Hexasubs i tuted cycLohexaπe compounds

The invention relates to hexasubs t i tuted cycLo- hexane compounds of the formula I

2 δ

Q Q wherein . _Z ¹ -(A ¹ -Z ² ) _p -A ² -R ¹ ^

Q i s and one of the groups <J is also OH and ^x i ^s

-OH or _^ SH, wherein

Z ¹ is -CO-X ¹ -, - ^-CO-, -CH _j -X ² -, -^-CH _j - or Z has one of the meanings of Z ¹ or is a sirrgle bond _. X is 0 or S,

X is 0, S, SO or S02

1 2 A and A in each case independently of one another are a 1 ,4-phenylene group which is uπsub- stituted or mono- or polysubs i tuted by halo¬ gen atoms and/or CH3 groups and/or CN groups, it also being possible for one or more CH groups to be replaced by N atoms, a 1,4- cyclohexylene group, it also being possible for one or two non-adjacent CHj groups to be replaced by -0- and/or -S-, a piperidine- 1,4-diyl group, a 1,4-bicycloC2.2.2]oc tylene group or a single bond,

_ΛΛΛΛΛ 00940 - 2 - p i s 0 o r 1 and the symbols R in each case independently of one another are alkyl with 1 to 20 C atoms, it also being possible for one or more non-adjacent CHj groups to be replaced by -0-, -S-, -CHCH3-,

-CHCN-, -CHHalogen-, -CO-, -Q-C0-, -CO-Q- aπd/or -CH=CH-, or H, F, Cl, 8r, I, OH, NH ₂ ,

COOH or CN, with the provisos that (a) R ¹ is only H, F, Cl, Br, I, OH, NHj, COQR,. C αr an alkyl group with 1 to 20 C atoms, one α-f tfre ^{; -} term — nal CH ₂ groups on the nucleus side being re.p.La;ce.c_ y .-

-0-, -S-, -Q-C0- or -C0-0-, if R is bστr e.d t'α a- cyc fc group A or A and (b) X is not N3 if all the groups . are acetoxy.

For Simplic ty, in the following "Cy" is a cyclo- hexaπe-1,2,3,4,5,6-hexayI group with six free valencies, Cyc is a trans-1,4-cyclohexyleπe group, it also being possible for one or two non-adjacent CHj groups to be replaced fay 0 and/or S, and Phe is a 1 ,4-phenyLene group, it also being possible for one or more CH groups to be replaced by N. The groups Cyc and Phe can be uπsubst tuted or laterally substituted.

Similar compounds, namely hexaalkaπoyI cyclohexaπes, are known (compare German Offeπlegungsschr ift 3,332,955; B. Kohne and K. Praefcke, Angew. Chem. £i (1984 ⁾ , 70-71; . Z. Luz, W- Poules, R. Poupko, K. Praefcke and 8. Scheuble, ^' 21st Buπseπ Colloquium, TU Berlin, September/October 1983; and German Offeπlegungsschrift 3,510,325 ⁾ . Like similar compounds, the compounds of the for¬ mula I can be used as components of discotic liquid crys¬ tal phases, in particular for displays based on the guest- host effect, the effect of deformation of aligned phases, the effect of dynamic scattering or a change in the ellip- tizatioπ of the light.

The invention was based on the object of discover¬ ing new stable liquid crystal mesogenic compounds which are suitable as components of disco ic liquid crystal

_ΛΛΛJΛ 00940 phases. This object was achieved by providing the com¬ pounds of the formula I.

It has been found that the compounds of the formula I are outstandingly suitable as components of discotic liquid crystal phases. In particular, stable discotic liquid crystal phases with a broad temperature range, which is favourably placed for elec troop i c al effects, of the mesophase and very favourable values for the dielectric anisotropy can ^' be prepared ith the aid of these compounds. The compounds of the formula I are furthermore suitable as an aπisotropic discotic matrix for spectro- scopic investigations.

Other compounds with discotic properties and their use in elec troopt i cal display elements a r s described, for example, in U.S. Patent Specifica ion 4,333,709. However, the discotic liquid crystals known for this field of use all have a relatively low value Δε for the dielectric anisotropy, since this anisotropy is to be attributed only to the anisotropy of the pol ar i zab i I i y of these molecules. Polar discotic liquid crystals of the phthalocyanine type are indeed already known from C. Piechocki and J. Simon, J. Chem. Soc, Chem. Commun. 1085 (5), 259, but the cyclo- hexaπe compounds according to the invention combine the advantages of non-polar cyclohexaπe compounds known from German Offenlegungsschr ft 3,510,325 and German Offenle- gungsschrift 3,332,955 with a permanent dipolar character. Surpr s ngly, the compounds of the formula I prove to be discotic liquid crystal compounds with in some cases very wide meso ranges and particularly favourable values of the dielectric anisotropy. The compounds of the formula I are discotic liquid crystals also with a Δε based on a permanent dipolar character, and therefore enable electro- optical display elements according to U.S. Patent Speci¬ fication 4,333,709 to be provided with substantially more favourable threshold voltages.

By providing the compounds of the formula I, the range of liquid crysta-l substances which are suitable for the preparat on of liquid crystal mixtures under various technological viewpoints is quite generally considerably

940 - « - e x t ended .

Compounds of the formula I are furthermore suit¬ able as intermediate products for the preparation of other substances which can be used as constituents of liquid crystal discotic phases.

