GB2130596A - Anthraquinone derivatives, method for preparing same, liquid-crystal material for electrooptical devices and electrooptical device - Google Patents

Abstract

The present invention relates to anthraquinone derivatives of the general formula (I): <IMAGE> wherein A, M, B, Z are the same or different substituents having meanings R<1>DX, R<2>EY, wherein R<1> and R<2> are the same or different and represent each a C4-C18 alkyl, <IMAGE> X, Y are the same or different and represent each oxygen or a group NH, NR<3>; E is an ordinary bond, <IMAGE> Y + E + R<2> = H, Cl, Br, NO2, NR<3>R<4>, wherein R<3> is a C1-C18 alkyl, R<4> is H or C4H9, or R<3> + R<4> = &lparstr& CH2 &rparstr& 5; n = 0 or 1, m = 0, 1, 2 excluding compounds, wherein A = M = B = Z = H, Cl, Br, NO2, NR<3>R<4>. These compounds are prepared by acylation of anthraquinone derivatives of the general formula (II): <IMAGE> wherein W, T, L, K are the same and/or different substituents representing each NH2, NHR<3>, OH, H, Cl, Br, NO2, NR<3>R<4>, wherein: R<3> is a C1-C8 alkyl, R<4> is hydrogen or C4H9, R<3> + R<4> = &lparstr& CH2 &rparstr& 5, by means of acid chlorides of the general formula (III): R<1>DCl (III> wherein R<1> and D are as identified in formula (I). The compounds corresponding to the above-given formula (I) are dyestuffs with a negative dichroism which are incorporated into a composition of a liquid-crystal material. The liquid-crystal material comprises a liquid-crystal matrix and at least one derivative of anthraquinone of the above-given formula (I). This liquid-crystal material is used in an electrooptical device as a dichroic working body (I) positioned between optically transparent plates (2) having on their sides transparent electrodes (3) provided with conductors (4) for connection to a power supply source.

Description

SPECIFICATION Anthraquinone derivatives, method for preparing same, liquid-crystal material for electrooptical devices and electrooptical device The present invention relates to novel dichroic dyes for liquid crystals and, more specifically, to novel derivatives of anthraquinone manifesting negative dichroism in liquid crystals, to a method for preparing these anthraquinone derivatives, a liquid-crystal material for electrooptical devices and to an electrooptical device.

The novel derivatives of anthraquinone find an extensive use in the manufacture of mesomorphic materials which are useful in the electronic industry for various electrooptical devices for presentation and processing of information operating on the "guest-host" effect.

Known in the art is a great number of dichroic dyes - anthraquinone derivatives manifesting positive dichroism in liquid crystals (cf. C.H. Heilmeier, L.A. Zanoni, Appl.Phys.Lett., 1968, v.3, p.91). From these dichroic dyes liquid-crystal materials are obtained which are useful for an electrooptical device ensuring presentation of different kinds of information (letters, figures and the like) as slightly coloured symbols against a strongly coloured background.

At the same time, for the provision of electrooptical devices ensuring presentation of information in the form of deeply coloured symbols against a slightly coloured background, symbols of one colour against a background of another colour or, finally, black-colour symbols against a colourless or desired-colour background, it is necessary to have dyes manifesting negative dichroism in liquid crystals.

The currently known range of dyes displaying negative dichrosim in liquid crystals is limited to derivatives oftetrazine and 2,2'-azoimidazole (cf. D.Demus, B.Krucke, F.Kuschel, H.U.Nothnick, G.Pelzi, H.Zaschke "3-n-alkyl-6-/4-n-alkyloxyphenyl/-1,2,4,5-tetrazines- new stable dyestuffs with liquid-crystalline properties", Mol.Cryst, 1979, v.56 (letters), p.115-121, Gordon and Breach Science Publishers, London-New York-Paris).

Dichroic dyestuffs - tetrazine derivatives - have an absorption band within the range of from 550 to 570 nm and ensure the production, in electrooptical devices, of red-violet symbols against a slightly coloured background of the same colour or red-violet symbols against a background of another colour, the latter being ensured by incorporation, into the liquid-crystal material, of an appropriate additional dyestuff exhibiting positive dichroism in liquid crystals (cf. G.Pelzl, H.Schubert, H.Zaschke, D.Demus "kristal und Technik, Bd.14, s.817-823, 1979, "Field-induced colour change of liquid Crystalline Dyes").

However, the absorption band of tetrazines showing negative dichroism (n-II* band) has a low intensity, so that in order to produce bright symbols in electrooptical devices, it is necessary to introduce very high amounts of these dyestuffs into the liquid-crystal material. For example, at a thickness of an electrooptical cell of 10 it is necessary to introduce more than 20% of a dyestuff into the liquid-crystal material. This results in a substantial deterioration of the performance characteristics of the liquid-crystal material. This may account for the fact that this range of dichroic dyestuffs so fat has not found any practical application.

Derivatives of 2,2'-azoimidazole have certain advantages over tetrazine derivatives, since they have two absorption bands in the visibie spectrum range: 430-440 nm and 530-560 nm, the former band showing positive dichroism in liquid crystals, the latter- negative one. These bands feature a high intensity, since they are produced by ll-II* transit; ,. For this reason, known liquid-crystal materials incorporating derivatives of 2,2'-azoimidazole contain only 1-2% of these dyestuffs, yet the required optical density of the absorption bands is reached.

An electrooptical device consisting of a dichroic working body comprising a layer of a liquid-crystal material containing 2,2'-azoimidazole derivatives interposed between optically transparent non-conducting plates having transparent electrodes of their inner sides, provided with a control circuit, ensures the production of red-violet symbols against a light brown background. If the dichroic working body, i.e. the layer of the liquid-crystal material, additionally contains a dyestuff with positive dichroism, the background will have a different colour which corresponds to the overall absorption of the positive-dichroism dyestuff and the derivatives of 2,2'-azoimidazole.

However, a device incorporating a dichroic working body based on 2,2'-azoimidazoles makes it possible to obtain symbols of red-violet or violet colour only, this restricting the range of its application.

The present invention is directed to the provision of novel dyestuffs from the series of anthraquinone derivatives exhibiting a negative dichroism in liquid crystals, and a method for preparing same; to the provision of a liquid-crystal material based on said compounds for electrooptical devices and an electrooptical device for representation and processing of information.

Said object has been accomplished by the provision of novel anthraquinone derivatives which, according to the present invention, have the following general formula (I):

wherein A, M, B, Z are the same or different substituents having meanings R1DX, R2EY, wherein R1, R2 are the same or different and represent each a C4-C18 alkyl;

X, Y are the same or different and represent each oxygen or a group NH, NR3, E is an ordinary bond,

or Y + E + R2 = H, Cl, Br, NO2, NR3R4, wherein R3 is a C1-C8 alkyl, R4 is hydrogen or C4H9, R3 + R4 = n = O or 1, m = 0, 1,2, excluding compounds, wherein A = M = B = Z = H, Cl, Br, NO2, NR3R4.

The derivatives of anthraquinone of the general formula (I) are dyestuffs of yellow, red or blue colour exhibiting negative dichroism in liquid crystals.

According to the present invention, the derivatives of anthraquinone are prepared by acylation of anthraquinone derivatives of the general formula (II):

wherein W, T, L, K are the same and/or different substituents: NH2, NHR3, OH, H, Cl, Br, NO2, NR3R4, where R3 is a C-C8 alkyl, R4 is H or C4H9, R3 + R4 = # CH2* by means of acid chloroanhydrides of the general formula (III): R'DCI (III) wherein R' is a C4-C18,

n = 0,1; m = 0,1,2 provided that when a compound of the general formula (II) contains Cl, Br, NO2 as substituents, the compound resulting from acylation is reacted with substituted amines of the general formula (IV): R2EQ (IV) wherein R2 is a C4-C18 alkyl, E is an ordinary bond,

Q = NH2, NHR3, wherein R3 is a C1-C8alkyl; n = 0,1; m = 0,1,2.

