DE3522023A1 - Perhydrochrysene derivatives - Google Patents
Perhydrochrysene derivativesInfo
- Publication number
- DE3522023A1 DE3522023A1 DE19853522023 DE3522023A DE3522023A1 DE 3522023 A1 DE3522023 A1 DE 3522023A1 DE 19853522023 DE19853522023 DE 19853522023 DE 3522023 A DE3522023 A DE 3522023A DE 3522023 A1 DE3522023 A1 DE 3522023A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- perhydrochrysenic
- compound
- perhydrochrysene
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ZEMKTMFBYLHVNN-UHFFFAOYSA-N 1,2,3,4,4a,4b,5,6,6a,7,8,9,10,10a,10b,11,12,12a-octadecahydrochrysene Chemical class C1CCCC2CCC3C4CCCCC4CCC3C21 ZEMKTMFBYLHVNN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006266 etherification reaction Methods 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012320 chlorinating reagent Substances 0.000 claims description 2
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- -1 3-ethylhexyl Chemical group 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010626 work up procedure Methods 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000006027 Birch reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical class C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- PKORYTIUMAOPED-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinazoline Chemical compound C1=CC=C2NCNCC2=C1 PKORYTIUMAOPED-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical group C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QQFSIGWYINAJOB-UHFFFAOYSA-N 1,4-dicyclohexylbenzene Chemical class C1CCCCC1C1=CC=C(C2CCCCC2)C=C1 QQFSIGWYINAJOB-UHFFFAOYSA-N 0.000 description 1
- LQDHVNHVHAYANB-UHFFFAOYSA-N 1-(2-bromoethyl)-3-methoxybenzene Chemical compound COC1=CC=CC(CCBr)=C1 LQDHVNHVHAYANB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- RAYZALBEMJMGEA-UHFFFAOYSA-N 1-cyclohexylnaphthalene Chemical class C1CCCCC1C1=CC=CC2=CC=CC=C12 RAYZALBEMJMGEA-UHFFFAOYSA-N 0.000 description 1
- SMHSPYVJAUGNOI-UHFFFAOYSA-N 2-cyclohexyl-1,4-dioxane Chemical class C1CCCCC1C1OCCOC1 SMHSPYVJAUGNOI-UHFFFAOYSA-N 0.000 description 1
- YJDDXMSIMBMMGY-UHFFFAOYSA-N 2-cyclohexylpyrimidine Chemical class C1CCCCC1C1=NC=CC=N1 YJDDXMSIMBMMGY-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001482 benzyl phenyl ethers Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RBBNOVKRLWDEGC-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;4-hexoxybenzoate Chemical compound CCCCCCOC1=CC=C(C([O-])=O)C=C1.CCCCCCCCCCCC[N+](C)(C)CC RBBNOVKRLWDEGC-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MSTLSCNJAHAQNU-UHFFFAOYSA-N heptylcyclohexane Chemical compound CCCCCCCC1CCCCC1 MSTLSCNJAHAQNU-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical class C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- OPYYWWIJPHKUDZ-UHFFFAOYSA-N phenyl cyclohexanecarboxylate Chemical group C1CCCCC1C(=O)OC1=CC=CC=C1 OPYYWWIJPHKUDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
- C07C13/66—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings the condensed ring system contains only four rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
Description
PerhydrochrysenderivatePerhydrochrysene derivatives
Perhydrochrysenderiv ate Die Erfindung betrifft neue Perhydrochrysenderivate der Formel I worin R1 Alkyl mit 1 - 10 C-Atomen und R2 Alkyl, Alkoxy oder Alkanoyloxy mit 1 - 10 C-Atomen, H, Br, C1 oder CV bedeuten.Perhydrochrysene derivatives The invention relates to new perhydrochrysene derivatives of the formula I where R1 is alkyl with 1-10 carbon atoms and R2 is alkyl, alkoxy or alkanoyloxy with 1-10 carbon atoms, H, Br, C1 or CV.
