PL177052B1 - 3,6 substituted cyclohex-2-en-1-ones and method of obtaining them - Google Patents

Abstract

1. The method of obtaining new 3,6-substituted cyclohex-2-en-l-ones of the general formula I, wherein Rl and R2 they are the same or different and represent a terminal group selected from the set: Y- (CH2) n- (O) m- (CH2) k- (O) l- (CH2) p-, Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, -COOCnH2n + 1, -NCS; n, p and k take the values from 0 to 7, m and 1 are 0 or 1; Z1 and Z2 are the same or different and represent a bond single, CH = CH, C = Calbo CH2-CH2, Al - is one of the fragments represented by formulas 2-10 and A2 is a bond single or one of the fragments marked with patterns 2-10, where X1, Χ2, Χ3, and X4 are independently hydrogen or fluorine or chlorine, or a -CH3 or -CN group and B, Bl and B2 are independently a single bond or a bridging group such as CH2-CH2, CsC, CH = CH, OCH2, CH20, wherein the condition is satisfied that if B in formulas 2-10 means a single bond is Z2 represents a group CH = CH; s = 0 and t = l, characterized in that the acetoacetic acid esters of formula 11, w where A2 is a single bond or one of the fragments denoted by the formulas 2-10, R2 is the group Y- (CH2) n- (O) m- (CH2) k- (O) l- (CH2) p- or Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl a terminal group such as -CN, OCF3, CF3, -COOCnH2n + 1, -NCS, R3 is an alkyl group containing from 1 to 10 carbon atoms, preferably two, a compound of formula 12, wherein Rl is Y- (CH2) n- (O) m- (CH2) k- (O) l- (CH2) p- or Y- (CH2) n-CH = CH- <CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, .CF3, -COOCnH2n + 1, -NCS, Al is one of the fragments represented by formulas 2-10, Z2 is a bond single, CH = CH; C = C or CH2-CH2;

Description

The subject of the invention is a process for the preparation of compounds of general formula I, in which R1 and R2 are the same or different and represent a terminal group selected from the set: Y- (CH ₂ ) n- (O) _m - (CH ₂ ) k- (O ) i- (CH2) p-, Y- (CH2) n ^ I ^ = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, -COOCnH2n + 1, -NCS; n, peak ranges from 0 to 7, m and 1 are 0 or 1; Z1 and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10 , where Xp Χ2, Χ3 and Χ4 are independently hydrogen or fluorine or chlorine, or -CH3 or -CN and B, B1 B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH , OCH2, CH2O, provided that if B in formulas 2-10 is a single bond, then Z2 represents a group CH = CH, s = 0, and t = 1, characterized in that acetoacetic acid esters of formula 11, in wherein A2 is a single bond or one of

177,052 fragments marked with the formulas 2-10, R2 represents the group Y- (CH2) n- (O) m- (CH2) k- (O) i- (CH2) or Y- (CH2) n-CH = CH- ( CH2) p-, where Y is H, F, Cl a terminal group such as -CN, OCF3, CF3, -COOC "H2n + i, -NCS, R3 is an alkyl group having 1 to 10 carbon atoms, preferably two, with a compound of formula 12 wherein R 1 is a Y- (CH2) n- (O) m- (CH2) k- (O) i- _(CH2) p-, or Y- (CH2) n-CH = CH - (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, CF3, -COOCnHn + i, -NCS, A1 is one of the fragments marked with formulas 2-10, Z2 is single bond, CH = CH; C = C or CH2-CH2; X is piperidyl, pyrrolidyl, morphonylyl or a dialkylamino group having from 1 to 15 carbon atoms, preferably a methyl, ethyl or propyl group, heated in organic solvents such as alcohols or ethers in the presence of alkoxides, inorganic bases or alkali metal salts, preferably NaOH or KOH, Na2CO3 or K2CO3 and then the condensation product is treated with an aqueous acid solution, preferably sulfuric acid, and separated from the reaction mixture by known methods, preferably by extraction.

The subject of the invention is a process for the preparation of compounds of general formula I, in which R1 and R2 are the same or different and represent a terminal group selected from the group: Y- (CH2) _n - (O) m- (CH2) _k - (O) 1- (CH2) p-, Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, - COOCnH2n + i, -NCS; n, peak ranges from 0 to 7, m and 1 are 0 or 1; Z1 and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10 where Xp Χ2, Χ3 and Χ4 are independently hydrogen or fluorine or chlorine, or a group -CH3 or -CN and B, BO B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH , OCH2, CH2O; s = 1 and t = 1. This method involves heating acetoacetic acid esters of formula 11, in which A2 is a single bond or one of the fragments marked with formulas 2-10, R2 is the group Y- (CH2) _n - (O) _m - (CH2) k- (O ) i- (CH2) p- or Y- (CH2) _n -CH = CH- (CH2) P-, where Y is H, F, Cl terminal group such as -CN, OCF3, CF3, -COOOHbn + and , -NCS, R3 is an alkyl group containing from 1 to 10 carbon atoms, preferably two, with a compound of formula 13, wherein R1 is a group Y (CH _{2) n} - (O) _m - (CH2) k- (O ) i- (CH2) p- or Y- (CH2) _n -CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, - COOCnH2n + 1, -NCS, A1 is one of the fragments represented by formulas 2-10, Z2 is a single bond, CH = CH; C = C or CH2-CH2; X is pipeline, pyrrolidyl, morphonylyl or a dialkylamino group having 1 to 15 carbon atoms, preferably a methyl, ethyl or propyl group. The reaction is carried out in organic solvents such as alcohols or ethers in the presence of alkoxides, inorganic bases or alkali metal salts, preferably NaOH or KOH, Na2CO3 or K2CO3, and then the condensation product is treated with an aqueous acid solution, preferably sulfuric acid, and separated from the reaction mixture by known methods, preferably by extraction.