The present invention also relates to a liquid-crystal material incorporating anthraquinone derivatives of the general formula (I) comprising dyestuffs manifesting negative dichroism in liquid crystals; according to the present invention, this material contains 0.1 to 10% by weight of at least one anthraquinone derivative of the general formula (I) and the balance is a liquid-crystal matrix with a positive or negative dielectric anisotropy comprising, when required, liquid crystals of a cholesteric type and/or other known dichroic dyestuffs.

The present invention has made it possible to obtain a liquid-crystal material enabling the production of symbols of any colour in an electrooptical device against a colourless or slightly-coloured background or a background having any other colour different from the colour of symbols and a high image contrast is obtained.

The present invention is also concerned with an elèctrooptical device comprising a dichroic working body in the form of a layer of a liquid-crystal material containing 0.1 to 10% by weight of at least one anthraquinone derivative of the general formula (I) positioned between two optically transparent non-conducting plates having transparent electrodes applied onto their inner sides for connecting to a power supply source.

The electrooptical device according to the present invention intended for information presentation and processing makes it possible to produce symbols or signs of any colour against a colourless or slightly-coloured background or a background having any colour different from that of symbols and signs with the provision of a high contrast of the image. When required, this device can be provided with one or two polaroids.

The present invention will be now more fully apparent from the following detailed description.

As it has been mentioned hereinabove, the present invention deals with novel anthraquinone derivatives corresponding to the general formula (I):

wherein A,M,B and Z are as identified hereinabove.

In the above formula (I) the following combinations of the substituents are possible: A = M = R'DX, B = Z = hydrogen A = Z = R1DX, M = B = hydrogen A = B = R1DX, M = Z = hydrogen A= M = B = R1DX, Z = hydrogen A = M = B = Z = R1DX; A = R1DX, M = R2EY, B = Z = hydrogen A = R1DX, Z = R2EY, M = B = hydrogen A = R1DX, M = Z = R2EY, B = hydrogen A = R1DX, B = Z = R2EY, M = hydrogen A = R1DX, M = B = R2EY, Z = hydrogen A= R'DX, M = B=Z= R2EY A = M = R'DX, B = R2EY, Z = hydrogen A = M = R'DX, B = Z = R2EY; A = Z = R1DX, M = R2EY, B = hydrogen A = Z = R'DX, M = B = R2EY; A = B = R'DX, M = R2EY, Z = hydrogen A = B = R1DX, M = Z = R2EY; A = M = B = R'DX,Z= R2EY;; The compounds having most advantageous characteristics as negative-dichroism dyestuffs are, for example, the following:

(Example 4)

(Example 34)

(Example 42)

(Example 35)

H15C7""'N0 / A oC7Hls "',7/xa H z N (5) (Example 41) Characteristics of these dyestuffs are shown in Table 1.

TABLE 1

Compound No. #,nm D11 - D1 S= D11+2D1 1 512 -0.36 2 580 -0.35 3 470 -0.36 # # 4 580 -0.32 618 -0.32 5 536 -0.36 Table 1 shows absorption bands (k, nm) and values of their dichroism (S) for 1% solutions of compounds 1-5 in a liquid-crystal matrix ZhK-807 comprising a mixture of 4-alkyl- and 4-alkoxy-4-cyanodiphenyls. In the formula for the determination of dichroism (S) D11 and D1 mean optical densities measured parallel (D71) and perpendicularly to the liquid crystal director (D1).

It is proposed to produce anthraquinone derivatives of the general formula (I) by acylation of corresponding anthraquinones of formula (11) containing amino, hydroxy or hydroxy and amino groups in the positions 1, 4, 5 and 8 by means of chlorides of corresponding organic acids of the above-given formula (III) in a medium of chlorinated benzenes or in nitrobenzene upon heating. In the case where the starting anthraquinones, along with amino, hydroxy or amino and hydroxy groups have Cl, Br or NO2 as substituents, it is desirable to substitute them with corresponding amino groups by reacting acyl derivatives of anthraquinone having CI, Br or NO2 as substituents and resulting from acylation of corresponding starting anthraquinones by means of substituted or unsubstituted amines.The reaction is carried out in a medium of a substituted or unsubstituted amine, chlorinated benzenes or nitrobenzene with heating.

The desired products obtained according to the present invention can be isolated from the reaction mass by any methods known in chemical technology, such as partial distilling-off of the solvent, filtration and subsequent recrystallization, or chromatographic purification; dilution of the reaction mass with another solvent, filtration and subsequent crystallization or chromatographic purification; chromatography of the reaction mass, and the like.

The best mode for carrying out of the present invention relating to the liquid-crystal material resides in that this liquid-crystal material consists of 1% by weight of a derivative of anthraquinone of formula (I), 1% by weight of a derivative of anthraquinone of formula (III), the balance being liquid-crystal matrix ZhK-807 consisting of 4-alkyl- and 4-alkoxycyanodiphenyls, or liquid-crystal matrix ZhK-654 consisting of liquidcrystal azoxy compounds and 4-alkylbenzoic acid 4-acyanophenyl ester. This material makes it possible to produce bright-crimson symbols against a substantially colourless background.

According to the present invention, the liquid-crystal material can incorporate at least one of the anthraquinone derivatives of the general formula (I) in an amount of from 0.1 to 100% by weight and the balance is a liquid-crystal matrix with a positive or negative dielectric anisotropy including, when required, liquid crystals of cholesteric type and/or other conventional dichroic dyestuffs.

The upper limit of the content of anthraquinone derivatives of the general formula (I) depends on the possibility of producing a liquid-crystal material ensuring the formation, in an electrooptical device, of symbols having mixed colours, e.g. green, blue-violet, red-violet, or black colour in thin cells of < 10 Wm.

The lower limit depends on the possibility of producing a liquid-crystal material incorporating dyestuffs with positive dichroism ensuring the production of light-coloured symbols against a coloured background (in the case of a liquid-crystal material with positive dielectric anisotropy) or coloured symbols against a pale background (in the case of a liquid-crystal material with negative dielectric anisotropy); minor amounts of the derivatives of anthraquinone corresponding to the general formula (I) make it possible to produce a neutral (light-grey) background or symbols of a neutral (light-grey) colour.

The liquid-crystal material according to the present invention can incorporate, in addition to anthraquinone derivatives, also other known dichroic dyestuffs, for example, those having positive dichroism. The use thereof is conditioned by the possibility of producing a liquid-crystal material ensuring the formation of symbols having one colour against a background of another colour in an electrooptical device. Various combinations of the anthraquinone derivatives of the general formula (I) with dyestuffs having positive dichroism make it possible to produce, in an electrooptical device, symbols of substantially any colour against a background having substantially any other colour.

The liquid-crystal material according to the present invention comprises a liquid-crystal matrix which is a mixture of compounds predominantly liquid-crystal ones. The latter can pertain to most different classes: derivatives of azoxybenzenes, phenylbenzoates, biphenyls, terephenyls, phenyl-trans-cyclohexanes, phenyl2,2,2-bicyclooctanes and the like. The simplest embodiment resides in that as the liquid-crystal matrix use can be made of already known liquid-crystal mixtures available from commercial companies specializing in the manufacture of liquid crystals and materials based thereon.

According to the present invention, the liquid-crystal material can incorporate liquid crystals of the cholesteric type. This is associated with the possibility of producing a mesomorphic material for devices operating on the effect of the "cholesteric-nematic" transition. Furthermore, the cholesteric-type liquid crystals can be incorporated into the liquid-crystal material according to the present invention for the purpose of improvement of its orientation in an electrooptical device, for example, in "twist"-indicators. In the latter case instead of the cholesteric-type liquid crystals use can be made of most different optically active compounds.