Diese Substanzen können wie ähnliche, z. B. aus der DE-OS 27 02 598 bekannte Verbindungen als Komponenten flüssig-kristalliner Dielektrika verwendet werden, insbesondere für Displays, die auf dem Prinzip der verdrillten Zelle, dem Guest-Host-Effekt,der Deformation aufgerichteter Phasen oder dem Effekt der dynamischen Streuung beruhen.These substances can be used like similar, e.g. B. from DE-OS 27 02 598 known compounds are used as components of liquid-crystalline dielectrics especially for displays based on the principle of the twisted cell, the Guest-host effect, the deformation of erect phases or the effect of the dynamic Scatter based.
Der Erfindung lag die Aufgabe zugrunde, neue stabile flüssig-kristalline oder mesogene Verbindungen auFzufinden, die als Komponenten flüssig-kristalliner Dielektrika geeignet sind.The invention was based on the object of providing new stable liquid-crystalline or to find mesogenic compounds, which are liquid-crystalline components Dielectrics are suitable.
Es wurde gefunden, daß die Perhydrochrysene der Formel I vorzüglich als Komponenten flüssig-kristalliner Dielektrika geeignet sind. Insbesondere sind mit ihrer Hilfe stabile flüssig-kristalline Phasen mit relativ geringer optischer Anisotropie und mit hohem nematischem Charakter herstellbar, die sich in elektrooptischen Anzeigelementen nach dem Prinzip der verdrillten Zelle und/oder dem Guest-Host-Effekt durch eine besonders günstige Winkelabhängigkeit des Kontrastes auszeichnen.It has been found that the perhydrochrysenes of the formula I are excellent are suitable as components of liquid-crystalline dielectrics. In particular are with their help stable liquid-crystalline phases with relatively low optical Anisotropy and with a high nematic character that can be produced in electro-optical Display elements based on the principle of the twisted cell and / or the guest-host effect characterized by a particularly favorable angle dependence of the contrast.
Weiterhin haben sie relativ hoch liegende Klärpunkte und eine außerordentlich niedrige optische Anisotropie. Sie sind daher besonders gut als Komponenten flü-ssigkristalliner Dielektrika für elektrooptische Anzeigeelemente nach der deutschen Patentanmeldung 30 22 818 geeignet, weiterhin aber auch zur Verbesserung des Kontrastes in Guest-Host-Flüssigkristall-Anzeigeelementen. Ferner weisen sie eine negative diamagnetische Suszeptibilitätsanisotropie auf, die sie zur Verwendung in elektrooptischen Modulatoren nach der EP-PS 1745 geeignet macht.Furthermore, they have relatively high clearing points and an extraordinary one low optical anisotropy. They are therefore particularly good liquid-crystalline components Dielectrics for electro-optical display elements according to the German patent application 30 22 818 suitable, but also to improve the contrast in guest-host liquid crystal display elements. Furthermore, they have a negative diamagnetic susceptibility anisotropy, which they are suitable for use in electro-optical modulators according to EP-PS 1745 power.
Mit der Bereitstellung der Verbindungen der Formel I wird außerdem ganz allgemein die Palette der flüssigkristallinen Substanzen, die sich unter verschiedenen anwendungstechnischen Gesichtspunkten zur Herstellung nematischer Gemische eignen, erheblich verbreitert.With the provision of the compounds of the formula I is also in general the range of liquid-crystalline substances, which are classified under different application-related aspects for the production of nematic mixtures, widened considerably.
Die Verbindungen der Formel I besitzen einen breiten Anwendungsbereich. In Abhängigkeit von der Auswahl der Substituenten können diese Verbindungen als Basismaterialien dienen, aus denen flüssig-kristalline Dielektrika zum überwiegenden Teil zusammengesetzt sind; es können aber auch Verbindungen der Formel I flüssigkristallinen Basismaterialien aus anderen Verbindungsklassen zugesetzt werden, um die optische Anisotropie oder die Winkelabhängigkeit des Kontrastes eines solchen Dielektrikums zu beeinflussen.The compounds of the formula I have a wide range of applications. Depending on the choice of substituents, these compounds can be used as Base materials are used, from which liquid-crystalline dielectrics are predominantly used Part are composed; But there can also be connections of the Formula I liquid-crystalline base materials from other classes of compounds added be to the optical anisotropy or the angular dependence of the contrast of a to influence such dielectric.