The compounds of the formula I are colourless in the pure state and form liquid crystal esophases in a temperature range which is favourably placed for electro- optical use. They are very stable towards chemicals, heat and light.

The invention thus relates to the compounds of the formula I. The invention furthermore relates to the use of the compounds of the formula I as components of discotic Liquid crystal phases. The inven ion furthermore relates to discotic

Liquid crystal phases containing at least one compound of the formula 1 and Liquid crystal display elements contain¬ ing such phases.

The invention furthermore relates to an electro- optical display element containing a discotic Liquid crys¬ tal material which can be switched electrically between two different optical states and is enclosed between two base electrode plates, each with an electrically conductive electrode layer. Above and belo.w, Q, X, Z ¹ , Z ² , X ¹ , X ² , A ¹ ,

2 1

A , p and R have the meaning given, unless expressly indicated otherwise.

The compounds of the formula I accordingly include those of the part formulae I a to I I:

940

- 5 -

Compounds of the part formulae I a, I b, I d, I f , I k and I 1 are preferred.

Of the compounds of the formula I or part formulae I a to I k, those in which four of the groups _ have the same meaning and one of the groups . has a different mean¬ ing are particularly preferred. This group . then parti¬ cularly preferably is OH, OR or OCOR . Especially pre¬ ferred compounds are those in which this group which differs structurally from the other four groups . is directly alongside the substituent X in the formula I . 2 Particularly preferred meanings of - ⁽ A -Z ⁾ _p -A - a r e :

^' C) ^fcCH 2 ^ca 2 ^{" '} ' " -^^O- • - r

940

- 6 -

Moreover, of the cyc-lohexaπes of the formula I, those in which the substituents in each case opposite a r equatorial and in the trans-position relative to one another are preferred. This corresponds to the configur¬ ation of scyl lo-inos i tol .

In compounds of the formula I wherein one of the groups Q is OH, this OH group is preferably in the v cinal position relative to the group X. In this case, all six subs ituents on the cyclohexaπe ring, with the exception of X or the vicinal OH group, a re preferably in the equa¬ torial position. The OH group itself or the group X is preferably in the axial position. This corresponds to the configurat on of myo-inos tol. Compounds are furthermore preferred in which all substituents are equatorial.

Compounds of the formula I which have one or more asymmetric C atoms can be in the racemic or optically active form, both forms being described by formula I.

If one of the groups Q is OH or OR , preferably OH, X is preferably OH and the other groups Q are preferably alkoxy or alkaπoyloxy groups with preferably 3 to 13 C atoms. Thus, the following formulae of I k and I I are preferred

The Q substituents are preferably identical in one compound and mean alkoxy or alkanoyloxy.

The symbols R are in each case preferably iden¬ tical or different alkyl radicals in which one (oxaalkyl or alkoxy ⁾ or two ⁽ dioxaalkyl) CHj groups can also be replaced by 0 atoms. These radicals can be straight-chain or branched. Preferably, they- are straight-chain, have 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13 C atoms and accor¬ dingly are preferably propyl, butyl, pentyl, hexyl, heptyl, octyl, πoπyl, decyl, uπdecyl, dodecyl, tridecyl, propoxy, butoxy, pentoxy, hexoxy, octαxy, nonoxy, decoxy, uπdecoxy, dodecoxy, tπ ^' decoxy, 2-oxapropyl (= methoxymethyl ) ,

0940 _? '

2- (= ethoxymethy I ) or 3-oxabutyl (= 2-methoxyethyL ⁾ , 2-,

3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl or 2-, 3-, 4-, 5- or 6-oxaheptyl, and furthermore ethyl, tetradecyl, peπtadecyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanoπyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or

9-oxadecyl, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-oxaundecyI ,

2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- or 11-oxadodecy 1 , 2-,

3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-oxa tr idecyI ,

2,4-dioxapenty1 , 2,4-, 2,5- or 3,5-d ioxahexyI or 2,4-, 2,5-, 2,6-, 3,5-, 3,6- or 4,6-di oxahepty I .

Compounds of the formulae I with branched groups 1 R can occasionally be of importance in the customary liquid crystal base materials because of a better solubil¬ ity, but in particular as chiral doping substances, if they are optically active. Branched groups of this type as a rule contain not more than one chain branching. P r e-

* * ferred branched radicals R contain a -CHCH-∑-, -CHCN- or -CHHalogen group and are preferably 2-butyl (= 1-methyl- propyl), isobutyl (= 2-methyIpropy L ⁾ , 2-methyLbutyI , iso- pentyl (= 3-methyIbutyl ) , 2-me thylpeήtyI , 3-methylpeπty L ,

2-ethyI hexyL , 2-propyI pentyL , 2-octyl, isopropoxy, 2-mechyl- propoxy, 2-methylbutoxy, 3-methyLbutoxy, 2-methyLpentoxy, 3-methy lpentoxy,.2-ethyI hexoxy, 1-methyIhexoxy, 2-oxa-3- ethylbutyl, 3-oxa-4-methy LpentyI , 2-octyloxy, 2-chloro- prop ionyloxy, 2-chloro-3-methyLbutyryloxy, 2-chloro-4- methyLvaleryloxy, 2-chloro-3-methyIvaleryloxy, 2-methyl- 3-oxy-peπtyl or 2-methyl-3-oxa-hexyl .

Of the compounds of the formulae I and I a to I j, those in which at least one of the possible radicals has one of the preferred meanings given are preferred.