An electrooptical device according to the present invention is illustrated hereinbelow by the accompanying drawing showing its principal diagram. The device comprises a dichroic working body 1 (a layer of a liquid-crystal material) interposed between two glass or other transparent nonconducting plates 2 positioned opposite to one another. On the inner sides of the plates 2 transparent electrodes 3 are applied, provided with conductors 4 for connection to a power supply source (not shown in the drawing).

In the electrooptical device use is made of a dichroic working body 1 with the thickness of 10 m with a definite orientation of the molecules, which is interposed between optically transparent plates 2 having electrodes 3 applied to the inner sides thereof, these electrodes being made from SnO2, shaped as particular symbols, and connected to a power supply source. When to the electrodes 3 a voltage is applied having a value above the threshold voltage of the liquid-crystal material, symbols of the desired colour appear against the background having different colour. When the voltage is removed, the symbols disappear. The colour of the symbols and of the background are determined, as it has been already mentioned hereinbefore, by a combination of the anthraquinone derivatives of the general formula (I) with dyestuffs having a positive dichroism.

For a better understanding of the present invention, some specific examples are given hereinbelow by way of illustration.

Examples 1 to 43 illustrate the preparation of novel derivatives of anthraquinone corresponding to the general formula (I), Examples 44 to 87 illustrate novel liquid-crystal materials and Examples 88 through 95 demonstrate the functioning of a novel electrooptical device according to the present invention.

Example 1 0.5 g (0.002 mol) of 1-aminoanthraquinone, 0.75 g (0.00275 mol) of butyldiphenylcarboxylic acid chloroanhydride in 10 ml of nitrobenzene are heated under reflux for 10 minutes, whereafter the reaction mixture temperature is lowered to 60"C and 30 ml of a hot (50-600C) of isopropanol are added at this temperature under stirring. The reaction mixture is cooled to a temperature of about 20"C, filtered, washed with isopropanol. The precipitate is dissolved in benzene and chromatographed on a column with silica gel ofthe grade Chemapol L40/100 Il. The eluent is benzene.Afterdistilling-offthe solvent there is obtained 0.25 g (24.75% of the theoretical) of 1 -/4-(4-butylphenylene)-benzamido/-anthraquinone. M. p. is 259-260"C.

Found,%: C81,15, H5.32, N2.97. C31H25NO3.

Calculated, %: C81.04, H 5.48, N 3.05.

Example 2 2 g (0.0077 mol) of 1-amino-4-chloroanthraquinone and 2.8 g (0.0117 mol) of heptylbenzoic acid chloroanhydride in 15 ml of nitrobenzene are heated at reflux for 20 minutes and recovered following the procedure similar to that described in Example 1 hereinabove. The precipitate is crystallized from heptane to give 2.12 g of 1-/4-heptylbenzamido/-4-chloroanthraquinone. The yield is 59.38% of the theoretical. M.p. is 140-141"C.

Found, %: C 73.02, H 5.91, Cl 7.79, N 3.15. C28H26C1 NO3.

Calculated, %; C73.11, H 5.7, Cl 7.7, N 3.04.

Example 3 Following the procedure similar to that described in Example 2, from 1.51 g (0.005 mol) of 1-amino-4-bromoanthraquinone and 2.47 g (0.0075 mol) of octyldiphenylcarboxylic acid chloroanhydride there are obtained 1.96 g (65.86% of the theoretical yield) of 1 -/4-octylphenylene-4-benzamido/-4- bromoanthraquinone.

Found, %: C 70.88, H 5.31, Br 13.52, N 2.21, C35H32BrNO3.

Calculated, %: C 70.7, H 5.42, Br 13.44, N 2.35.

Example 4 1.43 g (0.006 mol) of 1,4-diaminoanthraquine, 4.77 g (0.02 mol) of p-octyldiphenylcarboxylic acid chloroanhydride in 20 ml of nitrobenzene are heated for 30 minutes. The reaction mass temperature is lowered to about 60"C and 40 ml of a hot (about 60"C) isopropanol are added thereto at this temperature under stirring. The reaction mixture is cooled to room temperature, filtered, washed with 20 ml of isopropanol. The precipitate is dissolved in benzene, and passed through a chromatographic column with silica gel L 40/100 . The eluent is benzene. There are obtained 2 g (40.49% of the theoretical yield) of 1 ,4-bis44-octylphenylne-4-benzamido/-anthraquinone. M.p. 274-276"C.

Found, %: C 81.95, H 7.21, N 3.15. C56H58N2o4 Calculated, %: C 81.72, H 7.1, N 3.4.

Example 5 Following the procedure described in Example 4, from 1.19g (0.005 mol) of 1,4-diaminoanthraquinone and 3.6 g (0.015 mol) of p-n-heptylbenzoic acid chloroanhydride there is obtained 1.12 g of 1 ,4-bis-/ 4-hepthylbenzamido/-anthraquinone which is recrystallized from benzene. The product has M.p. of 207-21 0 C.

Found, %: C 78.60, H 7.35, N 4.28. C42H46N2o4 Calculated, %: C 78.47, H 7.21, N 4.36.

Example 6 Under the conditions of Example 4, from 4g(0.0116mol) of 1,4-diaminoanthraquinone and 12 g (0.053 mol) of p-n-hexyl-benzoic acid chloroanhydride 3.31 g of 1,4-bis/4-hexylbenzamido/-anthraquinone are botained (33.64% of theory). M.p. of the product is 198-200 C.

Found, %: C 78.13, H6.95, N 4.67. C40H42N204- Calculated,%; C 78.21, H 6.88, N 4.55.

Example 7 Under the conditions of Example 4, from 1.43 g (0.006 mol) of 1,4-diaminoanthraquinone and 2.95 g (0.015 mol) of p-n-butyl-benzoic acid chloroanhydride 1,83 g of 1,4-bis-/4-butylbenzamido/-anthraquinone are obtained (54.70% of theory). M.p. is 217-219 C.

Found,%: C 77.62, H 5.83, N 5.17, C36H32N2O4.

Calculated,%: C77.39, H 6.13, N 5.01.

Example 8 Under the reaction conditions described in Example 4 from 1.43 g (0.006 mol) of 1,4diaminoanthraquinone and 4 g (0.013 mol) of nonylbenzoic acid chloroanhydride 2.02 g of 1,4-bis-1 4-nonylbenzamido/-anthraquinone are obtained (48.21% of theory) M.p. 193-195"C.

Found, %: C 79.21, H 7.63, N 4.25. C45H54N2O4.

Calculated,%: C 79.05, H 7.79, N 4.01.

Example 9 Under the reaction conditions described in Example 4, from 1.43 9 (0.006 mol) of diaminoanthraquinone and 3.4 g (0.015 mol) of amyloxybenzoic acid chloroanhyride 2.36 g of 1 ,4-/bis-4-amyloxybenzamido/ -anthraquinone are obtained (63.61% of theory). M.p.229-231 C.

Found, %: C 73.59, H 6.08, N 4.67. C38H38N206 Calculated,%: C73,77, H6.19, N4.53.

Example 10 Under the reaction conditions described in Example 4, from 1.43 g (0.006 mol) of 1,4diaminoanthraquinone and 6.55 g (0.016 mol) of octadecyloxybenzoic acid chloroanhydride 3.69 9 of 1,4-bis-/4-octadecyloxybenzamido/-anthraquinone are obtained (64.73% of theory). M.p. is 177-178 C (form benzene).

Found, %: C 78.42, H 9.28, N 2.75. C64H90N2O6 Calculated, %: C 78.2, H 9.16, N 2.85.

Example 71 Under the reaction conditions described in Example 4, from 1.19 g (0.005 mol) of 1,4diaminoanthraquinone and 2.9 g (0.015 mol) of n-butyl-trans-cyclohexanecarboxylic acid chloroanhydride 0.69 g of 1,4-bis-/4-butyl-trans-cyclohexylamido/-anthraquinone is obtained (24.12% of theory). M.p. above 250 C.