Die Verbindungen der Formel I sind in reinem Zustand farblos und bilden flüssigkristalline Mesophasen in einem für die elektrooptische Verwendung günstig gelegenen Temperaturbereich. Chemisch, thermisch und gegen Licht sind sie sehr stabil.The compounds of the formula I are colorless in the pure state and form liquid crystalline mesophases in one favorable for electro-optical use located temperature range. They are very stable chemically, thermally and against light.
Gegenstand der Erfindung sind somit die Perhydrochrysene der Formel I sowie ein Verfahren zu ihrer Herstellung, das darin besteht, daß man ein Keton der Formel II zu einer Verbindung der Formel III worin X =0 oder (H,OH) bedeutet (gegebenenfalls stufenweise) reduziert und III (X = 0) durch Umsetzung mit einer Verbindung der Formel R'2-M, worin R'2 Alkyl mit 1 - 10 C-Atomen, M Li oder MgHal und Hal Chlor, Brom oder Jod bedeutet, Hydrolyse, Wasserabspaltung und Hydrierung in eine Verbindung der Formel I, worin R 2 Alkyl mit 1 - 10 C-Atomen bedeutet, überführt, oder III (X = H,OH) durch Wasserabspaltung und Hydrierung in eine Verbindung der Formel I, in der R2 H bedeutet, überführt, oder III (X = H,OH) durch Veretherung bzw. Veresterung in eine Verbindung der Formel I, in der R2 Alkoxy bzw. Alkanoyloxy mit 1 - 10 C-Atomen bedeutet, überführt, oder III (X = H,OH) durch Umsetzung mit einem Chlorierungsmittel bzw. Bromierungsmittel für Hydroxyverbindungen in eine Verbindung der Formel 1 überführt, in der R2 C1 bzw. Br bedeutet, und gegebenenfalls eine solche Verbindung oder einen Sulfonsäureester einer Verbindung der Formel III (X = H,OH) durch Umsetzung mit einem Metallcyanid in eine Verbindung der Formel I umwandelt, in der R2 CN bedeutet.The invention thus relates to the perhydrochrysenes of the formula I and a process for their preparation which consists in using a ketone of the formula II to a compound of the formula III in which X = 0 or (H, OH) means (optionally in stages) reduced and III (X = 0) by reaction with a compound of the formula R'2-M, in which R'2 is alkyl having 1-10 carbon atoms, M Li or MgHal and Hal denotes chlorine, bromine or iodine, hydrolysis, elimination of water and hydrogenation into a compound of the formula I in which R 2 denotes alkyl with 1-10 carbon atoms, or III (X = H, OH) by elimination of water and hydrogenation into a compound of the formula I in which R2 is H, or III (X = H, OH) by etherification or esterification into a compound of the formula I in which R2 is alkoxy or alkanoyloxy at 1-10C -Atoms is converted, or III (X = H, OH) is converted by reaction with a chlorinating agent or brominating agent for hydroxy compounds into a compound of the formula 1 in which R2 is C1 or Br, and optionally such a compound or a sulfonic acid ester a compound of the formula III (X = H, OH) by reaction with a metal cyanide into a Converts compound of formula I in which R2 is CN.
Weiterhin ist Gegenstand der Erfindung die Verwendung der Verbindungen der Formel I als Komponenten flüssigkristalliner Phasen. Gegenstand der Erfindung sind weiterhin flüssigkristalline Phasen mit einem Gehalt ar: mindestens einer Verbindung der Formel I sowie Flüssigkristallanzeigeelemente, insbesondere elektrooptische Anzeigeelemente, die derartige Phasen enthalten.The invention also relates to the use of the compounds of the formula I as components of liquid-crystalline phases. Subject of the invention are also liquid-crystalline phases with a content ar: at least one compound of the formula I and liquid crystal display elements, in particular electro-optical ones Display elements that contain such phases.
Vor- und nachstehend haben die Reste R1 und R2 die angegebene Bedeutung, sofern nicht ausdrücklich etwas anderes vermerkt ist.Above and below, the radicals R1 and R2 have the meaning given, unless expressly stated otherwise.