The essence of both reactions is the same. The difference between the compounds of formula 12 and the compounds of formula 13 is that the compound of formula 12 is monofunctional (it contains one group which is a precursor to the vinyl group) and the condensation reaction leads to the formation of one cyclohex-2-en-l- ring. onu as shown in Scheme 1. The compound of formula 13 is a difunctional compound and its use leads to the formation of a symmetrical molecule having two cyclohex-2-en-1-one rings as shown in Scheme 2. Designations in the formulas in Schemes 1 and 2 are the same as discussed above. The above-discussed methods for the preparation of liquid crystal cyclohex-2-en-1-ones 1 have an advantage over the method using chloroethyl ketones as a substrate, because the Mannich compounds (formulas 12 and 13) are easily obtained for a large number of structures. For example, Mannich compounds of the formulas 12 and 13 can be obtained in good yield, even when Z1 and Z2 are CH = CH. They are easily formed from benzylidene acetones, while the analogous styryl chloroethyl ketones are hardly available.

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The subject of the invention are compounds of the general formula 1, in which t = 1 and s represent the number 1 or 0, R1 and R2 are the same when s = t, and the same or different when s #t, and denote a terminal group from the set : Y- (CH2) _n - (O) _m - (CH ₂ ) k- (O) r (CH2) p-, Y- (CH ₂ ) n-CH = CHI- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, -COO (nH2n + i, -NCS; n, peak values are from 0 to 7, m and 1 are 0 or 1; Zi and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10, where Χ1 , Χ2, Χ3 and X4 are independently hydrogen or fluorine or chlorine, or a group -CH3 or -CN and B, BU B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH, OCH ₂ , CH2O, where for s = 0 it is met the condition that if B is a single bond then Z2 is the group · CH = CH.

The unsaturated cyclic ketones of the invention are often liquid crystalline compounds that exhibit nematic or smectic properties. They can be used as components of liquid crystal mixtures, especially as dopants for ferroelectric liquid crystal mixtures, but their chemical stability is not high, especially when the cyclohexenone ring is adjacent to the aromatic ring and the double bond to form a conjugated bond system. Therefore, they are of greater importance as intermediates for the synthesis of liquid crystal compounds with higher chemical and photochemical stability. In particular, they can be used to obtain 2,5-disubstituted cyclohexanone derivatives, which is the starting material for the preparation of liquid crystal compounds of cyclohexane or cyclohexene derivatives, as shown in Scheme 3, or aromatic derivatives, as shown in Scheme 4. Designations in the formulas in Schemes 3 and 4 are the same as discussed above after item Z3 and Z4, which represent a single bond or a CH2-CH2 group.

2,5-disubstituted cyclohexanone (formula 14) is obtained from 3,6-disubstituted cyclohex-2-enone (formula 1) by reduction with hydrogen in the presence of a palladium catalyst (preferably 10% Pd / C). The reduction is carried out in alcohols or ethers preferably in a mixture of isopropyl alcohol and dioxane (1: 1) in the presence of NaOH or KOH. The 2,5-disubstituted cyclohexanone is formed as a mixture of two isomers but with a predominance of the trans-isomer. The trans to cis isomer ratio is 4: 1 or higher. Which is an advantageous feature from the point of view of using it as a precursor of liquid crystal compounds. When the compound is obtained by other methods, the trans to cis isomer ratio is 2: 1 or less. ·.

Known methods of obtaining 2.5 disubstituted cyclohexan-1-ones rely on the use of 1,4-substituted cyclohex-1-enes, which are sequentially hydroborated by the action of LiBH4 and BF3 Et ₂ O and then oxidized with sodium dichromate in H2SO4, but the method turned out to be ineffective because compounds were formed as a by-product resulting from the opening of the cyclohexene ring (M. Hird et al., J.Chem. Soc. Perkin Trans., 2.2337 (1993). This method was used to obtain 5-pentyl-2- (4'-pentylbiphenyl-4-yl) cyclohexanone with a cis-trans isomer ratio of 1: 2. In the methods described so far for reducing cyldohexenones with hydrogen on palladium, the trans to cis isomer ratio is 2: 1 or lower (JP 62185036).