Found, %: C 75.88, H 8.02, N 4.76. C36H46N204- Calculated, %: C 75.76, H 8.12, N 4.91.

Example 12 Under the reaction conditions described in Example 4, from 0.95 g (0.004 mol) of 1,4diaminoanthraquinone and 2.1 g (0.009 mol) of n-hexyl-trans-cyclohexanecarboxylic acid chloroanhydride there is obtained 0.5 g of 1 ,4-bis-/4-hexyl-cyclohexylam ido/-anthraquinone melting at 269-2700C (benzene).

Found, %: C 76.48, H 8.91, N 4.39. C40H54N2O4.

Calculated, %: C 76.64, H 8.68, N 4.47.

Example 13 Under the reaction conditions described in Example 4, from 0.7 g (0.0029 mol) of 1,4diaminoanthraquinone and 2.25 g (0.0074 mol) of stearic acid chloride there is obtained 0.4 g (18.02% of the theoretical yield) of 1,4-bis-stearylamidoanthraquinone melting at 113-1 150C (benzene).

Found, %: C 78.11, H 9.54, N 3.78. C50H74N204- Calculated, %: C 78.28, H 9.72, N 3.65.

Example 14 3 g (0.01 mol) of 1,4-dichloro-5,8-dihydroxyanthraquinone and 26.9 g (0.1 mol) of octadecylamine are heated to the temperature of 155"C and maintained at a temperature within the range of from 155 to 1600C for 1.5 hour. The reaction mixture is cooled to the temperature of 60 C and added with 20 ml of methanol, while maintaining the temperature at 60"C. The reaction mixture is stirred for one hour at 60"C and filtered while hot. The residue is washed several times with methanol, squeezed, dissolved in benzene and chromatographically purified on a column with SiO2, grade L 40/100 . The eluent is chloroform. The blue-green fraction is collected.After distilling-off the solvent the residue is crystallized from ethanol to give 0.6 g of 1,4-bis-octadecylamine-5,8-dihydroxyanthraquinone.

Found,%: C77.64, H 10.53, N3.47. C50H82N204- Calculated,%: C77.47, H10.66, N3.61.

Example 15 0.75 g (0.0016 mol) of 1-/4-heptylbenzamido/-4-chloroanthraquinone prepared as described in Example 2, 1.3 g of octadecylamine (0.0048 mol), 0.6 g of sodium acetate and 0.003 g of copper powder are heated with stirring to the temperature of 1 55"C and kept at a temperature within the range of from 155 to 1 600C for one hour. The reaction mass is cooled to the temperature of 60"C, added with 25 ml of methanol, stirred for 30 minutes and filtered. The residue is washed with alcohol, dried, dissolved in benzene and chromatographed on a column with SiO2. The eluent is benzene. 0.3 g of 1-/4-heptylbenzamido/-4octadecylaminoanthraquinone is thus obtained.

Found, %: C 79.86, H 9.41, N3.96. C46H64N203- Calculated,%; C 79.72, H 9.31, N 4.04.

Example 16 0.35 g (0.0008 mol) of 1V4-heptylbenzamido/-4-chloroanthraquinone, 1.72 g (0.02 mol) of piperidine are boiled in the presence of 0.3 g of sodium acetate and 0.001 g of copper powder for one hour, then the reaction mixture is cooled and diluted with alcohol. The precipitate is filtered, washed with alcohol, dissolved in benzene and passed through a column with SlO2, the eluent is benzene. 0.2 g of 1-/4-heptylbenzamido/-4-piperidinoanthraquinone is thus obtained. M.p. is 140"C.

Found, %: C 77.72, H 7.35, N 5.61. C33H36N203- Calculated, %: C 77.92, H 7.13, N 5.50.

Example 17 Under the conditions described in Example 15, from 0.5 g (0.001 mol) of 1-/4-heptylbenzamido/ -4-chloroanthraquinone and 1.15 g (0.003 mol) of m-octadecylhydroxyaniline in the presence of potassium acetate and copper powder 0.2 g of 1 -/4-heptyl-benzamide/-4-/3-octadecylhydroxyanilino/-anthraquinone melting at 79-80"C is obtained.

Found, %: C 79.76, H 8.65, N 3.47. C52H68N2O4.

Calculated, %: C 79.55, H 8.73, N 3.57.

Example 18 2.4 g (0.01 mol) of quinizarine and 8.16 g (0.03 mol) of butyldiphenylcarboxylic acid chloride in 50 ml of pyridine are heated to 60"C and kept at this temperature for 2 hours. The reaction mixture is cooled and poured into a solution of a 10% hydrochloric acid. The resulting precipitate is filtered, washed with a 5% solution of hydrochloric acid, then with water to neutral reaction as indicated by an all-purpose indicator paper. The dried residue is dissolved in benzene and passed through a column with SiO2. The dyestuff is eluted with a benzene-chloroform mixture (1:1), recrystallized from a benzene-acetone mixture (2:1) to give 1.6 g of 1,4-bis-/4-butyldiphenylcarboxy/-anthraquinone (22.47% of theory). M.p. is 223.7-223.9 C.

Found,%: C 80.69, H 5.81, C48H4006- Calculated, %: C 80.88, H 5.66.

Example 19 0.76 g (0,003 mol) of 1,5-dihydroxyanthraquinone, 1.76 g (0.007 mol) of heptylbenzoic acid chloroanhydride in 30 ml of nitrobenzene are heated under reflux for one hour, cooled to the temperature of 60"C and added with isopropanol. The precipitate is filtered and washed with isopropanol. The product is crystallized from dichloroethane to give 1.05 g (54.4% of theory) of 1 ,5-bis-/4-heptylbenzamido/-anthraquinone melting at 295.5-297 C.

Found, %: C 78.29, H 7.40, N 4.29. C42H46N2O4.

Calculated, %: C 78.47, H 7.21, N 4.36.

Example 20 0.19 g (0.0008 mol) of 1-amino-4-hydroxyanthraquinone, 0.9 g (0.0027 mol) of p-octyldiphenylcarboxylic acid chloroanhydride in 10 ml of nitrobenzene are heated at reflux for 2 hours, The reaction mixture is cooled to about 20"C and diluted with isopropanol. The residue is filtered, washed with alcohol, dissolved in benzene and subjected to chromatographic purification in a column with silica gel. The eluent is benzene.

0.15 g of 1-/4-octylphenylene-4-phenylamido/-4-/4-octyldiphenylcarboxy/-anthraquinone is obtained (42.3% of theory).

Found, %: C 81.42, H.6.88, N 1.58. C56H5705N.

Calculated, %: C 81.62, H 6.97, N 1.7.

Example 2 1 0.4 g (0.0015 mol) of 1-amino-4-chloroanthraquinone,0.9 g (0.0027 mol) of p-octyldiphenylcarboxylic acid chloroanhydride in 15 ml of nitrobenzene are boiled for 2 hours and the product is isolated as described in Example 20. The residue is recrystallized from heptaneto give 0.6 g (72.72% of theory) of 1-/ 4-octylphenylene-4-benzamido/-4-chloroanthraquinone melting at 157 C.

Found,%: C 76,21, H 5.98, N 2.39, C35H32CINO3.

Calculated, %: C 76.42, H 5.86, Cl 6.44, N 2.55.

Example 22 From 0.3 g (0.0005 mol) of 1-/4-octylphenylene-4-benzamido/-4-chloroanthraquinone prepared as described in the foregoing Example 21 and 1.8 g (0.005 mol) of m-octadecyloxyaniline under the conditions of Example 15 (residence time is 3 hours) 0.1 g of 1-/4-octylphenylenebenzamido/-4-/3-octadecylbenzamido/ -anthraquinone melting at 115-117"C is obtained.

Found, %: C 80.79, H 8.64, N 3.32. C59H74N2O4.

