipophilic residues of the double chain 1,3-diol

8/6 and the related 1,2-diol 6/6 are identical, the occurrence

of a bicontinuous cubic phase instead of a columnar phase

again can be explained by the larger size of the 1,3-diol unit

of 8/6 in comparison to the 1,2-diol unit of compound 6/6.

The next question concerns the shape of these closed micelles.

Spherical, oblate and prolate shapes are under discussion for

micellar cubic phases of lyotropic systems. If one assumes the

existence of spherical micelles, than one micelle is located in

each corner of a simple cubic unit cells (see Fig. 12). Therefore,

the diameter of these micelles should be equal to the cubic

lattice parameter. In this case the diameter of the micelles

would be signiﬁcantly larger than twice the length of the single

molecules (see Table 7). This contradiction between molecular

size and cell dimensions is often observed in cubic phases.

Therefore, Fontell et al.50 suggested an alternative structure

for lyotropic micellar cubic phases located between the micellar

Investigation of the micellar cubic phases of the triple chain

amphiphiles. In order to prove the inverted micellar structure

of the cubic phases of the triple chain amphiphiles, proton

conductivity investigations have been carried out. If the cubic

phases under discussion are built up by closed inverted micelles,

then the hydrogen bonding networks between the head-groups

should be located inside the micelles and therefore they should

be isolated from each other by the lipophilic regions of the

alkyl chains. In a bicontinuous cubic phase and in the columnar

phase however, the hydrogen bonding network should be

extended over large distances. Since these hydrogen bonding

networks can act as proton conductors, the conductivity of

non-oriented samples is expected to decrease at the transition

from the hexagonal columnar to the inverted micellar cubic

mesophase. Those compounds with a columnar/cubic dimor-

phism are therefore especially useful for these investigations.

Indeed, a strong decrease of the speciﬁc conductivity is

found in all cases investigated at the transition from the

hexagonal columnar phase to the cubic phase. The dependence

of the speciﬁc conductivity k on the inverse temperature 1/T

for compounds 7/8 and 9/12 is shown in Fig. 11. This exper-

solution and the normal hexagonal phase (Cub ) of lyotropic

systems. They proposed that the cubic unit cell is built up by

I1

eight short rod-like aggregates with an axial ratio of less than

251. One of these rod-shaped micelles is placed in each corner

of the unit cell, one in the centre, and two at each surface of

the cell. The micelles centred at the corners and in the centre

should be statistically disordered or freely rotating, whereas

those at the surfaces are only rotationally disordered.50

We propose that the thermotropic cubic phases of the triple

chain compounds 3/9, 3/10, 3/12 and 7/8–7/12 have the same

structure. However, they are built up by inverted micelles and

appear in the absence of any solvent. Thus, the cubic lattice

should be built up by non-spherical micelles (short rods), each

consisting of approximately 40–50 individual molecules. In

order to organize these molecules in each of these closed

536

J. Mater. Chem., 1998, 8(3), 529–543

in a face centred lattice (0.74) which allow more eﬃcient

packing. Such arrangements have indeed been found in

lyotropic systems for some micellar cubic phases of the type

1;8 however they have never been observed for an inverted

system (see Fig. 1). Interestingly, Pm3n lattices have also been

found for thermotropic cubic phases of cone-shaped dendri-

mers.37 Here eight nearly spherical (spherical and tetrahedral

distorted) micelles were found in the cubic lattice. Because

these compounds diﬀer in chemical structure, they could not

be compared directly with the compounds described herein.

Triple chain benzamides with other hydrophilic groups. The

inﬂuence of the hydrophilic group on the mesomorphic proper-

ties is obvious from the comparison of the tridodecyloxy

benzamides 3/12, 7/12, 9/12, 10/12 and 11/12 given in Table 8.

All compounds have the same hydrophobic residue and diﬀer

only in the number of hydroxy groups and their position with

respect to each other.

It clearly shows that increasing the number of hydroxy

groups destabilizes the inverted micellar cubic mesophase in

favour of the hexagonal columnar phase. Hence, the tetraol

11/12 displays exclusively a columnar phase in contrast to the

triol 10/12 and the diols 7/12 and 9/12.

Fig. 12 Two possible models of the structure of the thermotropic

inverted micellar cubic mesophases Cub of the compounds under

discussion. The model based on rod-like closed micelles refers to a

proposal by Fontell et al. for normal micellar cubic phases in lyotropic

systems (ref. 50). (a) Arrangement of the micelles in the primitive cubic

lattice. The rod-like micelles are indicated a circles, the statistically

disordered micelles at the corners and in the centre are indicated by

black dots. (b) View upon a face of the cubic lattice. (c) Schematic

presentation of a rod-like micelle.

I2

The important inﬂuence of the position of the hydroxy

groups has already been discussed for the diols 7/12 and 9/12.

Comparing the N-methylglucamide 3/12 with the tetraol 11/12

reveals that, despite the fact that the number of hydroxy

groups of 3/12 is larger, it has a micellar cubic mesophase

whereas the tetrahydroxy compound 11/12 is only columnar.

In the case of 11/12 the connecting position is between the

four hydroxy groups. Here, all hydroxy groups are positioned

close to the hydrophilic–lipophilic interface giving rise to a

large area of the hydrophilic group at the interface. In the

open chain carbohydrate derivative 3/12 however, the lipo-

philic residue is attached to a terminal position of the polar

group. In this case, not all hydroxy groups are located directly

at this interface and therefore the hydrophilic group appears

to be smaller. This clearly shows that not only the number of

hydroxy groups but also their position in respect to the

lipophilic–hydrophilic interface is an important factor govern-

ing the hydrophilic–lipophilic interface curvature and thus the

type of mesophase. Therefore, the area at the polar–apolar

interface which is occupied by the N-methylglucamide group

is even nearly comparable with that of the 1-amidopropane-

2,3-diol group in compound 6/12. The small diameter of the

N-methylglucamido head group may be a result of the hindered

rotation about the MCH(OH)MCH(OH)M bonds which is

much more diﬃcult than that of alkyl or oxyethylene groups,

due to the larger steric interactions of OH compared to H.

