Liquidcrystalline cyclohexylbenzene derivatives their manufacturing and novel nematic admixtures containing same

Claim 2

A cyclohexylbenzene derivative of the general formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO, -CH₂O-. -OCH₂, -COCH₂-, -CHOHCH₂-, -CH=CH-,-CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂-, -CHOCH₃CH₂-; Y is a terminal group from the set: -NO₂, -NH₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, then k+1 also may assume the value of 1.

Claim 3

The compound as claimed in claim 1 wherein k=1 and l=0 and said formula is Ia: wherein R¹ is a normal or branched alkyl chain; X is the bridging group -COO- or -OCO-; Y is the terminal group -NCS -NO₂ or -Br or -Cl or -F.

Claim 4

The compound as claimed in claim 1 wherein k=0 and l=1 and said formula is Ib: wherein R¹ is a normal or branched alkyl chain or a normal or branched alkxoy group; X is the bridging group -COO- or -OCO-; Y is the terminal group -NO₂ or -NCS or -Br or -Cl or -F.

Claim 5

The compound as claimed in claim 1 wherein k=1 and l=1 and said formula is Ic: wherein R¹ is a normal or branched alkyl chain; X is bridging group from the set: -COO-, -OCO-, CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂-, -CHOCH₃CH₂-; Y is terminal group from the set: -NO₂, -NH₂, -NCS, -Br, -Cl, -F

Claim 6

The compound as claimed in claim 4 wherein said formula is Ic4C: wherein R¹ is a normal or branched alkyl chain of 1-12 carbon atoms.

Claim 7

The compound as claimed in claim 5 wherein R is butyl or pentyl or hexyl or heptyl.

Claim 8

The compound as claimed in claim 1 wherein k=0 and l=2 and said formula is Id: wherein R¹ is a normal or branched alkyl chain or a normal or branched alkoxy group; X is bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂-, -CHOCH₃CH₂; Y is a terminal group from the set: -NO₂, -NH₂,-NCS,-Br, -Cl, -F.

Claim 9

The compound as claimed in claim 1 wherein k=2 and l=0 and said formula is Ie: wherein R¹ is a normal alkyl chain; X is bridging group from the set:-COO-,-OCO-,-CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂-, -CHOCH₃CH₂-, Y is a terminal group from the set: -NO₂, -NH₂, -NCS, -Cl,-Br,-F.

Claim 10

Method of manufacturing cyclohexylbenzene derivative of the general formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n or a normal or branched alkoxy group H 2n+1 C n O, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂, -CHOCH₃CH₂-; Y is a terminal group from the set: -NO₂, -NH₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain somtimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, then k+1 also may assume the value of 1, is characterized in that a compound of the formula II.A is used: wherein r is 0 or 1; Z is a hydroxy group or halogen and the cyclohexane ring is a trans-1,4-disubstituted one and the benzene ring is 1,4-disubstituted one having sometimes additionally a fluorine atom in position 2 or 3, which is converted by known methods: a)directly to the compound of formula I, wherein Y is -NO₂ terminal gorup and then this compound is converted by known methods to the compound of formula I wherein Y is a -NH₂ o -NCS or -F or -Cl or -Br terminal group or b)to the compound of formula II: wherein Z is a hydroxy group or halogen atom, preferably chlorine or bromine; s and r are arbitrarily chosen numbers from the set of numbers 0 and 1; the cyclohexane ring is a trans-1,4-disubstituted one, and the benzene ring is 1,4-disubstituted one containing sometimes additionally a fluorine atom in position 2 or 3; Y is a terminal group form the set: -NH₂, -NCS, -F, -Cl, -Br, and besides if s is zero, also NO₂ and the compound II is next converted to compound I by known methods.