The compounds of the formula I are prepared by methods which are known per se, such as are described in the Literature (for example in the standard works such, as Houben-Weyl, Methoden ^" der Organischeπ Chemie (Methods of Organic Chemistry), Georg-Th ie e-Verlag, Stuttgart), and in particular under reaction conditions which are known and suitable for the reactions mentioned. It is also possible thereby to use variants which are known per se and are not mentioned in more detail here.

The starting substances are either known or they can be prepared without difficulty by methods which are known per se, analogously to known compounds. If desired, they can also be formed in situ such that they a re not isolated from the reaction ixture but a r e mmediately reacted further to give the compounds of the formula -I.

Ethers of the formula I (wherein, for example, at least one of the groups Z aπd ^' Z is -G-CHj- or -CHj-Q- ⁾ are obtainable by ether if icat ion of corresponding hydroxy compounds, the hydroxy compound advantageously being irst converted into a corresponding metal deriva ive, for example into the corresponding alkali metal alcoholate or alkali metal pheπolate by treatment with NaH, Na_H ₂ , NaOH, KOH, Na2Cθ3 or K2 O3. This can then be reacted with the cor- responding alkyl halide or sulfoπate or dialkyl sulfate, advantageously in an inert solvent, such as acetone, 1,2- dimethoxyethane, dimethylformamide ⁽ DMF ⁾ or di ethylsulf- oxide, or an excess of aqueous or aqueous-alcoholic NaOH or KOH, at temperatures between about 20° and 100° _* Esters of the formula I wherein, for example, at least one of the groups Z and Z is -Q-CO- or -CO-0- can be obtained by esteri fi cation of corresponding carboxy- l c ac ds.

Instead of the carboxylic acids and/or alcohols, their reactive derivatives can also be used.

Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, above all the chlorides and bromides, and furthermore the anhy¬ drides, for example also mixed anhydrides, azides or esters, in particular alkyl esters with 1 - 4 C atoms in the alkyl group. Possible reactive derivatives of the alcohols men¬ tioned are, in particular, the corresponding metal alcohol- ates, wherein the OH group ⁽ s ⁾ is replaced by OM groupCs) and wherein M denotes one equivalent of a metal, prefer- ably an alkali metal, such as Na or K.

The esterif ication is advantageously carried out in the presence of an inert solvent. Particularly su t¬ able solvents are ethers, such as diethyl ether, di-n- butyl ether, tetrahydrofuraπ, dioxaπe or anisoLe, ketoπes,

09 _. - - such as acetone, butanoπe or cyc lohexaπoπe, amides, such as d imethyI formam ide or phosphoric acid hexa ethyI tr i am i de, hydrocarbons, such as benzene, toluene or xylene, halogeno- hydrocarboπs, such as carbon tetrachlor ide or tetrachloro- ethylene, sulfoxides, such as di ethylsulfoxide or sulfo- lane, and carboxylic acids, such as tr i f I uoroace i c acid. Wa er-immisc ibIe solvents can advantageously be used simul¬ taneously for azeotropic removal, by distillation, of the water formed during the este i f icat ion. An excess of an organic base, for example pyridine, quiπoliπe or triethyl- amiπe, can occasionally also be used as the solvent for the es ter i f i c a ion . The es er i f i c a t i on can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate. The reaction temperature is usually between -50° and

+250°, preferably between -20° and +80°. At these tempera¬ tures, the es ter i f i cat ion reactions are as a rule ended after 15 inutes to 48 hours.

In detail, the reaction conditions for th.e esteri- ficatioπ depend largely on the nature of the starting sub¬ stances used. Thus, a free carboxylic acid is as a rule reacted with a free alcohol in the presence of a strong . acid, for .example a mineral acid, such as hydrochloric acid or sulfuric acid. A preferred reaction procedure is the reaction of an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in a basic medium, bases which are of importance being, in particular, alkali metal hydro ides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates or bi carbonates, such as sodium carbonate, sodi m bicarbonate, potassium carbon¬ ate or potassium bicarbonate, alkali metal acetates, such as sodium acetate or potassium acetate, alkaline earth me al hydroxides, such as calcium hydroxide, or organic bases, such as tr iethylamine, pyridine, lutidine, collidiπe or quinoline. Another preferred embodiment of the esteri- fication comprises a procedure in which the alcohol is first converted into the sodium alcoholate or potassium alcoholate, for example by treatment with ethanolic sodium hydroxide solution or potassium hydroxide solution, this

alcoholate is isolated and susp -ndβ TΠ ace one or di*thyl ether together with sodium bicarbonate or potassium carbon¬ ate, with stirring, and a solution of the acid chloride or anhydride -in diethyl ether, acetone or dimethylforma ide is added to this suspension, advantageously at tempera¬ tures between about -25° and +20°.