Table 7 Comparison of the lattice parameter of the micellar cubic

)

mesophases (a ) and of the hexagonal columnar mesophases (a

of the compounds 3/9, 7/8, 9/12 and 10/12, which have a Cub /Col

dimorphisma

cub

hex

H2

I2

a

/nm

a

/nm

cub

hex

compound

3/9

(T /°C)

L /nm

2.7

n

d /nm

n

(T /°C)

cell

1

mic

7.93

(121)

6.89

(75)

7.99

(67)

414

340

395

40

52

42

49

4.08

(52)

3.33

(50)

4.05

(40)

7/8

2.2

3.4

4.0

10/12

2.6

aAbbreviations: L =molecular length according to CPK models

(extended all trans-conformation of the alkyl chains), n =number of

molecules in each unit cell of the cubic lattice (calculated using the

cell

equation n=V (N /M)r and assuming a density of r=1 g cm−3);

mesophase.

cell

A

n

=number of molecules in each rod-like micelle of the cubic

mic

cylindrical micelles they should have an axial ratio d /d in

the order of about 1.551.51

The proposed model (Fig. 12) requires that two micelles are

2

1

Conclusions

arranged side by side at each cell surface of the cubic lattice.

Therefore the short diameter of these rods (d ) should amount

In summary we have investigated the inﬂuence of structural

variations of amphiphilic benzamides on their thermotropic

phase behaviour. Lamellar (S ), columnar (Col ) and two

1

to not more than one half of the cubic lattice parameter a

Indeed in all investigated compounds with a Col /Cub

.

cub

H2

I2

A

H2

dimorphism the hexagonal lattice parameter of the columnar

phases amounts to approximately half the lattice parameter of

the cubic mesophase (see Table 7). Thus, in all these cases the

types of cubic mesophases (Cub

and Cub ) have been

V2

I2

detected. The same diversity of diﬀerent microstructures as

known for lyotropic lipid–water systems,1 for polycatenar

thermotropic compounds18 and for polyelectrolytes4 can be

found in the thermotropic phase sequence of these amphiphilic

polyhydroxy derivatives. In strong analogy to lyotropic systems

the type of thermotropic mesophase depends on the surface

area of the hydrophilic parts of these molecules at the hydro-

philic–lipophilic interface and the size of the lipophilic groups,

which determine the mean interface curvature. The cylindrical

aggregates of the columnar mesophase are stable over a rather

broad range of variation of the structural parameter. The

average diameter of the columns of the double chain com-

pounds is signiﬁcantly larger than that of the corresponding

triple chain compounds. This could be due to a non-circular

short diameter (d ) of the rod-like micelles in the cubic meso-

phase is nearly identical to the diameter of the columns in the

1

hexagonal columnar mesophase below. Therefrom we can

conclude that these short rod-like micelles should result from

the collapse of the extended columns of the Col phase into

H2

small segments. Probably the arrangement of eight rod-like

micelles in each unit cell of such a cubic lattice represents an

energetic minimum which could be stabilized, for example by

quadrupole interactions.50 If spherically micelles were to form,

their packing coeﬃcient in a simple cubic lattice would amount

to only 0.52. Therefore it can be expected that spherical

micelles should preferably arrange in a body centred (0.68) or

J. Mater. Chem., 1998, 8(3), 529–543

537

Table 8 Comparison of the thermotropic phase transition temperatures of the 3,4,5-tridodecyloxybenzamides 3/12, 7/12, 9/12, 10/12 and 11/12

with diﬀerent hydrophilic groupsa and enthalpy values of the phase transitions of compounds 10/12 and 11/12 (lower lines)

T/°C

DH/kJ mol−1

compound

structure

K

Col

H2

Cub

Iso

12

3/12b

$

75

—

$

185

$

7/12

$

45/69

—

$

127

$

9/12

67

$

(62)

104c

10/12

63d

65.3

$

64

1.3

87e

1.0

11/12

$

40

67.8

$

142

1.6

—

$

aAbbreviations: see Table 1. bRef. 36. cObtained by microscopic investigations. In the DSC heating cycles the phase transition occurs at 108 °C.

dOnly partial crystallization was found. eObtained by microscopic investigations, in the DSC heating cycle the phase transition was found at 93 °C.

cross section of the cylinders formed by the double chain

compounds. On introduction of the third chain, an eﬃcient

packing in circular columns becomes possible. At a certain

degree of the interface curvature however, the transition from

the hexagonal columnar to a micellar cubic mesophase takes

place. This can be found for compounds consisting of three

long aliphatic chains and a polar group with a small area at

the polar–non-polar interface. On the basis of proton conduc-

tivity measurements and from packing considerations we pro-

pose that this cubic lattice is built up by eight closed micelles

which have a rod-like shape and represent small segments of

the extended columns of a columnar mesophase.

decrease in the number of alkyl chains gives rise to a noncircu-

lar cross section of the columns. Probably there is a strong

undulation within the columns of the double chain compounds

which increases with decreasing chain length. These columns

can fuse with formation of an interwoven network structure

ordered in a three-dimensional cubic lattice. On further

decreasing the chain length, the interface curvature becomes

zero by turning into a smectic layer structure.

On increasing the alkyl chain length of appropriate triple

chain compounds, density ﬂuctuations could occur in the polar

regions of the columns leading to a disruption of the hydrogen

bonding networks within the columns with formation of short

rod-like micelles. Probably the arrangement of eight such rod-

like micelles in a primitive cubic lattice represents an energetic

minimum which allows an eﬃcient packing of the molecules.

The analogy of these thermotropic mesophases with the

inverted phases of lyotropic systems is obvious. The hydrogen

bonding networks correspond to the aqueous regions in

The transition from the cylinders of the columnar phase to

the non-curved lamellar phase occurs via bicontinuous cubic

mesophases (Cub ).

V2

Therefrom we can propose a model for the transition

between the diﬀerent mesophases. If one starts with the inverted

columnar mesophase of the triple chain compounds, the

538

J. Mater. Chem., 1998, 8(3), 529–543

Table 9 Melting temperatures of the 3,4-dialkoxybenzoic acids and

the 3,4,5-trialkoxybenzoic acids and reference values from the literature

detergent–water systems. It can therefore be assumed that all

other phases which are known from lyotropic systems1,8,10 can

also be observed in the thermotropic phase sequence of appro-

priately designed polyhydroxy amphiphiles. Furthermore the

mesomorphic organization of these compounds can be largely

inﬂuenced by addition of protic solvents.36 Because these protic

solvents are incorporated into the head group region, signiﬁ-

cant changes of the mesophase types occur. Thus the molecules

reported represent typical examples of amphotropic com-

pounds,52 which bridge the gap between the thermotropic

liquid crystalline phases of rod-like, polycatenar and disc-like

molecules on the one hand and the lyotropic mesophases of

detergent–water mixtures on the other.

mp/°C

reported

mp/°C

reported

n

found

ref.

found

ref.