The trans isomer of 2,5-disubstituted cyclohexanone is used to prepare the trans isomer of the compounds of formulas 15.16 and 17 (scheme 3).

Fluorine disubstituted compounds of formula 15 (Scheme 3) are obtained by heating a ketone of formula 14 with sulfur diethylaminotrifluoride (DAST or its equivalents) in a solvent such as methylene chloride, benzene. Similar liquid crystal compounds containing two fluorine atoms in the geminal position were found in the work of M. Hird, et al.,

J.Chem.Soc.Perkin Trans 2, 1993 obtained by coupling 4- (alkyldifluorocyclohexyl) bromobenzene with phenylboronic acid derivatives in the presence of phosphine-palladium complexes (Pd (PPh3) 4). Due to the high price of the palladium catalyst and its high consumption, this method is generally only useful for the synthesis of small amounts of compounds. The compound of formula 16 is obtained by reducing the compound of formula 14 with hydrazine in the presence

177,052 strong bases, preferably KOH. The compound of formula 18 (scheme 3) is obtained in two steps. In the first step, the 2,5-disubstituted cyclohexanone is reduced with sodium borohydride or aluminum isopropylate to the alcohol of Formula 17, which is then dehydrated by heating in hydrocarbons, preferably toluene, in the presence of toluenesulfonic acid. The yield of the first stage of the reaction is close to 100%, the products formed are of high purity. The 1,4-substituted cyclohexene derivatives were synthesized by attaching Grignard compounds to cyclohexanones and the alcohol formed was dehydrated with concentrated H 2 SO 4 in THF. The mixture of cis and trans isomers may be used immediately after the reaction or the waste product after isolation of the trans isomer is used to prepare the compound of formula 18.

A preferred method of aromatizing a compound of formula 1 to obtain a compound of formula 19 (scheme 4) is to heat it with a two molar excess of PCl5 in aromatic or chlorinated hydrocarbons, preferably benzene, at a temperature above 50 ° C. A compound of formula 20 (scheme 4) is obtained from a compound of formula 1 by treating it with a Grignard reagent and the resulting product forms a diene by treatment with dilute acids, which is heated in high-boiling hydrocarbons, preferably xylenes in the presence of 10% palladium on carbon. A compound of formula 21 (scheme 4) is obtained by treating a compound of formula 1 with sodium boron hydride in alcohols at room temperature or elevated temperature, preferably 50 ° C, and the resulting diene is heated in the presence of Pd / C in aromatic hydrocarbons. The compound of formula 22 (scheme 4) is obtained by heating the compound of formula 1 in the presence of palladium on carbon in aromatic hydrocarbons, preferably xylene at a temperature of 200-220 ° C. The above-described methods are very convenient for obtaining laterally substituted terphenyl and quaterphenyl derivatives, the preparation of which by other methods is complex and multi-step. Known methods have used for this purpose coupling reactions of Grignard compounds (L.K.M.Chen, Mol.Cryst.Lią.Cryst., 123, 185 (1985)), obtained from biphenyl derivatives, with cyclohexanone.

Formulas 23 to 78 represent selected structures for the production of liquid crystals of the invention. Formulas 79 to 94 represent compounds which are obtained by hydrogenating the compounds of the invention.

The following are examples describing the preparation of compounds of formula 1, both relating to the condensation reaction and describing the preparation of 3,6-disubstituted cyclohex-2-en-l-ones and their use in the preparation of other liquid crystal compounds. The given examples illustrate the essence of the invention without limiting its scope.

Example 1. 3- (4-ethoxystyryl) -6-pentylcyclohex-2-enone-1

A mixture of α- (dimethylamino) ethyl 4-ethoxystyryl ketone hydrochloride (0.1 mol), 2-pentylacetylacetate (0.11 mol), sodium isopropylate (0.12 mol) and 200 ml of anhydrous isopropanol was refluxed 6 at The mixture was then cooled, acidified with 20% H2SO4 solution until acid. The oil that separated out was extracted with diethyl ether, the extract washed with water, dried over anhydrous Na2SO4 and filtered. The obtained precipitate, after evaporating the solvent, was crystallized from isopropanol.

3- (4-ethoxystyryl) -6-pentylcyclohex-2-enone-1 was obtained in the amount of 14.4 g (45%) with phase transition temperature: K 98.5-99.3 Sa 120.4-126.3 AND.

Heating the above-mentioned substrates under the same conditions in the presence of 0.11 mol KOH increases the yield to 55%.

The compounds listed in Table 1 were prepared analogously.