Claim 11

Method of manufacturing cyclohexylbenzene derivative of the general formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n or a normal or branched alkoxy group H 2n+1 C n O, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-, -CHFCH₂, -CHOCH₃CH₂-; Y is a terminal group from the set: -NO₂, -NH₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain somtimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, then k+1 also may assume the value of 1, is characterized in that a compound of the formula II.A is used: wherein r is 0 or 1; Z is a hydroxy group or halogen and the cyclohexane ring is a trans-1,4-disubstituted one and the benzene ring is 1,4-disubstituted one having sometimes additionally a fluorine atom in position 2 or 3, which is converted by known methods: a)directly to the compound of formula I, wherein Y is -NO₂ terminal gorup and then this compound is converted by known methods to the compound of formula I wherein Y is a -NH₂ o -NCS or -F or -Cl or -Br terminal group or b)to the compound of formula II: wherein Z is a hydroxy group or halogen atom, preferably chlorine or bromine; s and r are arbitrarily chosen numbers from the set of numbers 0 and 1; the cyclohexane ring is a trans-1,4-disubstituted one, and the benzene ring is 1,4-disubstituted one containing sometimes additionally a fluorine atom in position 2 or 3; Y is a terminal group form the set: -NH₂, -NCS, -F, -Cl, -Br, and besides if s is zero, also NO₂ and the compound II is next converted to compound I by known methods.

Claim 12

The method of manufacturing cyclohexylbenzene derivatives as claimed in claim 9 characterized in that the compound of formula II.A wherein r=1 and Z is a chlorine atom or the compound of formula II wherein Z is a chlorine atom, s=1, r=1 and Y is -Br or -Cl or -F acylates in an organic solvent the compound of formula III: wherein R¹, k and l have the same meaning as in formula I with the profiso that l=0 and the obtained keto compound of formula I.1: wherein R¹, k and l are the same as in formula III and Y is -NO₂ or -Br or -Cl or -F is transformed through a reduction with sodium borohydride to the compound of formula I.2: wherein R¹, k, l and Y are the same as in formula I.1, which after purification is the final product or substrate for further reactions; thus the compound of formula I.2 is heated in presence of a solvent, advantageously toluene, and acid, advantageously p-toluenesulfonic acid, and it is dehydrated to an ethylene derivative of formula I.3: wherein R¹, k, l and Y are the same as in formula I.2, which after purification is the final product or which by reduction with hydrogen in presence of palladium catalyst is further transformed to the compound with the -CH₂CH₂- bridging group of formula I.4: wherein R¹, k and l are the same as in formula I.3 and Y is -NH₂ or -Cl or -Br or -F ; or the compound of formula I.2 is heated with thionyl chloride and is converted to the compound of formula I.5: wherein R¹, k, l and Y are the same as in the formula I.2, which after purification is the final product or which is further transformed to a compound with the bridging group -CHCNCH₂- of formula I.6: wherein R¹, k, l and Y are the same as in formula I.5, by heating with KCN in dimethylsulfoxide and purified by known methods; or the compound of formula I.2 is heated with hydrobromic acid and is transformed to a compound with the -CHBrCH₂ bridging group of formula I.7: wherein R¹, k, l and Y are the same as in formula I.2, which after purification is the final product or is further transformed to a compound with the -CHFCH₂- bridging group of formula I.8: wherein R¹, k, l and Y are the same as in formula I.7, by heating with KF in ethylene glycol,which after purification is the final product.

Claim 13

Method of manufacturing cyclohexylbenzene derivatives as claimed in claim 9, characterised in that the compound of formula II.a, wherein Z is a chlorine atom or hydroxyl group and r=0, or the compound of the formula II wherein Z is a chlorine atom or hydroxyl group, s=1 and r=0 is treated with a compound of alcohol or phenol properties of the general formula IV: wherein p=0 and R¹, k and l are the same as in formula I, and the thus obtained ester is next separated and purified by known methods, advantageously by crystallization.