4

5

6

7

8

9

146

142

130

129

123

124

127

120

Experimental section

128

127

125

124

123

121

19d

39

41

53

46

51

56

40–41

58

55

56

Techniques

Transition temperatures (given in °C throughout) were meas-

ured using a Mettler FP 82 HT hot stage and control unit in

conjunction with a Nikon Optiphot 2 polarizing microscope

and these were conﬁrmed using diﬀerential scanning calor-

imetry (Perkin-Elmer DSC-7, heating and cooling rate:

10 K min−1). The accuracy of the transition temperatures is

about 0.5 K. All phase transitions, except those of cubic and

crystalline phases, were completely reversible. If not otherwise

stated the transition enthalpies of enantiotropic phases were

obtained from the ﬁrst heating scan, those of monotropic

phases from the second heating scan. The accuracy of the

enthalpy values is about 0.2 kJ mol−1.

10

12

(Merck, silica gel 60 F 254). Measurements of the optical

rotation were carried out with a Perkin-Elmer Polarimeter 341.

Synthesis of the benzamides 1–10

The appropriately substituted benzoic acid (1.5 mmol) and

thionyl chloride (10 ml) were reﬂuxed for 3 h. The excess

thionyl chloride was distilled oﬀ and the residue was dissolved

in dry methylene chloride (15 ml). The amino alcohol

(15 mmol) was dissolved in dry dimethylformamide (30 ml)

under inert conditions and DMAP (10 mg) was added. To this

solution the benzoyl chloride dissolved in methylene chloride

was added with stirring at 80 °C. The resulting mixture was

heated at this temperature for 4 h and was stirred for additional

24 h at room temp. Afterwards the solvent was evaporated in

vacuo and the residue was puriﬁed by crystallization or by

column chromatography.

X-Ray diﬀraction patterns were obtained on a Guinier

diﬀractometer (Huber) operating with a Cu-Ka beam. The

refraction patterns were recorded with a ﬁlm camera.

Phase diagrams were established by the penetration experi-

ments and by investigation of binary mixtures. These mixtures

were investigated by optical polarizing microscopy between

crossed polarizers.

Measurements of the conductivity (AC, f=1 kHz) were

carried out on cooling the samples from the isotropic melt in

a microcapacitor (A=2 cm2, d=0.02 cm) without orientation.

1

N-(3,4-Dibutoxybenzoyl)-1-amino-1-deoxy-D-glucitol 1/4.

Synthesized from 3,4-dibutyloxybenzoic acid (0.4 g, 1.5 mmol)

Materials

Ethyl 4-hydroxybenzoate, ethyl 3,4-dihydroxybenzoate

(Aldrich), ethyl 3,4,5-trihydroxybenzoate (Fluka), 1-amino-

ethanol (Merck), 1-aminopropane-2,3-diol (Merck), 2-amino-

propane-1,3-diol (Aldrich), 2-amino-2-hydroxymethylpropane-

1,3-diol (Serva), 1-deoxy-1-methylamino--gluctitol (Aldrich),

diallylamine (Aldrich) and the 1-bromoalkanes (Merck) were

used as obtained.

The substituted carboxylic acids were obtained by etheriﬁ-

cation of ethyl 3,4-dihydroxybenzoate or ethyl 3,4,5-trihydroxy-

benzoate with alkyl bromides and potassium carbonate in

cyclohexanone,53 followed by saponiﬁcation. The resulting

alkoxybenzoic acids were puriﬁed by repeated crystallization

from methanol. The melting temperatures of the benzoic acids,

together with the reported values from the literature are

collected in Table 9.

Conﬁrmation of the structures of the products was obtained

by 1H and 13C NMR spectroscopy (Varian Gemini 200, Varian

Unity 400 and Varian Unity 500) and mass spectrometry

(Intectra GmbH, AMD 402, electron impact, 70 eV). J Values

are given in Hz throughout.

Microanalyses were performed using a CHNF-932 (Leco

Co.) elemental analyzer. Owing to the hygroscopic properties

of some compounds moisture was absorbed during sample

preparation and therefore correct combustion analyses were

not obtained for some compounds. In these cases the water

content was determined by Karl–Fischer titration54 and the

amount of absorbed water was taken into account. The purity

of all compounds was checked by thin layer chromatography

and 1-amino-1-deoxy--glucitol (2.7 g, 15 mmol). The residue

was crystallized from methanol; Yield: 0.37 g (57%), K 174 (S

A

156) Iso (found: C, 58.78; H, 7.91; N, 3.39. C H O N requires:

C, 58.73; H, 8.21; N, 3.26%); [a] 20 3.3 (c 0.3, chloroform); d

21 35

8

D

H

(200 MHz; [2H ]DMSO; 27 °C) 0.96 (6H, t, J 6, CH ),

1.44–1.49 (4H, m, CH ), 1.69–1.76 (4H, m, CH ), 3.40–3.78

(8H, m, CHOH, CH OH, CH N), 4.05 (4H, t, J 4, OCH ),

6

3

2

4.32 (2H, t, J 4, OH), 4.44 (2H, m, OH), 4.87 (1H, d, J 5,

OH), 7.0 (1H, d, J 7, H-ar), 7.44 (2H, t, J 2, H-ar), 8.2 (1H,

br, NH); d (100 MHz; [2H ]DMSO; 27 °C) 166 (CO), 151,

C

6

148, 127, 121, 113 (C-ar), 72, 69, 68, 63 (CH OH, CHOH), 68

2

(CH ), 43 (CH N), 31, 18 (CH ), 14 (CH ); m/z 429 (M+ 5%).

2

3

N-(3,4-Dipentyloxybenzoyl)-1-amino-1-deoxy-D-glucitol 1/5.

Synthesized from 3,4-dipentyloxybenzoic acid (0.4 g, 1.5 mmol)

and 1-amino-1-deoxy--glucitol (2.7 g, 15 mmol). The residue

was crystallized from methanol; Yield: 0.34 g (50%), K 172 (M

162 S 168) Iso (found: C, 60.11; H, 8.49; N, 3.02. C H O N

A

23 39 8

requires: C, 60.36; H, 8.60; N, 3.06%); [a] 30 13.5 (c=0.2,

D

chloroform); d (200 MHz; [2H ]DMSO; 27 °C) 0.88 (6H, t,

J 6, CH ), 1.32–1.48 (8H, m, CH ), 1.64–1.74 (4H, m, CH ),

H

6

3

2

3.41–3.78 (8H, m, CHOH, CH OH, CH N), 3.97 (4H, t, J 4,

OCH ), 4.30 (2H, t, J 4, OH), 4.44 (2H, dd, J 5, OH), 4.84

(1H, d, J 5, OH), 7.0 (1H, d, J 4, H-ar), 7.44 (2H, t, J 2, H-

2

ar), 8.2 (1H, t, J 5, NH); d (100 MHz; [2H ]DMSO; 27 °C)

168 (CO), 153, 149, 128, 122, 114 (C-ar), 73, 71, 70, 65 (CH OH,

C

6

2

CHOH), 68 (CH ), 41 (CH N), 30, 29, 23 (CH ), 15 (CH );

m/z 458 (M+1 100%).