T ioethers of the formula I wherein at Least one of the groups and Z is -S-CHj- or -CHj-S- can be prepared, for example, by reacting a corresponding mesyl- ate, tr ifluoromesylate, tosylate or halogen compound (pre¬ ferably in the configuration of myo-inositol) ith a cor¬ responding thiol or - preferably - one of its sal.ts, in particular the corresponding Na thiolate. This reaction can be carried out in the presence or absence of an inert solvent, and in particular at temperatures between about -20 and 250°, preferably between 10 and 150°. Examples of suitable solvents are hydrocarbons, such as benzene, toluene, xylenes or mesitylenes; tertiary bases, such as triethylamine, pyridine or picoliπes; alcohols, such as ethanol, ethaπol or butanol; glycols and glycol ethers, such as ethyleπe glycol, diethyleπe glycol and 2-methoxy- ethaπol; ketoπes, such as acetone; ethers, such as tetrahydrofuran or dioxaπe; amides, such as dimethyl- formamide or phosphoric acid hexamethyl tr a ide (HMPT); or sulfoxides, such as di ethylsulfox ide. Mixtures of these solvents are also suitable. Vicinai cis-dioles of the formula I can be prepared f.e. by protecting two vicinal cis-OH-groups of the myo-inositol as a cyclic ketal, f.e. a cyclohexylidene ketal, followed by derivating the free OH-grups by one or more of the above mentioned methods and cleaving the ketal.

The discotic liquid crystal phases according to the invention consist of 2 to 25, preferably 3 to 12, com¬ ponents, at least one of which is a compound of the for¬ mula I. The other constituents are preferably selected from the known discotic liquid crystal substances, in par¬ ticular from the classes of hexasubsti tuted benzene or tri- pheπylene derivatives. The phases according to the inven¬ tion contain about 0.1 to 100, preferably 10 to 100 % of one or more compounds of the formula I. The discotic liquid crystal phases according to the invention are prepared in a manner which is customary per se. As a rule, the components are dissolved in one

940 . „ _

The discotic Liquid crystal phases according to the invention can furthermore be modified by suitable additives. For example, it is possible to add conductive salts to improve the conductivity, pleochroic dyestuffs or substances for modif ing the dielectric, anisotropy, the viscosity and/or the orientation of the discotic phases.

Surprisingly, the compounds of the formula I also form lyotropic phases and are therefore outstandingly suit¬ able for the preparation of aπisotropic polymer materials by polymerization of polymer i zabIe compounds, and in parti¬ cular the polymerization is carried out in the presence of at Least one compound of the formula I which produces lyo- trop i c phases .

Aπisotropic polymer materials are suitable, for example, as optical media in electronics.

Suitable polymer i zable compounds are both mono- or polyfunc ionaL ly ethylen i cal Ly uπsaturated monomers, oligo¬ mers or prepoly ers, or mixtures thereof, which are cap¬ able of polymerization which can be initiated by free radi- cals, and di- or polyfunct ionaL monomers, oligomers or pre¬ polymers, or mixtures thereof, wh i ch can be subjected to polycondensation or polyaddition. The prior art offers a wide selection of suitable compounds here.

Examples of suitable ethylen i cal Ly unsaturated com- pounds are ethylene, propylene, butene, isobutylene, buta¬ diene, isoprene, vinyl chloride, vinylideπe chloride, acrylonitrile, ethacryloπitrile, acryla ide, methacryl- amide, methyl, ethyl, π- or tert.-butyl, cyclohexyl, 2- ethylhexyl, benzyl, pheπoxyethyI , hydroxyethyI , hydroxy- propyl, lower alkoxyethyl or tetrahydrofurfuryl acrylate or ethacrylate, vinyl acetate, propionate, acrylate or succinate, N-viπylpyrrol idoπe, N-viπyI carbazole, styrene, divinylbeπzene, substituted styreπes and mixtures of such unsaturated compounds. Polyuπsaturated compounds, such as, for example, ethylene diacrylate, 1,6-hexanediol di- acrylate and propoxylated bispheπoL A diacrylate and di- methacryLate, can also be used in the process according to the invention. Ethylenical Ly uπsaturated compounds can be polymerized by free radicals, ioπically or by means of

metal complexes.

The free radicals required to initiate the poly¬ merization can be formed in various ways, thus, for example, by irradiation of the monomer with UV light, X-rays _, or radioactive radiation sources.

Sunlight or artificial lamps can be used as radi¬ ation sources. Advantageous examples are high pressure, medium pressure or low pressure mercury vapour lamps and xenon and tungsten lamps; laser light sources and electron beam tubes can also be used.

A chain start for the polymerization reaction is furthermore possible by disintegration of material initi¬ ators by warming or irradiation. Examples of suitable initiators are dibeπzoyl peroxide, azo-b s-i sobutyroπ tri Le, potassium persulfate, cumeπe hydroperox ide or di-tert.- butyl peroxide.

Orgaπα-alkal i metal compounds, such as pheπyl- lithiu , naphthaleπesod ium or sodium ethylate, or Lewis acids, such as boron trifluoride, aluminium chloride or tin tetrachlor de, for example, are suitable for triggering off a polymerization initiated ionically.

Finally, ethyleπically unsaturated compounds can also be polymerized by means of metal complexes. Examples of complexes which are suitable for this are those of aluminium or titanium (Ziegler-Natta catalysts).

The expression "polymerization" is to be under¬ stood in the broadest sense. It includes, for example, further polymerizat on or crosslinking of polymeric mate¬ rials, for example of prepoly ers, and homo-, co- and ter- polymerization of simple monomers.

It is not necessary for the compounds of the for¬ mula I used already to form lyotropic phases with the polymer zable compounds. Rather, the ability to form lyo¬ tropic phases can also first manifest itself in a "quasi- lyotropic" order of the polymer phase.