Die Verbindungen der Formel I besitzen mehrere Asymmetriezentren. Sie können daher bei ihrer Herstellung als Racemate oder, falls optisch aktive Ausgangsstoffe verwendet werden, auch in optisch aktiver Form erhalten werden. Falls Gemische von Racematen anfallen, können daraus die einzelnen Racemate, beispielsweise durch Umkristallisieren der Racemate selbst oder ihrer diastereomeren Derivate aus inerten Lösungsmitteln, in reiner Form isoliert werden.The compounds of the formula I have several centers of asymmetry. They can therefore be used in their preparation as racemates or, if optically active starting materials can also be used in optical active form can be obtained. If mixtures of racemates arise, the individual racemates, for example by recrystallizing the racemates themselves or their diastereomeric derivatives inert solvents, can be isolated in pure form.
Die Synthese wird jedoch vorzugsweise so geführt, daß überwiegend oder ausschließlich die bevorzugten Racemate der Konfiguration Ia gebildet werden: worin beide Substituenten R1 und R2 equatorial stehen.However, the synthesis is preferably carried out in such a way that predominantly or exclusively the preferred racemates of configuration Ia are formed: where both substituents R1 and R2 are equatorial.
Erhaltene Racemate können, falls erwünscht, nach an sich bekannten Methoden mechanisch oder chemisch in ihre optischen Antipoden getrennt werden.Racemates obtained can, if desired, according to known per se Methods can be separated mechanically or chemically into their optical antipodes.
In den Verbindungen der Formel I ist R1 eine Alkylgruppe mit 1 - 10 C-Atomen, also Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl oder Decyl.In the compounds of the formula I, R1 is an alkyl group with 1-10 C atoms, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
Prinzipiell können dabei die 3 und mehr C-Atome enthaltenden Gruppen geradkettig oder verzweigt sein; wenn eine Alkylgruppe R1 verzweigtkettig ist, enthält sie jedoch in der Regel nicht mehr als eine Kettenverzweigung. Dabei sind unter den verzweigten Alkylgruppen diejenigen bevorzugt, in denen sich an einer längeren Kohlenstoffkette in 2- oder 3-Stellung eine Methyl-oder Ethylgruppe befindet, also beispielsweise 2-oder 3-Methylbutyl, 2- oder 3-Methylpentyl oder 2-oder 3-Ethylhexyl. Sofern in den Verbindungen der Formel I auch der Rest R2 eine Kohlenstoffkette enthält, also Alkyl, Alkoxy oder Alkanoyloxy bedeutet, enthält gewöhnlich nur höchstens einer dieser beiden Reste eine einmal verzweigte Kohlenstoffkette. Wenn R2 Alkyl, Alkoxy oder Alkanoyloxy bedeutet, können R1 und R2 zusammen 2 bis 20 C-Atome enthalten. Dabei sind jedoch die Perhydrochrysenderivate der Formel I bevorzugt, in denen R1 und R2 zusammen 3 - 16, vorzugsweise 4 - 14 C-Atome enthalten. In den Verbindungen der Formel I, worin R2 Wasserstoff, Br, Cl oder CN bedeutet, enthält R1 vorzugsweise mindestens 2, insbesondere aber 3 oder mehr C-Atome.In principle, the groups containing 3 or more carbon atoms can be used be straight-chain or branched; when an alkyl group R1 is branched, contains however, they are usually no more than a chain branch. Thereby are under The branched alkyl groups are preferred to those in which a longer Carbon chain a methyl or ethyl group is located in the 2- or 3-position, for example 2- or 3-methylbutyl, 2- or 3-methylpentyl or 2- or 3-ethylhexyl. Unless in the compounds of formula I also contain the radical R2 a carbon chain, that is Alkyl, alkoxy or alkanoyloxy usually contains only at most one of these two residues a carbon chain which is once branched. When R2 is alkyl, alkoxy or alkanoyloxy, R1 and R2 together can contain 2 to 20 carbon atoms. However, the perhydrochrysene derivatives of the formula I are preferred in which R1 and R2 together contain 3-16, preferably 4-14, carbon atoms. In the connections of the formula I, in which R2 is hydrogen, Br, Cl or CN, R1 preferably contains at least 2, but in particular 3 or more carbon atoms.