2

3

J. Mater. Chem., 1998, 8(3), 529–543

539

N-(3,4-Diheptyloxybenzoyl)-1-amino-1-deoxy-

Synthesized from 3,4-diheptyloxybenzoic acid (0.5 g, 1.5 mmol)

and 1-amino-1-deoxy--glucitol (2.7 g, 15 mmol). Crystallized

twice from methanol; Yield: 0.40 g (52%), K 169 Col 203

D

-glucitol 1/7.

chloroform–ethanol, 1053) and crystallized twice from meth-

anol; Yield: 0.25 g (29%), K 68 Col 174 Iso (found: C, 64.53;

H2

H, 9.72; N, 2.17. C H O NΩ0.5H O requires: C, 64.83; H,

32 57

D

8

2

9.86; N, 2.36%); [a] 20 −5.8 (c 1, methanol); d (500 MHz;

H2

H

Iso; (found: C, 62.82; H, 8.94; N, 2.58. C H O N requires: C,

63.12; H, 9.23; N, 2.73%); [a] 20 40 (c 0.3, chloroform); d

[2H ]DMSO; 30 °C) 0.85 (6H, t, J 7, CH ), 1.25–1.43 (24H,

m, CH ), 1.65–1.72 (4H, m, CH ), 2.95 (3H, s, NCH ),

27 47

8

6

3

D

H

2

3

(500 MHz; [2H ]DMSO; 30 °C) 0.85 (6H, t, J 6, CH ),

1.26–1.45 (16H, m, CH ), 1.68–1.71 (4H, m, CH ), 3.35–3.76

(8H, m, CHOH, CH OH, CH N), 3.97 (4H, q, J 5, OCH ),

4.33 (2H, t, J 6, OH), 4.42 (1H, d, J 5, OH), 4.46 (1H, d, J 5,

OH), 4.87 (1H, d, J 5, OH), 6.96 (1H, d, J 4, H-ar), 7.42 (2H,

t, J 2, H-ar), 8.2 (1H, t, J 6, NH); d (126 MHz; [2H ]DMSO;

3.32–3.56 (8H, m, CHOH, CH OH, CH N), 3.92–3.97 (4H,

m, OCH ), 4.27–4.44 (4H, br, OH), 4.87 (1H, br, OH), 6.95

(3H, br, H-ar); d (126 MHz; [2H ]DMSO; 30 °C) 171 (CO),

149, 148, 129, 120, 113 (C-ar), 71, 70, 68, 63 (CH OH, CHOH),

6

3

2

C

6

2

68 (CH ), 31 (NCH ), 29, 25, 22 (CH ), 14 (CH ); m/z 583

(M+ 3.6%).

2

3

2

3

C

6

30 °C) 166 (CO), 151, 148, 126, 120, 112 (C-ar), 72, 69, 68, 63

(CH OH, CHOH), 68 (CH ), 31, 29, 28, 25, 22 (CH ), 14

(CH ); m/z 513 (M+ 9.3%).

N-(3,4-Dihexadecyloxybenzoyl)-1-deoxy-1-methylamino-D-

2

3

2

glucitol 2/16. Synthesized from 3,4-dihexadecyloxybenzoic acid

(0.9 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). The residue was crystallized twice from methanol;

N-(3,4-Dinonyloxybenzoyl)-1-amino-1-deoxy-

D-glucitol 1/9.

Yield: 0.60 g (51%), K 82 Col 194 Iso (found: C, 68.42; H,

10.90; N, 1,79. C H O NΩ1.5H O requires: C, 68.45; H, 10.99;

Synthesized from 3,4-dinonyloxybenzoic acid (0.6 g, 1.5 mmol)

and 1-amino-1-deoxy--glucitol (2.7 g, 15 mmol). The residue

was crystallized twice from chloroform–methanol, 1051; Yield:

H2

2

46 85

D

8

N, 1.74%); [a] 30 2.1 (c 0.6, chloroform); d (400 MHz;

H

[2H ]DMSO; 40 °C) 0.84 (6H, t, J 6, CH ), 1.22–1.42 (52H,

m, CH ), 1.67–1.70 (4H, m, CH ), 2.95 (3H, s, NCH ),

0.37 g (43%), K 166 Col 239 Iso (found: C, 65.10; H, 9.72;

6

3

H2

N, 2.31. C H O N requires: C, 65.35; H, 9.73; N, 2.46%);

[a] 20 8.9 (c 0.8, chloroform);

2

3

31 55

8

3.39–3.55 (8H, m, CHOH, CH OH, CH N), 3.92–3.97 (4H,

m, OCH ), 4.24–4.41 (4H, br, OH), 4.82 (1H, d, J 5, OH),

d

(500 MHz; [2H ]

2

D

H

6

DMSO; 30 °C) 0.85 (6H, t, J 7, CH ), 1.25–1.42 (24H, m,

CH ), 1.68–1.70 (4H, m, CH ), 3.36–3.75 (8H, m, CHOH,

CH OH, CH N), 3.98 (4H, q, J 6, OCH ), 4.25 (2H, t, J 6,

OH), 4.36 (1H, d, J 5, OH), 4.39 (1H, d, J 5, OH), 4.79 (1H,

d, J 4, OH), 6.95 (1H, d, J 9, H-ar), 7.42 (2H, br, H-ar), 8.16

(1H, s, NH); d (126 MHz; [2H ]DMSO; 30 °C) 166 (CO),

2

3

6.94 (3H, br, H-ar); d (126 MHz; [2H ]DMSO; 40 °C) 171

(CO), 149, 148, 129, 120, 113 (C-ar), 72, 71, 70, 68, 63 (CH OH,

CHOH), 31 (NCH ), 29, 25, 22, 21 (CH ), 14 (CH ); m/z 779

(M+ 0.6%).

C

6

2

3

2

3

C

6

N -(3,4,5-Trioctyloxybenzoyl)-1-deoxy-1-methylamino-D-

151, 148, 127, 120, 113 (C-ar), 72, 71, 70, 69, 68, 63 (CH OH,

2

glucitol 3/8. Synthesized from 3,4,5-trioctyloxybenzoic acid

(0.8 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). Puriﬁed by column chromatography (eluent chloro-

CHOH), 68 (CH ), 29, 25, 22 (CH ), 14 (CH ); m/z 569

(M+ 10%).