The polymer zat on reaction is easy to carry out. The polymer zation is carried out in the manner described above, for example by heating, irradiation or addition .of an initiator, by simply dissolving or stirring in resulting

, _ΛΛΛ ^ _{Λ 1 .} 00940 ~ 1 - ' ' mixtures of polymer i zabl e compounds and compounds which produce lyotropic phases. The polymerization can also be carried out in the presence of a non-polymerizing solvent. Suitable solvents are in principle all the lipophilic sol- vents, for example diet, yl ether, te rahydrofuran or di- oxane, or hydrocarbons, such as benzene, toluene or xyleπe.

The ratio of pol ymer i zabl e compounds to the com¬ pounds which produce lyotropic phases can be varied within wide limits. Usually, about 0.1 to 80 %, preferably 0.5 to 50 % and in particular 1 to 15 % of compounds which pro¬ duce Lyotropic phases is added.

The aπisotropic polymer materials thus obtained are distinguished by advantageous values of optical, magnetic and/or electric anisotropy and by advantageous mechanical, for example elastic or plastic, and/or thermal proper ties.

Because of their typical polymer properties, -such as the ability to form Layers, films and fibres, and their easy shaping, the anisotropic polyme . mater ials according to the invention open up diverse possible uses.

The following examples are intended to illustrate the invention,, without limiting it. m. = melting point, c. = clear point. Above and below, percentage data are percentages by weight; all the temperatures are given in degrees Celcius. "Customary working up" means: water is added, the mixture is extracted with methyleπe chloride, the organic phase is separated off, dried and evaporated and the product is purified by crystallization and/or chro atography . Example 1

A mixture of 450 g of N-acetyl-1-am i no- 1-deoxy- scyl Lo-inos i tol (obtainable from penta-0-acetyl-1-az ido- 1-deoxy-scyL lo-inos i ol (T. Sua i et al., Bull. Soc. Jap. 39 (1966), 170) via N-acetyl-penta-0-acetyl-1-amiπo-1- deoxy-scyllo-iπos i ol and hydrolysis thereof with 6N hydrochloric acid), 25 ml of pyridine and 2.15 g of n-hexa- πoyl chloride is heated at 50° for 6 hours,, with stirring. Customary working up give-s N-acetyl-penta-0-hexanoy1-1- amino-1-deoxy-scyl Lo-inos i tol , m. 76°, c. 192°.

. .

The following compounds are prepared analogously: N-acetyl-peπta-Q-propioπyL-1-amiπo-1-deoxy-scyllo- iπos i toI

N-acetyl-peπta-Q-butyryl-1-a iπo-1-deoxy-scyl lo-inos i tol N-acetyl-peπta-0-isobutyryL-1-a ino-1-deoxy-scyllo- inos i toI

N-ace yl-pen a-0-valeryl-1-amiπo-1-deoxy-scyllo-inosi ol N-acetyl-peπta-0-heptaπoyl-1-a_ino-1-deoxy-scyllo- iπos i toI N-acetyL-peπta-0-octanoyl-1-a iπo-1-deoxy-scyLlo-iπosi oL N-acetyl-peπta-Q-πoπaπoyl-1-a iπσ-1-deoxy-scyllα-iπαs o. N-acetyl-peπta-0-decaπoyL-1-a iπo-1-deoxy-scylLo-iπositoL N-acetyl-penta-0-undecaπoyL-1-a i no-1-deoxy-scyl Lo- inosι tol N-acetyl-penta-Q-dodecanoyl-1-amino-1-deoxy-scyl lo- inos i tol Example 2:

A mixture of 1.08 g of scyllo-iπosamine hydro- chloride (H.E. Carter et al., J. Biol. Chem. 175 (1948), 683) is reacted with 5.36 g o.f π-hexaπoyl chloride as described in Example 1. N-Hexaπoyl-peπta-Q-hexaπoyl.-1- amino-1-deoxy-scylLo-inos i tol , m. 34.8°, c. 259°, is obtained.

The following compounds are prepared analogously:. N-propioπyl-penta-0-valeryl-1-amiπo-1-deoxy-scyL lo- inos i tol

N-propiσnyl-peπta-Q-heptaπoyl-1-a πo-1-deoxy-scylLo- inos i tol N-prop onyl-peπta-Q-πoπaπoyl-1-amino-1-deoxy-scyllo- iπos tol

N-prop ionyI-penta-0-decanoyl-1-amino-1-deoxy-scyI lo- inos i tol

N-butyryl-penta-O-valer l—1-a no-1-deoxy-scyl lo-inos i tol N-butyryl-peπta-Q-heptaπoyl-1-am πo-1-deoxy-scyllo-iπositol N-butyryl-peπta-0-πonanoyl-1-amiπo-1-deoxy-scyl Lo-inos itoL N-butyryl-peπta-0-decanoyl-1-amiπo-1-deoxy-scyl lo-inos i tol

N-valeryl-penta-Q-heptanoyl-1-amino-1-deoxy-scyllo-iπosi tol

094* - 15 -

N-valeryl-peπta-Q-πoπanoyl-1-amino-1-deoxy-scyllo-inos itol N-valeryl-penta-Q-decaπoyL-1-amiπo-1-deoxy-scylLo-inositol

N-heptaπoyl-peπta-0-valeryL-1-a ino-1-deoxy-scyllo-inositoL N-heptanoyl-peπta-Q-heptaπoyl-1-a_ino-1-deoxy-scyllo- iπos i tol