Claim 14

Method of manufacturing cyclohexylbenzene derivatives as claimed in claim 9, characterised in that the compound of formula II, wherein Z is hydroxyl group s=0 and r=0, is converted to alcoholate by known method, and then treated with halogenide obtained from the compound of formula IV, wherein p=1, in organic solvent, advantageously in cyclohexane or dioxane or tetrahydrofurane, and next the obtained final product is separated and purified by known methods, advantageously by crystallization.

Claim 15

Method of manufacturing cyclohexylbenzene derivatives as claimed in claim 9, characterised in that the compound of formula II, wherein Z is a chlorine or bromine atom, s=0 and r=1, is treated with sodium or potassium phenolate or alcoholate obtained from the compound of formula IV, wherein p=0, advantageously in cyclohexane or dioxane or tetrahydrofurane, and next the obtained final product is separated and purified by known methods, advantageously by crystallization.

Claim 17

A liquid crystalline composition being an admixture of two at least components including at least one component expressed by formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, CH₂CH₂-, -CHClCH₂-, CHCNCH₂-, -CHBrCH₂-, CHFCH₂-, CHOCH₃CH₂-; Y is a terminal group from the set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group,then k+1 also may assume the value of 1.

Claim 18

A liquid crystalline composition being an admixture of two at least components including at least one component expressed by formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, CH₂CH₂-, -CHClCH₂-, CHCNCH₂-, -CHBrCH₂-, CHFCH₂-, CHOCH₃CH₂-; Y is a terminal group from the set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group,then k+1 also may assume the value of 1.

Claim 19

The liquid crystalline admixture as claimed in claim 15 wherein component of formula I is used in a quantity of 5 to 50 wt.%.

Claim 20

An improvement of the liquid crystalline admixture comprising 4-(trans-4-n-alkylcyclohexyl)benzeneisothio­cyanates characterised in that the improvement results from introducing compound of formula I wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH- -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, CHBrCH₂-, CHFCH₂-, -CHOCH₃CH₂-; Y is a terminal groupn from the set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disub­stituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, the k+1 also may assume the value of 1.

Claim 21

An improvement of the liquid crystalline admixture comprising 4-(trans-4-n-alkylcyclohexyl)benzeneisothio­cyanates characterised in that the improvement results from introducing compound of formula I wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH- -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, CHBrCH₂-, CHFCH₂-, -CHOCH₃CH₂-; Y is a terminal groupn from the set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disub­stituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, the k+1 also may assume the value of 1.

Claim 22

The improvement in an electrooptical cell comprising a liquid crystal dielectric disposed between two electrode plate, at least one of them is transparent, characterised in that the applied liquid crystal dielectric is an admixture comprising compound of formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-,-CHFCH₂-, -CHOCH₃CH₂-; Y is a terminal group fromt he set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, the k+1 also may assume the value of 1.

Claim 23

The improvement in an electrooptical cell comprising a liquid crystal dielectric disposed between two electrode plate, at least one of them is transparent, characterised in that the applied liquid crystal dielectric is an admixture comprising compound of formula I: wherein R¹ is a normal or branched alkyl group H 2n+1 C n - or a normal or branched alkoxy group H 2n+1 C n O-, n being an integer number from 1 to 12; X is a bridging group from the set: -COO-, -OCO-, -CH₂O-, -OCH₂-, -COCH₂-, -CHOHCH₂-, -CH=CH-, -CH₂CH₂-, -CHClCH₂-, -CHCNCH₂-, -CHBrCH₂-,-CHFCH₂-, -CHOCH₃CH₂-; Y is a terminal group fromt he set: -NO₂, -NCS, -Cl, -Br, -F; the cyclohexane rings are trans-1,4-disubstituted ones and the benzene rings are 1,4-disubstituted ones, and besides one of them may contain sometimes additionally a fluorine atom in position 2 or 3; k and l are integer numbers from the set: 0, 1, 2 fulfilling the condition that k+1=2 or 3; besides, if X denotes the -COO- or -OCO- group, the k+1 also may assume the value of 1.