Calculated,%; C 80.96, H 8.52, N 3.20.

Example 23 Under the conditions of Example 15 from 0.3 g of 1-/4-octylphenylene-4-benzamido/-4- chloroanthraquinone prepared as described in Example 21 and 0.5 g of 1-octyldiphenylethylamine (residence time is 8 hours) there is obtained, after chromatographic purification (eluate benzene), 0.12 g of 1 -/4-octylphenylene-4-benzamido/-4-/1 -(4-octyidiphenylene)-ethyl/-aminoanthraquinone.

Found, %: C 83.27, H 7.36, N 3.54. C57H62N203 Calculated, %; C 83.17, H 7.59, N 3.40.

Example 24 0.86 g (0.0023 mol)of 1-amino-4-(4-tert.butylphenox)-anthraquinone, 0.92 g (0.0028 mol) of 4 octyldiphenylcarboxylic acid chIoro. "1ydride in 20 ml of nitrobenzene are heated under reflux for 2 hours.

The reaction mixture is cooled to the temperature of 80"C, added with isopropanol. The residue is twice crystallized from a benzene-heptane mixture to give 0.63 g (41.45% of th theoretical value) of 1-/4-octylphenylene-4-benzamido/-4-/-tert. butylphenoxy/-anthraquinone melting at 187.5-198.2 C.

Found, %: C 81.95, H 7.03, N 2.17. C45H4NO4.

Calculated, %: C 81.44, H 6.78, N 2.11.

Example 25 Under the conditions of Example 4, from 0.95 g (0.004 mol) of 1,4-diaminoanthraquinone and 2.4 g (0.012 mol) of tert. butylbenzoic acid chloride in 20 ml of nitrobenzene there is obtained, after chromatographing through SiO2 (eluent- benzene) and recrystallization from alcohol, 0.23 g of 1,4-bis-/4-tert.butylbenzamido/ -anthraquinone melting above 330 C.

Found,%: C77.12, H6.14, N4.93. C36H34N2O4.

Calculated, %: C 77.40, H 6.13, N 5.01.

Example 26 2.23 g (0.005 mol) of 1-/4-hexylbenzamido/-4-chloroanthraquinone, 10 9 of n-octylamine, 0.66 g of anhydrous sodium acetate in the presence of copper powder are kept for one hour at a temperature within the range of from 150 to 155'C. The reaction mixture is cooled, added with 30 ml of 10% hydrochloric acid, the residue is washed with water to pH = 7, dried, dissolved in chloroform, chromatographed through SiO2 (eluent- chloroform) to give 0.81 g (30.1% of theory) of 1-/4-hexylbenzamido/-4-octylaminoanthraquinone melting at 173-175 C.

Found, %: C 78.23, H 7.98, N 5.37. C35H42N203- Calculated, %: C 76.03, H 7.86, N 5.20.

Example 27 From 2.23 g (0.05 mol) of 1-/4-hexylbenzamido/-4-chloroanthraquinone, 10 10g of dibutylamine in the presence of sodium acetate and copper powder under the conditions described in Example 26 (residence 2 hours) 0.9 g of 1-/4-hexylbenzamido/-4-dibutylaminoanthraquinone is obtained (33.4% of theory).

M.p. is 202-203 C.

Found,%: C77.81, H7.93, N5.17. C35H42N203- Calculated, %: C 78.03, H 7.84, N 5.20.

Example 28 2.23 g (0.005 mol) of 1-/4-hexylbenzamido/-4-chloroanthraquinone, 3.65 g (0.024 mol) of m-butoxyaniline in the presence of 0.6 g of sodium acetate and copper powder in 15 ml of nitrobenzene are heated to a temperature within the range of from 155 to 160 C and kept at this temperature for 4 hours. The reaction mixture is cooled to the temperature of 70 C and added with 30 ml of alcohol. The residue chromatographed on a column with SiO2(eluent- chloroform). There is obtained 1-/4-hexylbenzamido/-4-/3-butoxyphenyl/ -aminoanthraquinone melting at 126-127 C.

Found, %: C 77.56, H 6.54, N 4.78. C37HN2O4.

Calculated, %: C 77.2, H 6.8, N 4.9.

Example 29 From 3.3 9 (0.006 mol) of 1-/4-octylphenylene-4-benzamido/-4chloroanthraquinone and 10 g of butylaniline under the conditions of Example 27 (the residence time is 7 hours) there are obtained 2.32 g (58.4% of theory) of 1-/4-octylphenlene-4-benzamido/-4-/butylphenyl/-aminoanthraquinone melting at 176.4-179 C.

Found, %: C 81.33, H 7.21, N 4.35. C45H46N2O3.

Calculated, %; C81.54, H 6.98, N 4.22.

Example 30 From 2.23 g (0.004 mol) of 1-/4-octylphenylene-4-benzamido/-4-chloroanthraquinone and 2.16 9 of p-butylamine under the conditions of Example 28 (the residence time is 4 hours) 0.5 9 of 1-/ 4-octylphenylene-4-benzamido/-4-butylaminoanthraquinone is obtained (20.3% of theory). M.p. is 202.5204.5 C.

Found, %: C 80.13, H 7.31, N 4.63. C39H42N203.

Calculated,%: C79.86, H7.17, N4.78.

Example 31 Under the conditions of Example 26 (the time of residence is 2 hours at 145-150 C), from 2.23 g (0.004 mol) of 1-/4-octylphenylene-4-benzamido/-4-chloroanthraquinone and 1.73 9 (0.015 mol) of hepthylamine 0.49 g of 1-/4-octylphenylene-4-benzamido/-4-heptylaminoanthraquinone is obtained. M.p. is 193.5-195 C.

Found, %: C 80.34, H 7.53, N 4.38. C42H49N203.

Calculated, %: C 80.09, H7.84, N4.45.

Example 32 From 2.23 9 (0.004 mol) of 144-octylphenylene-4-benzamido/-4-chloroanthraquinone and 2 9 of dibutylamine under the conditions described in Example 260.55 g of 1-/4-octylphenylene-4-benzamido/ -4-dibutylaminoanthraquinone is obtained (20.37% of theory). M.p. is 199.5-202 C.

Found, %: C 80.02, H 7.98, N 4.22. C43H50N2O3.

Calculated, %; C 80.33, H 7.84, N 4.35.

Example 33 Under the conditions described in Example 28, from 1-/4-octylphenylene-4-benzamido/-4- chloroanthraquinone and 1-/4-tert.butylphenyl/-ethylamine 1-/4-octylphenylene-4-benzamido/-4-/1-(-4- tert.butylphenyl)-ethylamino)-anthraquinone is obtained. M.p. 225-227 C.

Found, %: C 81.33, H 7.59, N 4.28. C47H50N203- Calculated, %; C 81.64, H 7.29, N 4.14.

Example 34 From 2.7 g (0.005 mol) of 1-/4-octylphenylene-4-benzamido/-4-chloroanthraquinone and 1.9 g of octylamine under the conditions specified in Example 28, after chromatography, 0.79 g of 1-/4octylphenylene-4-benzamido/-4-octylaminoanthraquinone is obtained (24.6% of theory). M.p. 189-1 90.5'C.

Found,%: C8O.O5, H7.80, N4.15. C43H50N2O3.

Calculated, %: C 80.34, H 7.84, N.4.36.

Example 35 Under the conditions of Example 26, from 3.96 g (0.0075 mol) of 1 -/4-hexylphenylene-4-benzamido/ -4-chloroanthraquinone and 10 g of dibutylamine 3.0 g of 1 -/4-hexylphenylene-4-benzamido/-4dibutylaminoanthraquinone are obtained (64.23% of theory). M.p. 219-220"C.

Found, %: C 80.25, H 7.89, N 4.48. C41H46N203 Calculated, %; C 80.09, H 7.54, N 4.55.