2

3

form–ethanol, 1053); Yield: 0.26 g (25%), K 75 Col 147 Iso

N -(3,4-Diheptyloxybenzoyl)- 1- deoxy- 1- methylamino-

D

-

H2

(found: C, 66.04; H, 10.11; N, 1.94. C H O NΩ0.3H O

glucitol 2/7. Synthesized from 3,4-diheptyloxybenzoic acid

(0.5 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). Puriﬁed by column chromatography (eluent chloro-

form–ethanol, 1053) and crystallization from methanol; Yield:

38 69

9

2

requires: C, 66.21; H, 10.18; N, 2.03%); [a] 20−0.5 (c 1,

methanol); d (500 MHz; [2H ]DMSO; 30 °C) 0.86 (9H, t, J

6, CH ), 1.25–1.42 (30H, m, CH ), 1.62–1.70 (6H, m, CH ),

2.94 (3H, s, NCH ), 3.30–3.48 (8H, m, CHOH, CH OH,

CH N), 3.86 (2H, t, J 6, OCH ), 3.92 (4H, t, J 6, OCH ),

4.28–4.45 (4H, br, OH), 4.88 (1H, br, OH), 6.62 (2H, br, H-

D

H

6

3

2

0.21 g (27%), K 96 M 118 (S 118) Iso (found: C, 62.62; H,

3

2

A

9.34; N, 2.47. C H O N requires: C, 62.89; H, 9.58; N, 2.72%);

[a] 20 −3.0 (c 1, methanol); d (500 MHz; [2H ]DMSO;

2

28 49

8

D

H

6

ar); d (50 MHz; [2H ]DMSO; 27 °C) 166 (CO), 152, 138, 132,

119 (C-ar), 72, 71, 68, 63 (CH OH, CHOH), 68 (CH ), 51

30 °C) 0.86 (6H, t, J 6, CH ), 1.26–1.39 (16H, m, CH ),

1.65–1.72 (4H, m, CH ), 2.95 (3H, s, NCH ), 3.30–3.56 (8H,

C

6

3

2

3

(CH N), 31 (NCH ), 30, 29, 26, 22 (CH ), 14 (CH ); m/z 683

(M+ 15%).

m, CHOH, CH OH, CH N), 3.92–3.97 (4H, m, OCH ),

4.27–4.44 (4H, br, OH), 4.86 (1H, br, OH), 6.94 (3H, br, H-

2

3

2

3

2

ar); d (126 MHz; [2H ]DMSO; 30 °C) 170 (CO), 149, 148,

129, 120, 112 (C-ar), 72, 68, 63 (CH OH, CHOH), 68 (CH ),

C

6

N-(3,4,5-Trinonyloxybenzoyl)-1-deoxy-1-methylamino-D-

2

glucitol 3/9. Synthesized from 3,4,5-trinonyloxybenzoic acid

(0.8 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). Puriﬁed by column chromatography (eluent chloro-

31 (NCH ), 29, 28, 25, 22 (CH ), 14 (CH ); m/z 527 (M+ 1.8%).

3

2

3

N - (3,4 - Dioctyloxybenzoyl) - 1 - deoxy - 1 - methylamino - D -

form–methanol, 1051); Yield: 0.16 g (15%), K 50 Col 102

Cub 143 Iso (found: C, 68.13; H, 10.67; N, 2.06. C H O N

H2

glucitol 2/8. Synthesized from 3,4-dioctyloxybenzoic acid (0.6 g,

1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). Puriﬁed by column chromatography (eluent chloro-

form–ethanol, 1053) and crystallized from methanol; Yield:

I2

41 75 9

requires: C, 67.83; H, 10.41; N, 1.93%); [a] 20 −6.1 (c 1,

D

methanol); d (200 MHz; [2H ]DMSO; 27 °C) 0.87 (9H, t, J

6, CH ), 1.28–1.71 (42H, m, CH ), 2.96 (3H, s, NCH ),

3.49–3.52 (8H, m, CHOH, CH OH, CH N), 3.87–3.98 (6H,

m, OCH ), 4.25–4.55 (4H, br, OH), 4.80–5.05 (1H, br, OH),

H

6

3

2

3

0.28 g (34%), K 87 Col 155 Iso (found: C, 63.69; H, 9.62; N,

H2

2

2.32. C H O NΩ0.5H O requires: C, 63.98; H, 9.66; N, 2.49%);

30 53

8

2

[a] 20 −5.9 (c 1, methanol); d (500 MHz; [2H ]DMSO;

6.60–6.80 (2H, br, H-ar); d (100 MHz, [2H ]DMSO, 27 °C)

166 (CO), 152, 138, 132, 103 (C-ar), 72, 71, 68, 63 (CH OH,

D

H

6

C

6

30 °C) 0.85 (6H, t, J 6, CH ), 1.25–1.43 (20H, m, CH ),

1.67–1.72 (4H, m, CH ), 2.95 (3H, s, NCH ), 3.30–3.55 (8H,

3

2

CHOH), 31 (N-CH ), 30, 29, 28, 25, 22 (CH ), 14 (CH ); m/z

725 (M+ 28.6%).

2

3

2

3

m, CHOH, CH OH, CH N), 3.92–3.97 (4H, m, OCH ),

4.27–4.45 (4H, br, OH), 4.87 (1H, br, OH), 6.95 (3H, br, H-

2

ar); d (126 MHz; [2H ]DMSO; 30 °C) 170 (CO), 149, 148,

129, 120, 113 (C-ar), 71, 68, 63 (CH OH, CHOH), 68 (CH ),

N-(3,4,5-Tridecyloxybenzoyl )-1-deoxy-1-methylamino-D -

C

6

glucitol 3/10. Synthesized from 3,4,5-tridecyloxybenzoic acid

(0.9 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). The residue was puriﬁed by chromatography (eluent

chloroform–methanol, 1051) and crystallized twice from ace-

tone; Yield: 0.19 g (15%), K 59 Col 89 Cub 158 Iso (found:

2

31 (NCH ), 29, 26, 22 (CH ), 14 (CH ); m/z 555 (M+ 2.1%).

3

2

3

N - (3,4 - Dinonyloxybenzoyl) - 1 - deoxy - 1 - methylamino - D -

glucitol 2/9. Synthesized from 3,4-dinonyloxybenzoic acid

(0.6 g, 1.5 mmol) and 1-deoxy-1-methylamino--glucitol (2.9 g,

15 mmol). Puriﬁed by columnn chromatography (eluent

H2

9

I2

C, 68.60; H, 10.54; N, 1.89. C H O N requires: C, 68.80; H,

44 81

10.63; N, 1.82%); [a] 30 −5.6 (c 1, methanol); d (200 MHz;

D

H

540

J. Mater. Chem., 1998, 8(3), 529–543

[2H ]DMSO; 27 °C) 0.87 (9H, t, J 6, CH ), 1.27–1.72 (48H,

m, CH ), 2.96 (3H, s, NCH ), 3.44–3.52 (8H, br, CHOH,

(CHOH), 69, 68 (OCH ), 64 (CH OH), 43 (CH NH), 31, 29,

25, 22 (CH ), 14 (CH ); m/z 563 (M+ 78.3%).