Die Verbindungen der Formel I werden im übrigen nach an sich bekannten Methoden hergestellt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart; Organic Reactions, John Wiley & Sons, Inc., New York) beschrieben sind, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Da-Dei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The compounds of the formula I are otherwise known per se Methods produced as they are in the literature (e.g. in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart; Organic Reactions, John Wiley & Sons, Inc., New York), under reaction conditions which are known and suitable for the reactions mentioned. Da-Dei can also be used make use of variants known per se, not mentioned here in greater detail.
Die Ausgangsstoffe können gewünschtenfalls auch in situ gebildet werden, derart, daß man sie aus dem Reaktionsgemisch nicht isoliert, sondern sofort weiter zu den Verbindungen der Formel I umsetzt.If desired, the starting materials can also be formed in situ, so that they are not isolated from the reaction mixture, but immediately further to the compounds of formula I.
Die Ausgangsstoffe der Formeln II und III sind neu.The starting materials of formulas II and III are new.
Sie können beispielsweise wie folgt erhalten werden: Zunächst wird ein Cyclohexanon der Formel IV in Gegenwart einer Base, z.B. Morpholin, mit Methylvinylketon zum Diketon der Formel V kondensiert. Dieses wird anschließend in Gegenwart eines Alkalimetallhydroxids, z.». NaOH,zum Oktanydronaphthalinderivat der Formel VI cyclisiert.They can be obtained, for example, as follows: First, a cyclohexanone of the formula IV in the presence of a base, for example morpholine, with methyl vinyl ketone to form the diketone of the formula V condensed. This is then in the presence of an alkali metal hydroxide, z. ». NaOH, to the octanydronaphthalene derivative of the formula VI cyclized.
An VI wird in Gegenwart einer starken Base ein m-Alkoxyphenylethylhalogenid addiert.In the presence of a strong base, VI becomes an m-alkoxyphenylethyl halide added up.
In der dabei erhaltenen Verbindung der Formel VII wird zunächst die
Doppelbindung nach Art einer Birch-Reduktion selektiv reduziert und dann das Reduktionsprodukt
durch Behandlung mit einer starken Säure in einem wasserfreien organischen Lösungsmittel
zur Verbindung VIII cyclisiert.
Die Perhydrochrysenderivate der Formel I, worin R2 H bedeutet, können erhalten werden, indem entweder das Keton III (X = 0) einer Wolff-Kishner-Reduktion unterworfen wird, oder durch Wasserabspaltung aus dem Alkool III (X = H,OH) in Gegenwart einer Säure, gefolgt von Hydrierung der entstandenen ungesättigten Verbindung. Verbindungen der Formel I, worin R2 eine Alkoxygruppe ist, können aus dem Alkohol III (X = H,OH) durch Veretherung hergestellt werden, z.B. The perhydrochrysene derivatives of the formula I, in which R2 is H, can can be obtained by either the ketone III (X = 0) a Wolff-Kishner reduction is subjected, or by elimination of water from the alkool III (X = H, OH) in the presence an acid, followed by hydrogenation of the resulting unsaturated compound. links of the formula I, in which R2 is an alkoxy group, can be selected from the alcohol III (X = H, OH) be prepared by etherification, e.g.
durch Umsetzung mit einem Alkylhalogenid in Gegenwart einer Base. Durch Veresterung mit einer Carbonsäure R"2-COOH,worin R"2 eine Alkylgruppe mit 1 - 9 Kohlenstoffatomen bedeutet, oder einem reaktionsfähigen Derivat einer solchen Carbonsäure, zum Beispiel einem Carbonsäurechlorid oder Carbonsäureanhydrid, können aus dem Alkohol III (X =H,OH) die Perhydrochrysenderivate der Formel I hergestellt werden, in denen R2 eine Alkanoyloxygruppe bedeutet.by reaction with an alkyl halide in the presence of a base. By esterification with a carboxylic acid R "2-COOH, in which R" 2 has an alkyl group 1 - 9 carbon atoms, or a reactive derivative of such Carboxylic acid, for example a carboxylic acid chloride or carboxylic acid anhydride, can the perhydrochrysene derivatives of the formula I are produced from the alcohol III (X = H, OH) in which R2 is an alkanoyloxy group.