Example 36 Under the conditions of Example 26, from 3.34 g (0.0064 mol) of 1 -/4-hexylphenylene-4-benzamido/ -4-chloroanthraquinone and 15 g of octylamine 2.6 9 of 1 -/4-hexylphenylene-4-benzamido/-4octylaminoanthraquinone are obtained (66.67% of theory). M.p. 198-200 C.

Found, %: C 80.37, H 7.34, N 4.63. C41H46N2O3.

Calculated, %; C 80.13, H 7.49, N 4.56.

Example 37 From 1.95 g (0.0039 mol) of 1-/4-butylphenylene-4-benzamido/-4-chloroanthraquinone and 20 g of n-octylamine under the conditions of Example 26 (residence time is 2 hours) 1.76 g of 1 -/4-butylphenylene-4- benzamido/-4-octylaminoanthraquinone are obtained (77.2% of theory). M.p. 200-201 C.

Found, %: C 80.03, H 7.34, N 4.65. C39H42N203.

Calculated, %; C 79.86, H 7.17, N 4.78.

Example 38 0.44 g (0.00082 mol) of 1-/4-hexylbenzamido/-4-octylaminoanthraquinone and 0.8 g (0.0029 mol) of 4-butyldiphenylcarboxylic acid chloride in 15 ml of nitrobenzene are kept for 10 hours at a temperature within the range of from 180 to 1 85"C. The reaction mixture is cooled, the residue is filtered and washed with alcohol, recrystallized from acetone to give 0.2 g (31.75%) of 1-/4-hexylbenzamido/-4-/N-octyl-(4 butylphenylene-4-benzamido)/-anthraquinone. M.p. is 238-240"C.

Found, %: C 81.79, H 6.58, N 3.57. C52H49N2O4.

Calculated, %; C 81.57, H 6.40, N 3.66.

Example 39 0.15 g (0.0004 mole of 1-amino-4-/4-n-butylphenoxy/-anthraquinone and 0.3 (0.001 mol) of 4 hexyldiphenylcarboxylic acid chloroanhydride in 5 ml of nitrobenzene are kept at a temperature of from 160 to 164"C for 1.5 hour. The reaction mixture is cooled to the temperature of about 60"C and added with 20 ml of alcohol. The precipitate is filtered, washed with alcohol, dissolved in chloroform and eluted with SiO2 using a mixture of benzene-acetone (10:1) to give 0.17 g of 1 -/4-hexylphenylene-4-benzamido/-4-/ 4-n-butylphenoxy/-anthraquinone (65.9% of theory). M.p. 246-248 C.

Found, %: C 81.29, H 6.71, N 2.36. C43H41NO4.

Calculated, %: C 81.26, H 6.45, N 2.20.

Example 40 0.78 g (0.0028 mol) of 1,5-diamino-4,8-dihydroxyanthraquinone and 2.39 g (0.01 mol) of heptylbenzoic acid chloride in 20 ml of nitrobenzene are boiled for one hour, the reaction mixture is cooled to the temperature of 60"C and added with 30 ml of alcohol with stirring. The reaction mixture is then brought to boiling, then cooled to 20"C, filtered and washed with alcohol. The residue is dissolved in chloroform and chromatographed through SiO2. The eluent is chloroform. 1.5 9 of 1 ,5-bis-/4-heptylbenzamido/-4,8- dihydroxyanthraquinone are obtained (76.92% of theory). M.p. 251-2520C.

Found, %: C 74.61, H 6.75, N 4.17. C42H46N206- Calculated, %; C 74.80, H 6.90, N 4.10.

Example 41 Under the conditions of Example 40, from 0.5 9 (0.0018mol) of 1 ,8-diamino-4,5-dihydroxyanthraquinone, 1.3 9 (0.0054 mol) of heptylbenzoic acid chloride in 20 ml of nitrobenzene there is obtained, (a) after chromatography in a column with SiO2, 0.229 (13.6% of theory) of 1,8-bis-/4-heptylbenzamido/-4-/ 4-heptylbenzyloxy/-5-hydroxyanthraquinone (crimson spot). M.p. above 250 C.

Found. %: C76.54, H7.12, N 3.37. C66H64N207 Calculated, %: C 76.7, H. 7.4, N 3.2.

(b) A second spot of violet colour is eluted; after distilling-off the solvent there is obtained 0.25 9 of 1,8-bis-/4-heptylbenzamido/-4,5-dihydroxyanthraquingne (20% of theory). M.p. 226-227"C.

Found, %: C 74.57, H 6.82, N 4.03. C42H46N2O6.

Calculated, %: C 74.8, H 6.9, N 4.1.

Example 42 0.2 9 (0.0003 mol) of 1 ,8-bis-/4-heptylbenzamido/-4,5-dihydroxyanthraquinone in 20 ml of pyridine are heated nearly to boiling, added with 0.5 g (0.002 mol) of heptylbenzoic acid chloride and boiled for 15 minutes. The reaction mixture is cooled to 20"C, filtered and washed with ethanol. There is obtained 0.32 9 (quantitative yield) of 1,8-bis-/4-heptylbenzamido/-4.5-bis-/4-heptylbenzyloxy/-anthraquinone. M.p. is above 300 C.

Found, %: C 77.81, H 7.53, N 2.64. C70H82N208- Calculated, %; C 77.9, H 7.7, N 2.6.

Example 43 Under the conditions described in Example 42, from 0.2 9 (0.0003 mol) of 1,5-bis-/4-heptylbenzamido/ -4,8-dihydroxyanthraquinone and 0.5 9 (0.002 mol) of heptylbenzoic acid chloroanhydride there is obtained 0.32 g (quantitative yield) of 1,5-bis-/4-heptylbenzamido/-4,8-bis-/4-heptylbenzouloxy/anthraquinone. M.p. is above 280"C.

Found, %: C 77.74, H 7.58, N 2.35. C70H82N208- Calculated, %: C 77.9, H 7.7, N 2.6.

Examples 44 through 87 In 0.99 9 of a liquid-crystal mixture of ZhK-807 (a mixture of cyanobiphenyls) the dyestuff of Examples 1 to 43 is dissolved in an amount of 0.01 g, the mixture under stirring is brought to the isotropic state and cooled to room temperature. The mixture is ready for use. Table 2 shows spectral characteristics of the resulting liquid-crystal materials.

TABLE 2

u) Dyestuff of No Example No. nm S c 430 -0,04 n t O N 434 -0,09 45 2. H15c7CONH / \ Cl 0 0 IX K 440 -0,08 46 3. H17C6ffTh\mNH Br o 0 t U HpC8ff\C0NH NHCO ffThC\\i W B E A I I I I o Z Q C D llJ N N t X Z ~ t m t t

o o v I Dyestuff of Dyestuff formula ,nm S No Example No.