6

3

2

3

2

3

CH OH, CH N), 3.84–3.98 (6H, m, OCH ), 4.31–4.51 (4H,

br, OH), 4.85–5.05 (1H, br, OH), 6.60–6.76 (2H, br, H-ar); d

2

C

1-(3,4,5-Trihexyloxybenzoylamino)propane-2,3-diol

7/6.

(100 MHz, [2H ]DMSO, 27 °C) 165 (CO), 152, 138, 132, 104

(C-ar), 72, 71, 68, 63 (CH OH, CHOH), 31 (N-CH ), 30, 29,

25, 22 (CH ), 14 (CH ); m/z 767 (M+ 11.4%).

6

Synthesized from 3,4,5-trihexyloxybenzoic acid (0.6 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Puriﬁed by column chromatography (eluent: chloroform–etha-

nol 1053) followed by preparative thin layer chromatography

(Chromatotron, eluent: chloroform). Yield: 0.19 g (26%); K 49

Col 91 Iso (found: C, 67.50; H, 9.69; N, 2.78. C H O N

2

3

2

3

N-(3,5-Didodecyloxybenzoyl)-1-amino -1-deoxy-

4/12. Synthesized from 3,5-didodecyloxybenzoic acid (0.7 g,

D

-glucitol

H2

28 49

6

1.5 mmol) and 1-amino-1-deoxy--glucitol (2.7 g, 15 mmol).

Crystallized twice from methanol; Yield: 0.10 g (10%), K 45

requires: C, 67.85; H, 9.96; N, 2.83%);

d

(500 MHz,

H

[2H ]DMSO; 30 °C) 0.88 (9H, t, J 4, CH ), 1.2–1.45 (18H, m,

CH ), 1.6–1.75 (6H, m, CH ), 3.3–3.4 (5H, m, CH NH, CHOH,

CH OH), 3.85 (2H, t, J 6, OCH ), 4.0 (4H, t, J 6, OCH ),

1

6

2

3

K

87 Col 175 Iso (found: C, 67.44; H, 10.59; N, 2.0.

2

H2

C H O NΩ0.2H O requires: C, 67.59; H, 10.33; N, 2.13%);

37 67

[a] 20 2.3 (c 1, methanol); d (500 MHz; [2H ]DMSO; 30 °C)

2

8

2

4.53 (1H, t, J 6, OH), 4.75 (1H, d, J 5, OH), 7.15 (2H, s, H-

ar), 8.3 (1H, t, J 6, NH); d (126 MHz; [2H ]DMSO; 30 °C)

166 (CO), 152, 140, 129, 106 (C-ar), 72 (CHOH), 70, 68

D

H

6

0.84 (6H, t, J 6, CH ), 1.23–1.39 (36H, m, CH ), 1.65–1.69

3

2

C

6

(4H, m, CH ), 3.35–3.74 (8H, m, CHOH, CH OH, CH N),

3.95 (4H, t, J 6, OCH ), 4.32 (2H, t, J 4, OH), 4.41 (1H, d, J

5, OH), 4.46 (1H, d, J 5, OH), 4.85 (1H, d, J 5, OH), 6.56

2

(OCH ), 64 (CH OH), 43 (CH NH), 31, 30, 29, 25, 22 (CH ),

14 (CH ); m/z 495 (M+ 7.4%).

2

3

(1H, s, H-ar), 6.96 (2H, s, H-ar), 8.28 (1H, t, J 5, NH); d

C

(50 MHz; [2H ]DMSO; 27 °C) 166 (CO), 159, 136, 106, 104

6

1-(3,4,5-Triheptyloxybenzoylamino)propane-2,3-diol

7/7.

(C-ar), 72, 71, 69, 68, 63 (CH OH, CHOH), 68 (CH ), 31, 29,

2

Synthesized from 3,4,5-triheptyloxybenzoic acid (0.7 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Puriﬁed by column chromatography (eluent: chloroform–etha-

nol 1053) and by preparative thin layer chromatography

(Chromatotron, eluent: chloroform). Yield: 0.22 g (27%); K 46

Col 92 Iso (found: C, 68.97; H, 10.44; N, 2.57. C H O N

25, 22 (CH ), 14 (CH ); m/z 653 (M+ 5.0%).

2

3

1-(4-Dodecyloxybenzoylamino)propane-2,3-diol 5/12. Syn-

thesized from 4-dodecyloxybenzoic acid (0.5 g, 1.5 mmol) and

1-aminopropane-2,3-diol (1.4 g, 15 mmol). The residue was

puriﬁed twice by column chromatography (eluent: chloroform–

ethanol 1053; chloroform–methanol 1051). Yield: 0.38 g (33%);

H2

31 55

6

requires: C, 69.22; H, 10.31; N, 2.61%);

d

(500 MHz,

H

[2H ]DMSOt; 30 °C) 0.86 (9H, t, J 5, CH ), 1.2–1.45 (24H,

m, CH ), 1.6–1.75 (6H, m, CH ), 3.1–3.3, 3.5–3.7 (5H, m,

K

80 K 89 S 132 Iso (found C, 69.74; H, 9.85; N, 3.70.

6

3

1

2

A

C H O N requires: C, 69.62; H, 9.83; N, 3.69%);

22 37

(200 MHz, CDCl ; 27 °C) 0.85 (3H, t, J 6, CH ), 1.2–1.5 (18H,

m, CH ), 2.2–2.4 (2H, m, CH ), 3.1–3.2 (2H, m, OH), 3.6 (5H,

d

2

4

H

CH NH, CHOH, CH OH), 3.87 (2H, t, J 6, OCH ), 3.98 (4H,

t, J 6, OCH ), 4.52 (1H, t, J 6, OH), 4.75 (1H, d, J 5, OH),

2

3

2

7.1 (1H, s, H-ar), 8.3 (1H, t, J 6, NH); d (126 MHz;

m, CH NH, CHOH, CH OH), 3.95 (2H, t, J 6,OCH ), 6.55

C

[2H ]DMSO; 30 °C) 166 (CO), 152, 140, 129, 106 (C-ar), 72

6

2

(1H, t, J 3, NH), 6.9 (2H, d, J 2, H-ar), 7.7 (2H, d, J 2, H-ar);

(126 MHz; [2H ]DMSO; 30 °C) 166 (CO), 161, 129, 126,

114 (C-ar), 71 (CHOH), 67 (OCH ), 64 (CH OH), 43

(CHOH), 70, 68 (OCH ), 64 (CH OH), 43 (CH NH), 31, 30,

d

2

C

6

29, 28, 25, 22 (CH ), 14 (CH ); m/z 537 (M+ 81.4%).