177 052

Table 1

No. Relationship name Phase transition temperatures K. S. N AND 1 3- (4-ethoxystyryl) -6-butylcyldohex-2-enone-1 85 * - 118 2 3- (4-ethoxystyryl) -6-pentylcyclohex-2-enone-1 99 * - 128 3 3- (4-fluorostyryl) -6-pentylcyclohex-2-enone-1 68 - - 4 3- (4-ethoxystyryl) -6-hexylcyldohex-2-enone-1 65 * - 128 5 3- (4-chlorostyryl) -6-pentylcyclohex-2-enone-1 72 - * (66) 6 3rd Jan ^ yo-6-bi ^ 't ^^ oc ^ ldoh ^ k ^ - ^: ’- i ^ non-1 62 - - 7 3- (4-ethoxystyryl) -6-phenylethyl-2) cyclohex-2-enone-1 127 * - 132 8 3- (4-phenylstyryl) -6-butylcyclohex-2-enone-1 75 * - 89

Example 2. 3- (3,4-difluorophenyl) -6- [1- (4-trans-pentylcyclohexyl) ethyl-2] cyclohex-2-enone-1

A mixture of α- (dimethylamino) -3,4-difluoropropiophenone hydrochloride (0.1 mol), ethyl 2- (trans-4-pentylcyclohexylethyl-2) acetylacetate (0.12 mol), and sodium isopropylate (0.12 mol) 150 ml of isopropanol was heated under reflux for 8 hours. Then the mixture was cooled and the product was isolated in the same way as in Example 1.

3- (3,4-difluorophenyl) -6- [1- (4-trans-pentylcyclohexyl) ethyl-2] cyclohex-2-enone-1 was obtained in the amount of 20 g (52%) with K 95 phase transition temperature, 0-96.6 (84 N) I.

Similarly obtained:

3- [4- (4-trans-propylcyclohexyl) phenyl] -6- [1- (4-trans-pentylcyclohexyl) ethyl2] cyclohex-2-enone-1 in the amount of 22.8 g (48%) with transition temperature phase K 83 Sa 246 N 24581;

3- [4- (4-trans-ethylcyclohexyl) phenyl] -6- [1- (4-trans-pentylcyclohexyl) ethyl-2] cyclohex-2-enone-1;

3- (4-methylcyclohexenyl-1) -6- [1- (4-ethoxyphenylethyl-2)] cyclohex-2-enone-1, K 62 Sx 75 I;

3- (4-pentylbiphenylyl-4 ') - 6- (2-cyanoethyl) cyclohex-2-enone-1, K92.0 N 1591

Example 3. 3- [4 ^ (4 - ^^ i trans-propylcyclohexyl) phenyl] ^^] ^ (6 ^ I ^ (^ nt ^] ^^ (^ lkl ^] ^ i ^ k ^ - ^ and ^ - ^^ non-1

A mixture of "- (dimethylamino) propyl 4 - [(trans-4-propylcyclohexyl)] phenylketone hydrochloride (0.1 mol), ethyl 2-pentylacetylacetate (0.12 mol), sodium isopropylate (0.12 mol), 150 ml of isopropyl alcohol was heated under reflux for 8 hours. Then it was cooled down and the product was isolated in the same way as in Example 1.

The obtained was 27.5 g of the compound (75%) with the phase transition temperature K 77 S 148 N 156 I. The compounds presented in Table 2 were obtained analogously.

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Table 2

No. Relationship name Phase transition temperatures K. S. N AND 1 3-phenyl-6-ethylcyclohex-2-enone-1 33 - - 2 3-phenyl-6-pentylcyclohex-2-enone-1 - - 3 3- (4-bromophenyl) -6-ethylcyclohex-2-enone-1 - - 4 3- (4-fluorophenyl) -6-ethylcyclohex-2-enone-1 - - 5 3- (4-methylphenyl) -6-ethylcyclohex-2-enone-1 48 - - 6 3- (4-ethylphenyl) -6-ethylcyclohex-2-enone-1 36 * - (21) 7 3- (4-hexylphenyl) -6-ethylcyclohex-2-enone-1 31 * - 34 8 3- (4-ethoxytphenyl) -6-methylcyclo _t hex-2-enone-1 62 - - 9 3- (4-ethyloxyphenyl) -6-propylcyclohex-2-enone-1 56 * - 67 10 3- (4-cetothyphenyl) -6-butylcyclohex-2-enone-1 55 * - 79 11 3- (4-ethoxyphenyl) -6-pentylcyclohex-2-enone-1 70 * - 86 12 3- (4-propoxyphenyl) -6-pentylcyclohex-2-enone-1 58 ♦ - 94 13 3- (4-butoxyphenyl) -6-methylcyclohex-2-enone-1 71 - - 14 3- (4-butoxyphenyl) -6-propylcyclohex-2-enone-1 67 * - 97 15 3- (4-butoxyphenyl) -6-butylcyclohex-2-enone-1 67 * - 96 16 3- (4-butoxyphenyl) -6-pentylcyldohex-2-enone-1 41 * - 109 17 3- (4-pentyloxyphenyl) -6-propylcyclohex-2- enon-1 55 * - 96 18 3- (4-pentyloxyphenyl) -6-pentylcyclohex-2-enone-1 53 * - 110 19 3- (4-hexyloxyphenyl) -6-pentylcyclohex-2-enone-1 56 * - 109 twenty 3- (4-nonylox; yphenyl) -6-pentylcyclohex-2-enone-1 59 * - 109 21 3- (4-decyloxyphenyl) -6-pentylcyclohex-2-enone-1 60 * - 113 22 3- (4-hexylphenyl) -6-butyl> cyclohex-2-enone-1 75 - - 23 3- (4-hexylphenyl) -6-pentylcyclohex-2-enone-1 90 - - 24 3- (4-trifluoromethoxyphenyl) -6-pentylcyclohex-2- enon-1 37 - - 25 3- (biphenylyl) -6-propylcyclohex-2-enone-1 119 * - (104) 26 3- (biphenyl) -6-butylcyclohex-2-enone-1 110 * - 116 27 3- (biphenylyl) -6-pentylcyldohex-2-enone-1 101 * - 120 28 3- (4'-Fluorobiphenylyl-4) -6-pentylcyclohex-2enon-1 89 * 114 * 141 29 3- (4'-bromobiphenylyl-4) -6-pentylcyclohex-2- enon-1 91 * 114 * 219 thirty 3- (4'-methylbiphenylyl-4) -6-pentylcyclohex-2- enon-1 117 * - 179 31 3- (4'-ethylbiphenylyl-4) -6-pentylcyclohex-2- enon-1 83 * - 171 32 3- (4'-ethylbiphenylyl-4) -6-hexylcyclohex-2- enon-1 94 * - 191 33 3- (4'-pentylbiphenyl-4) -6-ethylcyclohex-2- enon-1 93 * - 157 34 3- (4'-ethoxybiphenylyl-4) -6-propylcyclohex-2- enon-1 118 * - 204 35 3- [4- (4-phenyl-2) phenyl] -6-pentylcyclohex- 2-enone-1 66 * - (54) 36 3- (4-ethoxyphenyl) -6-aHylcyclohex-2-enone-1 71 - -