N-heptaπoyl -pen a-0-πonanoy1-1 -a i no- 1-deoxy-scyI Lo- inos i tol

N-heptaπoyl-peπta-0-decaπoyl-1-amino-1-deoxy-scyl lo- inos i toL

N-nonanoyl-penta- ^Q -valeryl-1-amiπo ^' -1-deoxy-scyllo-iπos i tol N-noπanoyl-peπta-0-heptaπoyl-1-amino-1-deoxy-scyll"o- iπos i tol

N-πoπaπoyL-penta-Q-nonaπoyl-1-amiπo-1-deoxy-scyl lo- inos i toL N-nonaπoyl-peπta-Q-decaπoyl-1-amiπo-1-deoxy-scyllo- inos i toI

N-decanoyl-peπta-Q-valeryl-1-amiπo-1-deoxy-scyllo-iπos itol N-decaπoyl-peπta-0-heptanoyl-1-amiπo-1-deoxy-scyl Lo- inos i toL N-decaπoyl -pen ta-0-πonanoyl-1-amiπo-1-deoxy-scyl Lo- inos i tol

N-decanoyl-penta-0-decanoyl-1-amino-1-deoxy-scyl lo- inos i tol .

Example 3 A mixture of 600 mg of 1-azido-1-deoxy-scyI Lo- inositoL ⁽ obtainable from peπta-0-acetyl-1-az ido-l-deoxy- scyl Lo-i πos i tol by reaction with CH3OH/NH3), 30 ml of pyridine and 2.8 g of n-hexaπoyl chloride is stirred at 50° for 6 hours. Customary working up gives penta-0- hexaπoyl-1-az ido-1-deoxy-scyI lo-inos i tol , m. below room temperature, c. 152°.

The following compounds are prepared analogously: penta-Q-propioπyl-1-azido-1-deoxy-scyllo-inositol peπta-0-butyryl-1-azido-1-deoxy-scyl lo-inos i tol peπta-0-valeryL-1-azido-1-deoxy-scyl Lo-inos i tol

peπta-0-heptaπoyl-1-azido-1-deoxy-scyl lo-inos itoL peπta-0-octaπoyl-1-azido-1-deoxy-scyl Lo-inos i tol peπta-Q-πoπanoyl-1-azido-1-deoxy-scyllo-inosi ol penta-0-decaπoyL-1-azido-1-deoxy-scyL Lo-inos i tol peπta-0-undecaπoyl-l-azido-1-deoxy-scyllo-iπos itol peπta-Q-dodecanoyl-1-azido-1-deoxy-scyllo-inositol

Examp.le 4

A mixture of 14.95 g of 1 ,2-Q-cyc LohexyI ideπe-

3,4,5,6-tetra-Q-hexyl-myo-inos itol , 350 ml of glacial acetic acid and 90 ml of H2O is heated at 1Q& ^σ far

4 hours. After the solvent has been d i st iLle . α f> ^ttte. ^™ oiLy residue is purified by column chro a σg-raphy on sitica gel (600 ml) with CHCI3 as the elutiπg agent. A pale yellow oil is formed and after drying under 0.1 mm Hg soli— difies to a highly viscous discotic mass: 3,4,5,6-tetra-

0-hexyl-myo-i πos i ol, c. 35-36°.

The following compounds are prepared analogously:

3,4,5,6-tetra-O-butyl-myo-iπos tol

3,4,5,6-tetra-Q-peπtyl-myo-iπos i tol 3,4,5,6-tetra-O-heptyl-myo-inos tol

3,4,5,6-tetra-O-octyl-myo-inositol

3,4,5,6-tetra-Q-πoπyl-myo-inositoL

3,4,5,6-tetra-O-decyl-myo-inositoL

3,4,5,6-tetra-Q-undecyl-myo-inos itol 3,4,5,6-tetra-O-dodecyl-myo-iπositoL

3,4,5,6-tetra-O-tr decyl-myo-iπositol

3,4,5,6-tetra-0-butyryl-myo-iπositol

3,4,5,6-tetra-O-peπtaπoyL-myo-iπositol

3,4,5,6-tetra-O-hexanoyl-myo-inos i toL , m. 120-122° 3,4,5,6-tetra-G-octaπoyl-myo-inos itol

3,4,5,6-tetra-O-nonanoyl-myo-inositol

3,4,5,6-tetra-0-decanoyl-myo-iπosi tol

3,4,5,6-tetra-0-undecaπo l-rayo-iπos tol

3,4,5,6-tet a-Q-dodecano I-my0-inos i tol 3,4,5,6-tetra-Q-tr decaπoyl-myo-iπositol

Example 5

A mixture of 2.6 g (4 mmol) l,2-0-cyclohexylidene-3,4,5,6- tetra-O-hexanoyl-myo-inositol (obtainable from myo-inositol by reaction with cyclohexanone to form a cyclic ketal with two cis-OH-groups from the myo-inositol and esterification of the 4 free OH-groups with n-hexanoyl chloride/pyridine) and 20 ml acetic acid (80 %) is heated for 4 hours at 100 °C. A colourless solid is formed after usual working up and column chromatography on 300 ml of silica gel with petrolether (30°-70°C) ethyl acetate 2:1 as the eluting agent: 3,4,5,6-tetra-O-hexanoyl-myo-inositol, m. 120°-122°C.