4 5 I 2 3 X 5. o N 00 L d 1N 0 0 11 1, 7. H9C4CONH Q \ NHG0mC/\ & s 508 -0,33 7 1 z I o o Z co E a) X 2 X N U) tD E > j o [OD

< o Example Dyestuff of Dtff formula O " No Example No. yesu I 2 3 4 5 X 8. H19C9CCNH o o NHCCCH 510 -0,36 S N 520 -0,29 52 9. HC5OOONH / \ NHCQm\OC5Hn o 0 ~ 53 10. )iz,C18OCONH / \ NHCOOCH 520 -0,30 o 0 x7i W 11. H9C0NH z r O I 0 O I O 0 XVIII I so Z a en E C] Xj CO Q X t N ID

o Dyestuff of 9 Dyestuff formula o o No Example No. I c c z t N o o (o 56 13. HC17CONH / \ 500 -0,13 CONHq7H3 o" r, o I In I o NHG15H o 0 Xi, HO "O OH 582 -0,24 I o C X I o o I o z O xii I vo Z m to E Q X {.D (D o CO

mm o o o' No Example No. Ò Ò Ò 5 I 2 3 4 LO U) t 0 0 WllI 60. 17. H15O7O0NH / \ Oo H 595 -0,21 I t 61. 18. HG4ffTh\CO0 / \ 00C & f\C4H9 415 -0,19 O 0 I 9 0 I Xo zo Q iSi C a X c c $ o oz o

s Dyestuff of No Example No. nm S O 62. 19. H15C7O0NH m X 0 0 If L / I 63. 20. HC8Mff\Coo / \ 500 -0,13 Oh o 21. H1708Mm/\oONH o o Cl ~ X X I O I c T > I o q 7 O a :I Q E 2 ILi N < S r $ z N e

N - - ~ V) u, N No Example No. o' I E 65. 22. Hi? C8 ffTh\C0NH t o NH00 H 590 -0,22 u, 66. 23. 576 -0,25 -HN NH-CH C8H17 l78 CH30 0 - xx,, CH 67. 24. NHOO Mff\C8 H 446 -0,22 I0iW y-o CH3 $ I t0 I (9,9 I so Z Q aw E O an 2 X CN O CN E $ o S &commat;

U) W) o O N I I No Example No. nm S 3 c 68. 25. CH c o LD S CH ~~ "I OH3 XXXII NHCO C-CH3 OH3 69. 26. 0 0--00-0 578 -0,23 XThxiII N QNHC8 H17 70. 27. 0 NHCO06 H3 580 -0,2 N 8 i H)2 0X0 X 0S so Z Q vo E 2 X {g) N tN E $ ao (D N

vJu, N of a) No Example No. k,nm S I 2 3 4 5 71. 28. 0 N'HCO Os H1 590 -0,13 u, o aJ co u, 1 XXXV NHD 0C4H9 72. 29. 0 NHCO mTh\CaH17 605 -0,22 N II f E cS H3 73- 30 0 NHCOMff\H 580 -0,29 90 Z Q uz E tD X cO o CS n Q E

O r v, m Dyestuff of O O O O No I I I No.

E S 2 3 4 5 S 31 Is -0,30 V)(D Loud 621 -0,31 $1') O HN OQ) O oo 75. 32. 0 NHOO ffTh\C8H17 658107 N H)2 76. 33 550 -0,28 m I N Nil cH p I CH3 CH o Z Q X Q

S CS N r Example Dyestuff of Dyestuff formula No Example No. ,nm 5 E 77. b 0NHC0 ffTh\oa Co 580 b NIIW 0 I I 78. 35 580 -0,32 ONHCO \C6 o" 618 -0,32 K11N N O NCH92 79. 36 578 -0,31 617 -0,31 0 I 0 I I U i 0S0 0S 0X0 o o Z Q uz E 2 X N t Co (D Q E $ o oo

u, Dyestuff of 1 No Example No. I S E XI f cco cr, a, u, 80. 37 o U 0 NHO49 616 -0,32 N Wiv o NHC9 H17 81. 38 496 -0,34 o NH613 508 N VA S H17 h ffTh\/\O4H9 82. 39 445 -0,24 o NHOO $.llw t; li H9 oXo oW Xo o o Z it &commat; Q tO E ao X > x r n uj N CO X X z oo co tD

r r- n cr, Ò Ò O O of S No Example No. Dyestuff formula ;',nrn 2 3 4 5 83. 4 NHG0C7H15 562 N O CD X (D O (D O tt LO 600 -0,18 1&commat;1 0 OH 600 84. I I I r 0 0 OH 85. 41(b) 536 -0,36 m 0 NHO0O7H15 N II X7tX %0D0O7H15 D Z < O 0X0 0X0 9= Z < I ItI 3 : < o 1 1 O ,h, n C I o o Z C] X N t e t E $ O n 00 CO

O cs v, m g of o o No Example No. nm S I 2 3 4 5 86. t t oo N NII H15ŎCO 0 OCOO7His 87. b( I I O n 0X0 030 o oo D I I I I o Q u, E > 4 X CS N E uj Z ~ O oo Examples 88 through 95 W-. liquid-crystal material for electrooptical devices, which simultaneously serves as a dichroic working body of an electrooptical device, is prepared by mixing of a known liquid-crystal matrix with a known dyestuff having a positive or negative dichroism and one or more dyestuffs with a negative dichroism corresponding to the general formula (I).Specific compositions of the dichroic working body (liquid-crystal t-'aterial) are shown in Table 2 hereinbelow. The device, wherein this dichroic working body is employed, is illustrated by the accompanying drawing.

The liquid-crystal material, i.e. dichroic working body 1, is placed between two transparent plates 2 transparentelectrndes 3 and orienting layers (not shown). The thickness of the dichroicworking body 1 (liquid-crystal material) of 10-20 Fm is adjusted by means of gaskets (not shown). The initial orientation of the liquid crystal is planar. The background may be of any colour and it depends mainly on the dyestuff with 3 positive or negative dichroism.

The device operates in the following manner.

In the initial state, voltage is applied to the dichroicworking body 1 interposed between transparent electrodes 3 and supported by the orientating layers. Upon application of an AC voltage of 5-10 V the orientation of the molecules of the iiquid-crystal material is changed to the homeotropic and a symbol appears with its colour differing from the background colour. The colour changes perceived by man's eye for various embodiments of the liquid-crystal material are shown in Table 3. The colour switching-over is observed with a greater contrast in the case of using a polaroid.

TABLE 3

Example Dichroic working body (liquid-crystal material) Degree of Colour No. Liquid- Dichroic dyestuff and its content, % ordering of switching crystal by weight the dyestuff observed matrix molecules 2 3 4 5 S8 RO-SA-605 Blue dyestuff with positive dichroism 0.6 (600 nm) Blue-green oftheformula: -0.29 (410 nm) n ~u N N N-- N NsiNO2 LTI + 1% by weight of yellow dyestuff of formula (I) of Example 18 89 P.C3-SA-605 Blue dvesruffwith positive dichroism 0.6 (600 nm) Blue-red other . mule: -0.14(510nm) %1{{NT7INMNO2 NO2 + 2% of red dyestuff of formula (I) of Example 6 90 Zhi < -8074- or 0.5% of yellow dyestuff with positive 00.22 (430 nm) Yellow-bluish ZhK-614* or dichroism of the formula: -0.12 (595 nm) -green OhI+N=N ~ ff11 ZhK-91 0 + 2% of blue dyestuff with negative dichroism of formula (I) of Example 17 TABLE 3 (continued)

2 3 4 5 91 ZhK-807 or 0.5% of yellow dyestuff with positive 0.6 (430 nm) Yellow-red ZhK-614 or dichroism of the formula: -0.05 (506 nm) ZhK-910 A Sz 7 7 7 and 2% of red dyestuff of formula (I), Example 6 92 ZhK-807 or 0.3% red dyestuff with positive 0.62(500 nm) Red-blue ZhK-910 or dichroism + 4% of blue dyestuff with -0.11 (630 nm) ZhK-614 or negative dichroism of Example 15 Zh K-654* 93 ZhK-807or 0.5%ofyellowdyestuffwith positive - Orange-black ZhK-910 or dichroism of Example 49 + 2% of blue ZhK-614 or dyestuff with negative dichroism of ZhK-654 Example 17 + 1% of orange dyestuff with zero dichroism of the formula: N aN1 H37 C,8 H37 94 ZhK-807 or 1.2% of dyestuff having a band in the 0.55(420 nm) Yellow-red ZhK-910 or yellow region of spectrum with positive -0.29 (516 nm) ZhK-614 dichroism and a band at 550 nm with negative dichroism of the formula:: H,7C8 Nt\NN =CH N II N CH = N- N4ThNooCeHl7 + 2% of red dyestuff with negative dichroism of Example 6 95 ZhK-807 or 5% by weight of tetrazine of the formula: -0.3 (530 nm) Pale red-red ZhK-910or N-N tiqfI /7 N=N ffc6H13 ZhK-614 vNN9 or ZhK-654 + 1% of red dyestuff with negative dichroism, Example 6 *RO-SA-605 - liquid-crystal material with positive dielectric anisotropy available from the company Hoffman La Roche ZhK-807 - liquid-crystal material with positive dielectric anisotropy based on alkyl- and alkoxycyanobiph nyls TABLE 3 (Continued) ZhK-614 - liquid-crystal material with positive dielectric anisotropy based on alkylcyano phenyl esters ZhK-654 - liquid-crystal material with positive dielectric anisotropy based on alkyl cyanophenyl esters and azooxy compounds ZhK-910 - liquid-crystal material with positive dielectric anisotropy based on alkyl cyclohexanecarboxylic acid