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Table 3

No. Relationship name Phase transition temperatures K. S. AND 1 3- (4-methylphenyl) -6- (phenylethyl-2) cyclohex-2- enon-1 89 - 2 3- (4-methoxy-3-fluorophenyl-4) -6- (phenylethyl- 2) cyclohex-2-enone-1 98 - 3 3- (4-methoxy-2-fluorophenyl-4) -6- (phenylethyl2) cyclohex-2-enone-1 78 - 4 3- (4-fluorophenyl-4) -6- (phenylethyl-2) cyclohex-2- enon-1 126 - 5 3- (4-ethoxyphenyl-4) -6- (phenylethyl-2) cyclohex-2- enon-1 94 (78)

Table 4

^L p. Relationship name Tem peratury by phases K. S. N AND 1 1,4-bis- (6-pentylcyclohex-2-enyl-3) benzene 109 * - 164 2 1,4-bis- (6-methylcyclohex-2-enyl-3) biphenyl 209 * 214 * 259 3 1,4-bis- (6-pentylcyclohex-2-enyl-3) biffenyl 180 * 254 * 257 4 1,4-bis- (6-pentylcyclohex-2-enyl-3) biphenyleth.ane 133 * - 197

Table 5

^L p. Relationship name Tem peratury by phases K. S. N AND 1 3- (4- (trans-4-butylcyclohexylphenyl) -6- (4- hexylphenyl) -cyWohefc5en-2-enone-l 126 * - 150 2 3- (4- (trans-4-hexylcyclohexylphenyl) -6- (4- butylphenyl) - (yklohexen-2-enone-1 127 * - 164 3 3- (4- (trans-4-hexylcyclohexylphenyl) -6- (4hexylphenyl) -cyclohexen-2-enone-1 120 * - 160 4 3- (4- (trans-4-pentylcyclohexylbiphenyl) -6-phenyl- lyclohexen-2-enone-1 125 * 175 * 189 5 3- (4- (trans-4-pentylcyclohexylbiphenyl) -6- (4- methoxyphenic)) - cyldoheld; en-2-enone-1 137. * - 238 6 3- (4- (trans-4-pentylcyclohexylbiphenyl) -6- (4- fluorophenyl) -cyldohexen-2-enone-1 136 * 150 * 189

Table 6

^L p. Relationship name t. top. Vol. Sep. —— n d 1 3- (4-trans-butylcyclohexylphenyl) -6- allylcylkohe] sen-2-enone-1 210 (3 mm Hg) 1.5063 2 3- (4-trans-butylcyldohexylphenyl) -6pentyl ^ c; ^ ldl ^] ^^ lk ^ {^ i ^^: ^ - ^ (^] ^ one-1 260 (15 mm Hg) 1.4962 3 3- (4-trans-methylcyldohexyl) -6- (1-phenylethyl2) cyclohexene-2-enone-1 56 4 3- (4-trans-methoxyphenylethyl) -6- pentylcyldoheld5en-2-enone-1 26