Characteristic spectroscopic data:

IR(CHC1 ₃ ): 1745 cm ^"1 (C=0)

^■ hi-NMR (Bruker W 400, DMSO-d6) : δ = 5.54 (d, 2-OH); 5.14 ppm (d, 1-OH) .

¹³ C- MR (Bruker WM 270, Off-Resonance, CDC1 ₃ ): δ = 174.19, 172.61, 172.53 and 172.41 (4s, all C=0); 72.61, 70.89, 70.73, 70.46, 70.13 and 69.23 ppm (6d, all ring-CH). MS (170 °C): m/z-572 (M ⁺ , « 1 %); 99 (100 %).

Example 6

A mixture of 14.95 g (25 mmol) 1,2-O-cyclohexylidene- 3,4,5,6-tetra-O-hexyl-myo-inositol [obtainable from 1,2-O-cyclohexylidene-myo-inositol (Example 5) by esterification with n-hexyl bromide/potassium hydroxide] and 350 ml glacial acetic acid/90 ml water is heated for 4 hours at 100 °C. A colourless highly viscous mass is formed after usual working up and column chromatography on 600 ml of silica gel with chloroform as eluting agent: 3,4,5,6-tetra-O-hexyl-myo-inositol.

- 1 8 -

_Ch aracteristic spectroscopic data:

IR(CHC1 ₃ ): 3590 cm ^"1 (OH)

-' ^• H- MR (Bruker WM 400, DMSO-d6): δ = 4.5 (d, 2-OH); 4.51 ppm (d, 1-OH) . ¹³ C-NMR (Bruker AM 270, Off-Resonance, CDC1 ₃ ): δ = 83.32, 81.45, 80.91, 80.59, 71.70 and 68.84 (6d, all ring-CH); 73.97, 73.80, 73.75 and 71.02 ppm (4t, all 0-CH ₂ ) . MS (175 °C): m/z=516 (M ⁺ , « 1 %); 241 and 157 (100 % ) .

Example 7

607 mg (1 mmol) 2-0-benzyl-3,4,5,6-tetra-O-hexyl-scyllo- inositol [obtainable from 3,4,5,6-tetra-O-hexyl-myo- inositol (Example 6) by esterification of the equatorial OH-group with benzyl chloride/potassium hydroxide] and isomerisaton of the axial OH-group by reaction with methanesulfonyl chloride to form the mesylate, followed by substituation with a hydroxide ion via potassium superoxide/18-crown-6] is dissolved in 20 ml glacial acetic acid and hydrogenated with Pd-catalyst (10 % Pd/C) for 24 hours at room temperature and at 4 bar. A colour- less highly viscous mass is formed after usual working up and column chromatography on 150 ml of silica gel with chloroform/ethyl acetate 15:1 as the eluting agent: 3,4,5,6-tetra-O-hexyl-scyllo-inositol.

Characteristic spectroscopic data:

IR(CHC1 ₃ ): 3600 cm ^"1 (OH).

^■ " ^■ H-NMR (Bruker WM 400, DMSO-d6): δ = 4.72 ppm (2d, 1- and

2-OH);

¹³ C-NMR (Bruker AM 270, off-Resonance, CDC1 ₃ ): δ = 83.14,

82.33 and 73.61 (3d, intensity in the ratio of 1:1:1, all ring-CH); 73.88 and 73.73 ppm (2t, intensity in the ratio of 1:1, all 0-CH ₂ ).

MS (145 °C): m/z=516 (M ⁺ , < 1 %); 241 and 157 (100 %) .

Example 8

A mixture of 8.79 g (17 mmol) 3,4,5,6-tetra-O-hexyl-myo- inositol (Example 6), 4.2 g (25.4 mmol) n-hexyl bromide, 48 g potassium hydroxide powder and 300 ml benzene is heated for 7 hours under reflux. A pale yellow oil is formed after usual working up and column chromatography on 300 ml of silica gel with heptane/ethyl acetate 10:1 as eluting agent: 1,3,4,5,6-penta-o-hexyl-myo-inositol, insoluble in DMSO.

Characteristic spectroscopic data:

IR(CHC1 ₃ ): 3550 cm ^"1 (OH)

¹³ C-NMR (Bruker AM 270, Off-Resonance, CDC1 ₃ ): δ = 83.18, 80.86, 80.46 and 67.29 (4d, intensity in the ratio of 1:2:2:1, all ring-CH); 74.03, 73.88 and 71.08 ppm (3t, intensity in the ratio of 1:2:2, all 0-CH ₂ ). MS (100 °C): m/z=600 (M ⁺ , < 1 %); 254, 241 and 85 (100 %)

Example 9

A mixture of 3.4 mg (5 mmol) 2-0-methanesulfonyl-l,3,4,5,6- penta-O-hexyl-myo-inositol [obtainable from 1,3,4,5,6- penta-O-hexyl-myo-inositol (Example 8) by reaction with methanesulfonyl chloride in pyridine] and 20 ml dry dimethylsulfoxide is added to a mixture of 1.07 g (15 mmol) potassium superoxide, 0.4 g (1.5 mmol) 18-crown-6 and 30 ml dry dimethylsulfoxide with stirring at room temperature. The mixture is stirred for 70 hours at room temperature excluding moisture. A colourless oil is obtained after pouring into ice water, usual working up and column chromatography on 300 ml of silica gel with heptane/ethyl acetate 10:1 as the eluting agent: 2,3,4,5,6- penta-O-hexyl-scyllo-inositol, insoluble in DMSO.