Die Verbindungen der Formel I, in denen R2 Cl oder Br bedeutet, sind aus dem Alkohol III (X = H,OH) durch Behandlung mit einem Chlorierungs- oder Bromierungsmittel, zum Beispiel Thionylchlorid oder -bromid, erhältlich.The compounds of formula I in which R2 is Cl or Br are from alcohol III (X = H, OH) by treatment with a chlorinating or brominating agent, for example thionyl chloride or bromide.
Die Herstellung der Perhydrochrysenderivate der Formel I, worin R2 CN bedeutet, kann durch Umsetzung der Chlor- oder Bromverbindungen mit einem Cyanid, z.B. Kaliumcyanid oder Silbercyanid erfolgen. Anstelle der Chlor- oder Bromverbindungen I (R2 = Cl, dr) können auch reaktionsfähige Ester des Alkohols III (X = H,OH), z.B. das Tosylat, verwendet werden.The preparation of the perhydrochrysene derivatives of the formula I, in which R2 CN means, can by reacting the chlorine or bromine compounds with a cyanide, e.g. potassium cyanide or silver cyanide. Instead of the chlorine or bromine compounds I (R2 = Cl, dr) can also be reactive esters of alcohol III (X = H, OH), e.g. the tosylate, can be used.
Die erfindungsgemäßen flüssigkristallinen Phasen bestehen aus 2 bis 15, vorzugsweise 3 bis 12 Komponenten, darunter mindestens einer Verbindung der Formel I. Die anderen Bestandteile werden vorzugsweise ausgewählt aus den nematischen oder nematogenen Substanzen (insbesondere den bekannten Substanzen) aus den Klassen der Azoxybenzole, Benzylidenaniline, Biphenyle, Terphenyle, Phenyl- oder Cyclohexylbenzoate, Cyclohexan-carbonsäurephenyl- oder -cyclohexylester, Phenylcyclohexane, Cyclohexylbiphenyle, Cyclohexylcyclohexane, Cyclohexylnaphthaline, 1,4-Bis-cyclohexylbenzole, 4,4'-Bis-cyclohexylbiphenyle, Phenyl- oder Cyclohexyl-pyrimidine, Phenyl- oder Cyclohexyldioxane, gegebenenfalls halogenierten Stilbene, Benzylphenylether, Tolane, substituierten Zimtsäuren, Naphthaline, Di-, Tetra- und Dekahydronaphthaline.The liquid-crystalline phases according to the invention consist of 2 to 15, preferably 3 to 12 components, including at least one compound of Formula I. The other ingredients are preferably selected from the nematic or nematogenic substances (in particular the known substances) from the classes the azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, Cyclohexanecarboxylic acid phenyl or cyclohexyl ester, phenylcyclohexanes, cyclohexylbiphenyls, Cyclohexylcyclohexane, cyclohexylnaphthalenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, Phenyl- or cyclohexyl-pyrimidines, phenyl- or cyclohexyldioxanes, if appropriate halogenated stilbenes, benzylphenyl ethers, tolanes, substituted cinnamic acids, naphthalenes, Di-, tetra- and decahydronaphthalenes.
Die wichtigsten als Bestandteile derartiger flüssigkristalliner Phasen in Frage kommenden Verbindungen lassen sich durch die Formel X charakterisieren, R-A-B-D-R' X worin A und D je ein carbo- oder heterocyclisches Ringsystem aus der aus l,4-disubstituierten BenZol- und Cyclohexanringen, 4,4'-disubstituierten Biphenyl-, Phenylcyclohexan- und Cyclohexylcyclohexansystemen, 2,5-disubstituierten Pyrimidin- und 1,3-Dioxanringen, 2,6-disubstituiertem Naphthalin, Di-, Tetra- und Dekahydronaphthalin, Chinazolin und Tetrahydrochinazolin gebildeten Gruppen, B -CH=CH- -N(O)=N--CH=CY- -CH=N(O)--C-C- -CH2-CH2--CO-O- -CH2-O--CO-S- -CH2-S--CH=N- -COO-Ph-COO-oder eine C-C-Einfachbindung, Y Halogen, vorzugsweise Chlor, oder -CN, und R und R' Alkyl, Alkoxy, Alkanoyloxy oder Alkoxycarbonyloxy mit bis zu 18, vorzugsweise bis zu 8 Kohlenstoffatomen, oder einer dieser Reste auch -CN, -NC, -NO2, -CF3, F, C1 oder Br bedeuten.The most important as components of such liquid-crystalline phases Compounds in question can be characterized by the formula X, R-A-B-D-R 'X wherein A and D are each a carbo- or heterocyclic ring system from the from 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted biphenyl, Phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di-, tetra- and decahydronaphthalene, Quinazoline and tetrahydroquinazoline formed groups, B -CH = CH- -N (O) = N - CH = CY- -CH = N (O) - C-C- -CH2-CH2 - CO-O- -CH2-O - CO-S- -CH2-S - CH = N- -COO-Ph-COO- or one C-C single bond, Y halogen, preferably chlorine, or -CN, and R and R 'alkyl, Alkoxy, alkanoyloxy or alkoxycarbonyloxy with up to 18, preferably up to 8 Carbon atoms, or one of these radicals also -CN, -NC, -NO2, -CF3, F, C1 or Br mean.