Table 7

No. Relationship name Phase transition temperatures K. S. AND 1 3-phenyl-6-acctylocyclohex-2-enone-1 96 - 2 3- (4-methylphenyl) -6-acetylcyclohex-2-enone-1 93 - 3 3- (4-methoxyphenyl) -6-acetylcyclohex-2-enone-1 103 - 4 3- (4-ethoxyphenyl) -6-acetylcyclohex-2-enone-1 86 (67) 5 3- (4-butoxyphenyl) -6-acetylcyclohex-2-enone-1 79 (77) 6 3- (4-propoxybiphenylyl) -6-acetylcyclohex-2- enon-1 99 156

Table 8

^L p. Relationship name Phase transition temperatures K. S. N AND 1 3- [4- (4-propylcyclohexyl) phenyl] -6-butylcyclohexen-2-enone-1 57 * 125 * 149 2 3- [4- (4-propylcyclohexyl) phenyl] -6pentylcyclohexen-2-enone-1 76 * 148 - 154 3 3- [4- (4-propylcyclohexyl) phenyl] -6-hexylcy- clohexene-2-enone-l 83 * - 152 4 3- [4- (4-propylcyclohexyl) phenyl] -6-ethylcyclo- hexene-2-enone-1 87 * - 121 5 3- [4- (4-pentylcyclohexyl) phenyl] -6-butylcyclo- hexene-2-enone-1 66 * 144 * 153 6 3- [4- (4-pentylcyclohexyl) phenyl] -6pentylcyclohexen-2-enone-1 58 * * 149 7 ' 3- [4- (4-propylcyclohexyl) phenyl] -6-allylcyclo- hexene-2-enone-1 84 * ♦ 102 8 3- [4- (4-propylcyclohexyl) ethylphenyl] -6-ethyl- cyclohelken-2-enone-1 66 * * 104. 9 3- [4- (3-Methyl-4-pentylcyclohexyl) biphenylyl] 6-pentylcyldohelc5en-2-enone-1 65 * * 234 -} 10 3- [4- (4-propylcyclohexyl) phenyl] -6-phenyl- ethylcyclohexen-2-enone-1 117 * * 170 11 3- [4- (4-propylcyclohexyl) phenyl] -6 - [(4-ethoxy- phenyl) ethyl] cyldohelken-2-enone-1 121 * 172 * 193 12 3- [4- (4-pentylcyclohexyl) phenyl] -6 - [(4-pentyl- phenyl) ethyl] yy! dohek5en-2-enone-l 143 * * 204 13 3- (4-ethoxyphenyl) -6- (6-pentylcyclohexene-2- enoyl-3) -cyclohex-2-enone-1 92 * 130 * 154 14 3- (4-ethoxyphenyl) -6- (6-ethylcyclohexen-2-enoyl- 3) -cyclohex-2-enon-l 91 * - 112 15 3- [4-trans-propylcyUohe] k> yl) phenyl] -6- (6- pentylcyldohelphi-in-2-enoyl-3) -cyclohex-2-enone-1 153 * - 194

Example 4. 2-Butyl-5- [1- (4-ethoxyphenyl) ethyl-2] cyclohexanone-1- (0.1 mol) 3- (4-ethoxystic ^] ^ o) -6 ^ b-ut ^] ^ (^^ ld (^ l ^ <^ l ^ - ^; ^ - (^ and ^^^^ - 1 and 30 g of KOH were dissolved in 150 ml of isopropanol and hydrogenated with hydrogen gas at 50 ° C in the presence of 1 g of a catalyst) (10% Pd / C) until the uptake of hydrogen ceased. The catalyst was filtered off, the solvent was evaporated, the residue was poured onto water, extracted with hexane. After evaporation of the hexane, it was recrystallized several times from ethyl alcohol. Pure 2-trans-butyl-5- [1- (4) was isolated. -ethoxyphenyl) ethyl-2] yldohexanone-1 with phase transition temperature K 57 (N 20) I in the amount of 13 g (43% yield). Post-crystallization liquors were collected and after evaporation

177,052 yields 15 g of a mixture of cis and trans isomers that can be used for conversion to cyclohexene-L derivatives

The trans isomers of the compounds were isolated in an analogous way:

2-methyl-5- [1- (4-eton-yphenyl) ethyl-2] cylnheln> anon-1

2-otyl-5- [1- (4-otonsyphenyl) ethyl-2] cyclohexanone-1

2-propyl-5- (4-pentylbiphenylyl-4) cyvohexanone-1, K103 Sb 155 I

2-methoxy-5- (4-pentylphenylyl-4) cyclohexanone-1, K128 Sb 1841

177 052

NV

Formula 3 —Β

Β

Formula 4

Formula 6

Formula 8

Formula 9

177,052 —Β

oh — V

COORj

Formula 10

CH, C <

Formula 11

ABOUT

Model 12 xch ₂ -ch

Formula 13

Pattern 26

R

Formula 27 «2

177 052

Pattern 32

Pattern 33

Pattern 36

177 052

Pattern 38

H = CH —F

Formula 39 ^Ri · κζ> —p— * 1 Xj

Pattern 40 //

CH = CH2

Pattern 41

Pattern 44

R //> <Xl Xj * 2

Pattern 45

177 052

Pattern 47

about

Pattern 53

177 052

Pattern 54

Pattern 55

Pattern 58

X ·, ® * 3 * 4

Model 61 m 052

Pattern 64

^X 1

Pattern 66

Pattern 68

Pattern 70

177 052

Pattern 73

Pattern 74

Pattern 76

Pattern 78

177 052 ρ ~ CH ₂ C.