2

3

2

(CH NH), 31, 29, 28, 25, 22 (CH ), 14 (CH ).

2

3

1-(3,4,5-Trioctyloxybenzoylamino)propane-2,3-diol

7/8.

Synthesized from 3,4,5-trioctyloxybenzoic acid (0.8 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Puriﬁed twice by column chromatography (eluent: chloroform–

ethanol, 1053; chloroform–methanol, 1051). Yield: 0.41g (47%);

K 59 Col 74 Cub 85 Iso (found: C, 70.26; H, 10.75; N, 2.30.

1-(3,4-Dihexyloxybenzoylamino)propane-2,3-diol 6/6. Syn-

thesized from 3,4-dihexyloxybenzoic acid (0.5 g, 1.5 mmol) and

1-aminopropane-2,3-diol (1.4 g, 15 mmol). The residue was

puriﬁed twice by column chromatography (eluent: chloroform–

ethanol, 1053; chloroform–methanol, 1051) and crystallized

H2

I2

C H O N requires: C, 70.41; H, 10.61; N, 2.42%); d

34 61

(500 MHz, [2H ]DMSO; 30 °C) 0.85 (9H, t, J 6, CH ), 1.2–1.35

twice from methanol. Yield: 0.22 g (24%); K 79 Col 87 Iso

6

H

H2

(found C, 65.76; H, 9.40; N, 3.20. C H O NΩ2H O requires:

6

3

22 37

5

2

(24H, m, CH ), 1.4–1.48 (6H, m, CH ), 1.6–1.65 (2H, m, CH ),

C, 65.28; H, 9.24; N, 3.47%);

d

(200 MHz, [2H ]

DMSO; 20 °C) 0.9 (6H, t, J 6, CH ), 1.25–1.5 (12H, m, CH ),

1.65–1.75 (4H, m, CH ), 3.5 (5H, m, CH NH, CHOH, CH OH,

5H), 3.9 (4H, t, J 3, OCH ), 4.6 (1H, t, OH), 4.8 (1H, d, J 5,

OH), 6.9 (1H, d, J 9, H-ar), 7.45 (2H, d, J 3, H-ar), 8.3 (1H,

2

H

6

1.7–1.75 (4H, m, CH ), 3.1–3.2, 3.3–3.4, 3.5–3.7 (m, 5H,

CH NH, CHOH, CH OH), 4.50 (1H, t, J 6, OH), 4.75 (1H,

d, J 5, OH), 7.25 (1H, s, H-ar), 8.3 (1H, t, J 6, NH); d

(126 MHz; [2H ]DMSO; 30 °C) 166 (CO),152, 140, 129, 106

(C-ar), 72 (CHOH), 70, 68 (OCH ), 64 (CH OH), 43 (CH NH),

2

3

2

C

2

6

br, NH); d (100 MHz; [2H ]DMSO; 27 °C) 166 (CO), 151,

148, 127, 121, 113, 112 (C-ar), 71 (CHOH), 69, 68 (OCH ), 63

2

C

6

31, 31, 30, 29, 25, 22 (CH ), 14 (CH ); m/z 579 (M+ 100).

2

3

2

(CH OH), 43 (CH NH), 31, 29, 25, 22 (CH ), 14 (CH ); m/z

395 (M+ 23.5%).

2

3

1-(3,4,5-Trinonyloxybenzoylamino)propane-2,3-diol

7/9.

Synthesized from 3,4,5-trinonyloxybenzoic acid (0.8 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Crystallized three times from methanol. Yield: 0.33 g (35%);

1-(3,4-Didodecyloxybenzoylamino)propane-2,3-diol

6/12.

Synthesized from 3,4-didodecyloxybenzoic acid (0.7 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Puriﬁed by column chromatography (eluent: chloroform–meth-

anol, 1051) and crystallized four times from methanol. Yield:

K 49 Cub 104 Iso (found: C, 70.76; H, 10.61; N, 2.19.

C H O NΩ0.2 H O requires: C, 71.04; H, 10.86; N, 2.24%);

I2

37 67

H

6

2

6

d (500 MHz, [2H ]DMSO; 30 °C) 0.84 (9H, t, J 7, CH ),

1.2–1.35 (30H, m, CH ), 1.4–1.48 (6H, m, CH ), 1.58–1.66

(2H, m, CH ), 1.68–1.74 (4H, m, CH ), 3.12–3.2, 3.3–3.4,

3.58–3.64 (5H, m, CH NH, CHOH, CH OH), 3.87 (2H, t, J

6, OCH ), 3.95 (4H, t, J 6, OCH ), 4.5 (1H, t, J 6, OH), 4.75

(1H, d, J 5, OH), 7.15 (2H, s, H-ar), 8.3 (1H, t, J 6, NH); d

(126 MHz; [2H ]DMSO; 30 °C) 168 (CO), 152, 140, 129, 106

(C-ar), 72 (CHOH), 71, 69 (OCH ), 64 (CH OH), 43 (CH NH),

31, 30, 29.0, 26, 22 (CH ), 14 (CH ); m/z 621 (M+ 100%).

J. Mater. Chem., 1998, 8(3), 529–543

3

0.44 g (52%); K 98 Col 148 Iso (found: C, 72.22; H, 10.97;

H2

2

N, 2.47. C H O N requires: C, 72.42; H, 10.90; N, 2.48%);

34 61

5

2

d (200 MHz, [2H ]DMSO; 27 °C) 0.9 (6H, t, J 6, CH )

1.2–1.5 (36 H, m, CH ), 1.6–1.8 (4H, m, CH ), 3.5–3.7 (5H, m,

CH NH, CHOH, CH OH), 4.0 (4H, t, J 6, OCH ), 4.6 (1H,

t, J 5, OH), 4.8 (1H, d, J 5, OH), 7.0 (1H, d, J 9, H-ar), 7.5

H

6

3

2

C

6

(2H, br, H-ar), 8.3 (1H, br, NH); d (50 MHz; [2H ]DMSO;

C

6

2

25 °C) 166 (CO), 151, 148, 127, 121, 113, 112 (C-ar), 71

2

3

541

1-(3,4,5-Tridodecyloxybenzoylamino)propane-2,3-diol 7/12.

Synthesized from 3,4,5-tridodecyloxybenzoic acid (1.0 g,

1.5 mmol) and 1-aminopropane-2,3-diol (1.4 g, 15 mmol).