Claims (12)

1. Anthraquinone derivatives of the general formula (I):

wherein A, M, B, Z are the same or different substituents having a meaning: R' DX or R2EY, wherein R1 and R2 are the same or different alkyls C4 to C18,

X, Y are the same or different and represent each oxygen or a group Nh, NR3, E is an ordinary bond,

or Y+E+R2=H,Cl,Br,NO2, NR3R4, wherein R3 is a C1-C8 alkyl, R4is H or C4H9, or R3 + R4= #CH2#5, n=0 or 1, m = 0,1 or 2; excluding compounds wherein A = M = B = Z = H = Cl, Br, NO2, NR3R4.

2. An anthraquinone derivative according to claim 1, selected from: 1,4-bis-[4-(4-octylphenylene)-benzamido]=anthraquinone (Compound 1); 1-[4-(4-octylphenylene)-benzamido]-4-octylaminoanthraquinone (Compound 2); 1 ,8-bis-(4-heptylbenzamido)-4,5-bis-(4-heptylbenzoyloxy)-anthraquinone (Compound 3); 1-[4-(4-heXylphenylene)-benzamido]-4-dibutylamino-anthraquinone (Compound 4); and 1,8-bis-(4-heptylbenzamido)-4-(4-heptylbenzoyloxy)-5-hydroxy-anthraquinone (Compound 5);

3.An anthraquinone derivative according to claim 1, selected from: 1 -[4-(4-butyl phenyl)-benzamido]-anth raqu inone; 1 -(4-heptylbenzamido)-4-chloroanthraquinone; 1,[4-(4-octylphenylene)-benzamido]-4-bromoanthraquinone; 1 ,4-bis-(4-heptylbenzamido)-anthraquinone; 1 ,4-bis-(4-hexylbenzamido)-anthraquinone; 1,4-bis-(4-butyl benzamido)-anthraquinone; 1 ,4-bis-(4-nonylbenzamido)-anthraquinone; 1 ,4-bis-(4-amyloxybenzamido)-anthraquinone; 1,4-bis-(4-octadecyloxybenzamido)-anthraquinone; 1,4-bis-(4-butyl-trans-cyclohexylamido)-anthraquinone; 1,4-bis-(4-hexyl-cyclohexylamido)-anthraquinone; 1,4-bis-stearlyamidoanthraquinone; 1,4-bis-octadecylamino-5,8-dihydroxyanth 1-(4-heptylbenzamido)-4-octadecylaminoanthraquinone; 1-(4-heptylbenzamido)-4-piperidinoanthraquinone; 1 -(4-heptylbenzamido)-4-(3-octadecyloxyanilino)-anthraquinone; 1,4-bis-(4-butyldiphenylcarboxy)-anthraquinone; 1 ,5-bis-(4-heptylbenzamido)-anthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-(4-octylidiphenylcarboxy)-anthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-chloroanthraquinone; 1 -[4-(4-octylphenyl)-benzamido]-4-(3-octadecyloxyanilino)-anthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-[1-(4-octyldiphenyl)-ethylamino]-anthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-(4-t-butylphenoxy)-anthraquinone; 1,4-bis-(4-t-butylbenzamido)-anthraquinone; 1 -(4-hexylbenzamido)-4-octylaminoenthraquinone; 1 -(4-hexylbenzamido)-4-dibutylaminoanthraquinone; 1 -(4-hexylbenzamido)-4-(3-butoxyphenylamino)-anthraquinone; 1 -[4-(4-octylphenyl)-benzamido]-4-(4-butylphenylamino)-antraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-butylaminoanthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-(1-ethylpentylamino)-antraquinone; 1 -[4-(4-octylphenyl)-benzamido]-4-dibutylaminoanthraquinone; 1 -[4-(4-octylphenyl)-benzamido]-4-[1 -(4-t-butylphenyl)-ethylamino]-anthraquinone; 1-[4-(4-octylphenyl)-benzamido]-4-octylanthraquinone; 1 -[4-(4-butyl phenyl )-benza mido]-4-octylanthraqu inone; 1-(4-hexylbenzamido)-40[N-octyl-(4-[4-butylphenyl]-benzamido)]-anthraquinone; 1-[4-(4-hexylphenyl)-benzamido]-4-(4-n-butylphenoxy)-anthraquinone; 1,5-bis-(4-heptylbenzamido)-4,8-dihydroxyanthraquinone; 1,8-bis-(4-heptylbenzamido)-4,5-dihydroxyanthraquinone; and 1,5-bis-(4-heptylbenzamido)-4,8-bis-(4-heptylbenzoyloxy)-anthraquinone.

4. Amethod for preparing anthraquinone derivatives as claimed in claim 1, comprising acylation of anthraquinone derivatives of the general formula (ll):

wherein W, T, L, K are the same andior different substituents NH2, NHR3, OH, H, Cl, Br, NO2, NR3R4, wherein R3 is a C,-C8 alkyl, R4 is H or C4H9, R3 + R4 = + CH2 5 by means of acid chlorides of the general formula: R1DCl (III) wherein R1 is a C4-Cn8 alkyl,

n = 0, 1; m = 0, 1, 2, in an organic solvent medium, provided that when a compound of the general formula (II) contains Cl, Br, NO2 as a substituent, then the compound resulting from acylation is subjected to treatment with substituted amines of the general formula (IV): R2EQ (IV) wherein R2 is a C4-C18 alkyl, E is an ordinary bond,

n =0or1,m = 0,1,2, Q = NH2, NHR3, wherein R3isaC1-C8alkyl.

5. A liquid-crystal material comprising a liquid-crystal matrix and at least one derivative of anthraquinone of the general formula (I):

wherein A, M, B, Z are the same or different substituents having meanings R1DX, R2EY, wherein R1 and R2 are the same or different and represent each a C4-C18 alkyl,

X, Y are the same or different and represent each oxygen or a group NH, NR3, E is an ordinary bond,

or Y + E + R2 = H, Cl, Br, NO2, NR3R4, wherein R3 is a C1-C8 alkyl, R4 is hydrogen or C4Hs, R3 + R4 = + CH2, = O or 1, m = 0, 1,2, excluding the compounds, wherein A = M = B = Z = H, Cl, Br, NO2, NR3R4, and, when required, an optically active additive and/or a dyestuff having positive dichroism.

6. A liquid-crystal material according to claim 5, containing at least one compound according to claim 2.

7. A liquid-crystal material according to claim 5, containing at least one compound according to claim 3.

8. A liquid-crystal material according to any of claims 5 - 7, wherein the anthraquinone derivative is used in an amountoffrom 0.1 to 10% byweight.

9. An electrooptical device comprising a dichroic body which is a liquid-crystal material according to any of claims 5 - 8, interposed between optically transparent plates having transparent electrodes applied to their inner sides and provided with a power supply source.

10. An anthraquinone derivative of a method for preparing same substantially as described in the Specification and Examples 1 to 43 hereinbefore.

11. A liquid-crystal material substantially as described in the Specification and Examples 44 to 87 hereinbefore.

12. A electrooptical device substantially as described in the Specification and Examples 88 to 95 herein before.