Pattern 79

* 1 * 2

Formula 80 i ^> ^ch 2 ^ch ^ - ^ = ^ _ ^{R2 X} 2 ^X 3 * 4

Formula 81 'i ^_ ^ 3> ^_cH2CHr ' ^ = ^ ^- CD ^- * ^{2 X} 1 * 2

Formula 82 * 1 - ^ ~ y ~ CH ₂ CH — OC ^H 2 ^-

Pattern 83 * 1

Pattern 84

CH ₂ CH ₂

<1 * 2 r, _ζ2 ^ - ^^^ Η ₂ 0Η _Γ - ^ 2 ^ - «2

Pattern 85

* 1 x ₂

^X 1 ^X 2

Pattern 86

Pattern 87

177 052

^εΗ 2 ° ^Η 2

Pattern 88

CH ^ Cj

Formula 89 * 1 ~ C ~~ ^ - ^CH 2 ^CH - ^CH 2 ^CH 2- ~ ^ ~ ^ ~ ^R 2 '1 * 2 ^X 3 ^X 4

Pattern 90

O x «

Pattern 91 i O ~ ^ch 2 ^ch 2-CZ) ^- '

Formula 92 ^R 1—- ^CH 2 ^CH 2 ~~ —CHjCHj - CHjCHj-—

S ^X 2 ^X 3 ^X 4 ^X 5 ^X 6

Pattern 93

I ^c H ₂ CH _{2 -} e ~ ^ C ^H ^ ^H f-

S ^X 2

Pattern 94

177 052

R ^ -A — Z2 — β — CHj — CH ₂ X + O

COCH,

And ³

CH-Aj — R ₂ coor ₃

COCH,

Ri-A-Zz-f, c-CH;

-CH;

ABOUT

R-j-Aj-Zg

^A 2 ^R 2

Scheme 1 xch ₂ ch ₂ part ₁ a ₁ Zj c ch ₂ ch ₂ x

CH -— COCH, ³ I ^{3 ha HA} 2- ^R 2 coor ₃

COCH, COCH, Ł ³ I ³

A ^ -C —CH — CH ^ -CZ - ^ - Z ^ C-CH ^ -CH ^ -e ^ - ^r 2

COOR,

Scheme 2

177 052

Scheme 3

DAST h ₂ n-nh ₂

NaBH ₄ or

AI (OC ₃ H ₇ ) ₃

-TD— · :; Hjł Pd / C u ^zi ~ ę5 ~ r 7-4> 4; , - ^Z 4— --.-ABOUT-·.!,· 4 ^ζ <-Ο-τ OH η ¹ H ⁺ , At -and he:

pattern pattern 14 pattern 15 pattern 16 pattern 17 pattern 18

177 052

PCL

1, ch ₃ i

2. Pd / C

1. NaBH

2. Pd / C

Pd / C

Scheme 4 rtgl

pattern pattern19 pattern20 pattern 21 pattern22

Publishing Department of the UP RP. Circulation of 70 copies

Price PLN 4.00.

Claims (3)