Puriﬁed by chromatography (eluent: chloroform–ethanol,

1053) and crystallized twice from methanol. Yield: 0.82 g

(73%); K 45 K 69 Cub 126 Iso (found: C, 73.98; H, 11.67;

additional 24 h at room temp. Afterwards the solvent was

evaporated in vacuo and the residue was puriﬁed by column

chromatography (eluent chloroform–methanol, 1051) to give

N,N-diallyl-3,4,5-tridodecyloxybenzamide. Yield: 0.86 g (76%);

mp 32 °C. N,N-Diallyl-3,4,5-tridodecyloxybenzamide (0.75 g,

1 mmol) and N-methylmorpholine N-oxide (0.23 g of a 60%

solution in water, 2 mmol) were dissolved in acetone (20 ml).

1

2

I2

N, 1.87. C H O N requires: C, 73.85; H, 11.45; N, 1.87%);

46 85

(500 MHz, [2H ]DMSO; 40 °C) 0.84 (9H, t, J 6, CH ),

6

d

OsO (5 ml of a 0.01  solution in tert-butyl alcohol) was

added and the mixture was stirred at room temp. for 24 h.

Afterwards Na SO (5 ml of a saturated solution) was added

H

6

3

4

1.2–1.8 (CH , m, 60H), 3.35–3.65 (5H, m, CH NH, CHOH,

CH OH), 3.8–4.0 (6H, br, OCH ), 4.45 (1H, t, J 6, OH), 4.68

(1H, d, J 4, OH), 7.18 (2H, s, H-ar), 8.24 (1H, br, NH); d

(126 MHz; [2H ]DMSO; 40 °C) 166 (CO), 152, 140, 135, 129,

106 (C-ar), 72 (CH-OH), 70, 68 (OCH ), 64 (CH OH), 43

(CH NH), 31, 30, 29, 25, 22 (CH ), 14 (CH ); m/z 747

(M+ 100%).

2

3

and the resulting slurry was stirred for 2 h at 25 °C. The

mixture was ﬁltered over a silica bed. The residue was washed

twice with acetone (50 ml). The organic solutions were com-

bined and the solvent was evaporated. The residue was dis-

solved in diethyl ether, washed with water (25 ml), 5% H SO

C

6

2

3

2

4

(25 ml), saturated NaHCO solution (25 ml) and brine (25 ml).

The organic layer was dried with Na SO and the solvent was

3

2-(3,4-Dihexyloxybenzoylamino)propane-1,3-diol 8/8. Syn-

thesized from 3,4-dihexyloxybenzoic acid (0.5 g, 1.5 mmol) and

2-aminopropane-1,3-diol (1.4 g, 15 mmol). Puriﬁed by column

chromatography (eluent: chloroform–ethanol 1053) and by

preparative thin layer chromatography (Chromatotron, eluent:

chloroform). Yield: 0.35 g (59%); K 64 K 108 (Cub 50) Iso

2

4

distilled oﬀ. The residue was crystallized twice from methanol.

Yield: 0.31 g (38%); K 40 Col 142 Iso (found: C, 71.12;

H, 10.85; N, 1.68. C H O N requires: C, 71.42; H, 11.15;

N, 1.70%); d (200 MHz, [2H ]DMSO; 40 °C) 0.84 (9H,

J 6, CH ), 1.24–1.69 (60H, m, CH ), 2.47–2.51 (10H, m,

N(CH CHOHCH OH) ), 3.85–3.95 (6H, m, OCH ), 4.46 (2H,

H2

26 57

9

H

6

3

2

1

2

V2

(found: C, 66.48; H, 9.37; N, 3.37. C H O N requires: C,

22 37

66.79; H, 9.43; N, 3.54%); d (500 MHz, [2H ]DMSO; 25 °C)

2

5

br, OH),4.88 (2H, br, OH), 6.69 (2H, s, H-ar); d (50 MHz;

C

[2H ]DMSO; 40 °C) 171 (CO), 152, 132, 106 (C-ar), 69, 68, 51

6

H

6

0.87 (6H, t, J 6, CH ), 1.2–1.35 (8H, m, CH ), 1.4–1.5 (4H, m,

CH ), 1.65–1.75 (4H, m, CH ), 3.5 (5H, t, J 6, CHNH,

CH OH), 3.9–4.05 (4H, m, OCH ), 4.6 (2H, t, J 5, OH), 6.98

(1H, d, J 8, H-ar), 7.45 (2H, m, H-ar), 7.74 (1H, d, J 3, NH);

(50 MHz; [2H ]DMSO; 27 °C) 163 (CO), 151, 148, 127,

121, 103, 102 (C-ar), 69 (OCH ), 61 (CH OH), 54 (CHNH),

31, 29, 25, 22 (CH ), 13 (CH ); m/z 395 (M+ 20.7%).

3

2

[N(CH CHOHCH OH) ], 72, 41, 39, 38, 31, 30, 29, 26, 21

2

(CH ), 14 (CH ); m/z 821 (M+ 16%).

2

3

2

This

work

was

supported

by

the

Deutsche

d

C

6

Forschungsgemeinschaft and the Fonds der Chemischen

Industrie.

2

3

2-(3,4,5-Tridodecyloxybenzoylamino)propane-1,3-diol 9/12.

Synthesized from 3,4,5-tridodecyloxybenzoic acid (1.0 g,

1.5 mmol) and 2-aminopropane-1,3-diol (1.4 g, 15 mmol).

Crystallized twice from methanol. Yield: 0.65 g, (58%); K 67

(Col 62) Cub 104 Iso (found: C, 73.82; H, 11.64; N, 1.78.

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46 85

(200 MHz, [2H ]DMSO; 27 °C) 0.95 (9H, t, J 6, CH ), 1.2–1.8

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H

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64 Cub 87 Iso (found: C, 71.25; H, 10.98; N, 1.68.

I2

C H O NΩ0.6H O requires C, 71.55; H, 11.27; N, 1.78%); d

47 87

7

2

H

(500 MHz, [2H ]DMSO; 40 °C) 0.84 (9H, t, J 7, CH ), 1.2–1.45

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2 3

4.7 (3H, t, J 6, OH), 7.05 (2H, s, H-ar), 7.15 (1H, s, NH); d

2

C

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6

2

3 3

(CH ), 13 (CH ); m/z 777 (M+ 17.9%).

2

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¨

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¨

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¨

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¨

9, 527.

Paper 7/05359B; Received 24th July 1997

J. Mater. Chem., 1998, 8(3), 529–543

543

Article Doi

Tailoring thermotropic cubic mesophases: Amphiphilic polyhydroxy derivatives

DOI: 10.1039/a705359b

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Article abstract of DOI:10.1039/a705359b

Full text of DOI:10.1039/a705359b

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