4

Characteristic spectroscopic data:

IR(CHC1 ₃ ): 3550 cm ^"1 (OH).

¹³ C-NMR (Bruker AM 270, off-Resonance, CDC1 ₃ ): δ = 83.23,

82.84 and 82.25 (3d, intensity in the ratio of 1:2:2, all ring-CH); 74.08, 73.89 and 73.67 ppm (3t, intensity in the ratio of 1:2:2, all 0-CH ₂ ).

MS (160 °C): m/z=600. (M ⁺ , 1 %); 241 (100 %) .

Example 10

A solution of 1.75 mg (17.5 mmol) chromium trioxide in 350 ml glacial acetic acid is stirred and heated to

100 °C. A mixture of 3.0 g (5 mmol) 1,3,4,5,6-penta-O- hexyl-myo-inositol (Example 8) and 50 ml glacial acetic acid is added dropwise to this solution. The mixture is stirred at 100 ^* °C for 2 hours and then evaporated. A pale yellow oil is obtained after stirring the residue with 20 g potassium carbonate and 200 ml water, usual working up and column chromatography on 300 ml of silica gel with heptane/ethyl acetate 15:1 as the eluting agent: penta-O-hexyl-myo-inositose, m. 7 °C.

Characteristic spectroscopic data:

IR(CHC1 ₃ ): 1735 cm ^"1 (C=0).

¹³ C-NMR (Varian CFT 20, Off-Resonance, CDC1 ₃ ): δ = 202.96 ⁽ C=0 85.04, 82.62 and 81.60 (3d, intensity in the ratio of 2:1:2, all ring-CH); 74.39, 74.17 and 72.22 ppm (3t, intensity in the ratio of 1:2:2, all 0-CH ₂ ).

MS (120 °C): m/z=598 (M ⁺ , 8 %); 56 (100 %) .

094

Example 11

A mixture of 5.77 g of 1 ,3,4, 5 ,6-ρeπ a-0-hex L -

2-0-mesyl-myo-iπositoL, 1.7 g of sodium azide, 144 ml of 2-methoxy-ethanol and 26 ml of H2Q is heated at 130° (bath temperature) for 72 hours, with stirring. After the solvent has been distilled off, the oily residue is puri¬ fied by column chromatography on silica gel (300 ml ⁾ with heptane/ethyl acetate 15:1 as the mobile phase. An almost colourless oil is obtained and solidifies after drying under 0.1 mm Hg to give a cloudy discotic mass: 1-azido- 1-deoxy-2,3,4,5,6-penta-0-hexyl-scyI lo-inos i tol , c. 32.7°. The following compounds were prepared analogously: -azido-1-deoxy-2,3,4,5,6-penta-0-butyl-scyllo-inositol -azido-1-deoxy-2,3,4,5,6-penta-0-peπt l-sc llo-iπositol -azido-1-deoxy-2,3,4,5,6-peπta-0-heptyl-scyllo-inositol -azido-1-deoxy-2,3,4,5,6-peπta-Q-octyl-scylLo-iπositol -azido-1-deoxy-2,3,4,5,6-peπta-0-πonyl-scyl Lo-inos itol -azido-1-deoxy-2,3,4,5,6-penta-0-decyl-scyllo-inositol -azido-1-deoxy-2,3,4,5,6-peπta-Q-uπdecyl-scyl lo-inos itol -az ido-1-deoxy-2,3,4,5,6-penta-Q-dodecyl-scyL lo-iπositoL -az i-do-1-deoxy-2,3,4,5,6-penta-0-tr idecyl-scyl lo-inos itol -azido-1-deoxy-2,3,4,5,6-peπta-Q-butyryl-scyllo-iπσsitol -az ido-1-deoxy-2,3,4,5, -peπta-0-pentanoyl-scyL lo-inos itol

-azido-1-deoxy-2,3,4,5,6-penta-Q-hexanoyl-scyllo-inositol

-azido-1-d.eoxy-2,3,4,5,6-peπta-Q-octanoyl-scyllo-inosi ol

-azido-1-deoxy-2,3,4,5,6-penta-Q-nonanoyl-scyllo-inositoL

-azido-1-deoxy-2,3,4,5,6-peπta-0-decaπoyl-scyllo-inosit ol

-azido-1-deoxy-2,3,4,5,6-peπta-0-undecaπoyl-scyllo- πos i tol

-azi o-1-deoxy-2,3,4,5,6-peπta-0-dodecanoyl-scyllo- nos i toL

-az ido-1-deoxy-2,3,4,5,6-penta-Q-tr ideeanoyl-scyL lo- πos i tol

Example A:

A mixture of 100 mg of N-valeryL-peπta-0-va ler L- 1-amiπo-1-deoxy-scyI lo-inos i tol, 12.5 mg of azo-bis-iso- butyroni tr Le and 400 mg of styrene is heated at 60 C for 18 hours, while gassing w th nitrogen. An elastic polymer is obtained and exhibits high birefr ngence under a polarization microscope. Example S:

A mixture of 100 mg of N-valeryl-peπta-Q-valeryl- 1-amino-1-deoxy-scyl Lo-inos i tol , 12.5 mg of azo-bis-iso- butyroπ i tr i le and 400 mg of methylmethacryI ate is heated at 6Q°C for 18 hours, while gassing with nitrogen. An elastic polymer which shows high birefπ ^' ngent properties is obtained.