Patent claims 1. The method of obtaining new 3,6-substituted cyclohex-2-en-l-ones of the general formula 1, in which R 1 and R 2 are identical or different and represent a terminal group selected from the set: Y- (CH ₂ ) to- ( O) _m - (CHb) k- (O) i- (CH2) pr, Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, -COOCnH2n + 1, -NCS; n, peak ranges from 0 to 7, m and 1 are 0 or 1; Z1 and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10 where Xi, Χ2, Χ3 and Xt are independently hydrogen or fluorine or chlorine, or -CH3 or -CN and B, B11 B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH , OCH2, CH2O, with the proviso that if B in formulas 2-10 is a single bond then Z2 is CH = CH; s = 0, and t = 1, characterized in that acetoacetic acid esters of formula 11 in which A2 is a single bond or one of the fragments represented by the formulas 2-10, R2 is the group Y- (CH2) n- (O) "- (CH2) k- (O) i- (CH2) or Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl terminal group such as -CN, OCF3, CF3 , -COOCnH2n + 1, -NCS, R3 is an alkyl group having 1 to 10 carbon atoms, preferably two, with a compound of formula 12, in which Ri is Y- (CH2) n- (O) m- (CH2) k- (O) i- (CH2) p- or Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, CF1 -COOCHnH2n + i, -NCS, A1 is one of the fragments represented by the formulas 2-10, Z2 is a single bond, CH = CH; C = C or CH2-CH2; X is piperidyl, pyrrolidyl, morphonylyl or a dialkylamino group containing 1 to 15 carbon atoms, preferably a methyl, ethyl or propyl group, heated in organic solvents such as alcohols or ethers in the presence of alkoxides, inorganic bases or alkali metal salts, preferably NaOH or KOH, Na2CO3 or K2CO3 and then the condensation product is treated with an aqueous acid solution, preferably sulfuric acid, and separated from the reaction mixture by known methods, preferably by extraction. 2. The method of obtaining new 3,6-substituted cyclohex-2-en-1-ones of the general formula 1, in which R1 and R2 are identical or different and represent a terminal group selected from the set: Y- (CH2) n- (O ) "- (CH2) k- (O) i- (CH2) p-, Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl or a terminal group such as -CN, -OCF3, -CF3, -COOC, H2n + 1, -NCS; n, p and k take values from 0 to 7, m and 1 are 0 or 1; Z1 and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10 where Xa X2, X3 and Χ4 are independently hydrogen or fluoro or chloro, or a group -CH3 or -CN and B, B11, B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH, OCH2, CH2O, with the proviso that if B in formulas 2-10 is a single bond then Z2 is CH = CH; s = 0, and t = 1, characterized in that acetoacetic acid esters of formula 11 in which A2 is a single bond or one of the fragments represented by the formulas 2-10, R2 is the group Y- (CH2) n- (O) "- (CH2) k- (O) i- (CH2) or Y- (CH2) n-CH = CH- (CH2) p-, where Y is H, F, Cl terminal group such as -CN, OCF3, CF3 , -COOCnH2n + 1, -NCS, R3 is an alkyl group of 1 to 10 carbon atoms, preferably two with a compound of formula 13, in which R1 is Y- (CH2) ^ - (O) ", - (CH2) k- (O) i- (CH2) p- or Y- (CH2) n-CH = CH- (CH2) p-, where Y is 177,052 H, F, Cl or a terminal group such as -CN, -OCF3, CF3, -COOCnH2n + i, -NCS, Ai is one of the fragments marked with the formulas 2-10, Zi and Z2 is a single bond, CH = CH; C = C or CH2-CH2; X is piperidyl, pyrrolidyl, morphonylyl or a dialkylamino group having from 1 to 15 carbon atoms, preferably a methyl, ethyl or propyl group, heated in organic solvents such as alcohols or ethers in the presence of alkoxides, inorganic bases or alkali metal salts, preferably NaOH or KOH, Na2CO3 or K2CO3 and then the condensation product is treated with an aqueous acid solution, preferably sulfuric acid, and separated from the reaction mixture by known methods, preferably by extraction. 3.New 3,6-substituted cyclohex-2-en-1-one in the general formula, where mt = 1 and s is the number 1 or 0, Ri and R2 are the same when s = t and the same or different when s At, i denote a terminal group selected from the set: Y- (CH2) n- (O) _m - (CH2) k- (O) i- (CH2) p-, Y- (CH2) n-CH = CH- (CH2) p- where Y is H, F, Cl, or a terminal group such as -CN, -OCF3, -CF3, -COOCHHIN + i, -NCS; n, peak ranges from 0 to 7, m and 1 are 0 or 1; Zi and Z2 are the same or different and represent a single bond, the group CH = CH, C = C or CH2-CH2, A1 - means one of the fragments marked with formulas 2-10 and A2 means a single bond or one of the fragments marked with formulas 2-10 where Χ1, Χ2, Χ3 and Χ4 are independently hydrogen or fluorine or chlorine, or -CH3 or -CN and B, B11 B2 are independently a single bond or a bridging group such as CH2-CH2, C = C, CH = CH, OCH2, CH2O, with s = 0 fulfilling the condition that if B is a single bond then Z2 is CH = CH. The invention relates to novel 3, S-substituted cyclohox-2-en-1-ones and a method for their preparation. These compounds are used in particular for the preparation of liquid crystals used in information imaging devices. Disubstituted 3,6-diaryl- or arylalkylcyclohex-2-en-1-ones are known (JP 88: 203634,87: 185036,8S: 2S8S4S, 92: 193844 and Brettle et al., Proceedings of the Fourth Intornationa] Forroe ] octric Liquid Crystal Conference, Tokyo 1993, Japan p. 231), which are used to prepare saturated cyclohexanes used as admixtures of ferroelectric (JP 92: 193844) or nematic ((JP 87: 185036, DE 3.510434, 86: 268646) mixtures or for the preparation of liquid crystalline compounds containing a laterally ni-substituted cyclohexanone ring (JP 88: 203634). These compounds have been obtained by condensation of chloroethyl ketones with acetoacetate derivatives (JP 87: 185036, Brettle et al., Chem. Lett., p. 1663, (1993)) ). 3,6-cyclohex-2-en-1-one derivatives are known from the patent application De 3827675 A. These compounds are obtained by combining smaller molecules containing a cyclohex-2-en-1-one ring, e.g. by coupling 4-octyloxybromobenzene with cyclohok-2-en-1-one in the presence of a catalyst - complexes of palladium salts and triphenylphosphine.