Bei den meisten dieser Verbindungen sind R und R' voneinander verschieden, wobei einer dieser Reste meist eine Alkyl- oder Alkoxygruppe ist. Aber auch andere Varianten der vorgesehenen Substituenten sind gebräuchlich. Viele solcher Substanzen oder auch Gemische davon sind im Han- del erhältlich. Alle diese Substanzen sind nach literaturbekannten Methoden herstellbar.In most of these compounds, R and R 'are different from one another, one of these radicals is usually an alkyl or alkoxy group. But others too Variants of the intended substituents are common. Lots of such substances or mixtures thereof are in the trade del available. All these Substances can be produced by methods known from the literature.
Die erfindungsgemäßen Dielektrika enthalten in der Regel mindestens 30, vorzugsweise 50 - 99, insbesondere 60 - 98 Gewichtsprozent der Verbindungen der Formel I und X. Hiervon entfallen bevorzugt mindestens 5 Gewichtsprozent meist auch 10 - 40 Gewichtsprozentau f eine oder mehrere Verbindungen der Formel I. Jedoch werden von der Erfindung auch solche flüssigkristallinen Dielektrika umfaßt, denen beispielsweise zu Dotierungszwecken nur weniger als 5 Gewichtsprozent zum Beispiel 0,1 bis 3 Gewichtsprozent einer oder mehrerer Verbindungen der Formel I zugesetzt worden sind. Andererseits können die Verbindungen der Formel I bis zu 60 Gewichtsprozent der erfindungsgemäßen Dielektrika ausmachen. Vorzugsweise enthalten die flüssigkristallinen Dielektrika nach der Erfindung 10 bis 30 Gewichtsprozent einer oder mehrerer Verbindungen der Formel I.The dielectrics according to the invention generally contain at least 30, preferably 50-99, in particular 60-98 percent by weight of the compounds of the formulas I and X. Of these, at least 5 percent by weight are usually absent also 10-40 percent by weight of one or more compounds of formula I. However the invention also includes such liquid-crystalline dielectrics, which for example for doping purposes only less than 5 weight percent for example 0.1 to 3 percent by weight of one or more compounds of the formula I are added have been. On the other hand, the compounds of the formula I can contain up to 60 percent by weight make up the dielectrics according to the invention. Preferably contain the liquid-crystalline Dielectrics according to the invention 10 to 30 percent by weight of one or more compounds of formula I.
Die Herstellung der erfindungsgemäßen Dielektrika erfolgt in an sich üblicher Weise. In der Regel werden die Komponenten ineinander gelöst, zweckmäßig bei erhöhter Temperatur.The dielectrics according to the invention are produced in and of themselves usual way. As a rule, the components are dissolved in one another, expediently at elevated temperature.
Durch geeignete Zusätze können die flüssigkristallinen Dielektrika nach der Erfindung so modifiziert werden, daß sie in allen bisher bekannt gewordenen Arten ton Flüssigkristallanzeigeelementen verwendet werden können.With suitable additives, the liquid-crystalline dielectrics be modified according to the invention so that they are in all previously known Kinds of tone liquid crystal display elements can be used.
Derartige Zusätze sind dem Fachmann bekannt und in der Literatur ausführlich beschrieben. Beispielsweise können Leitsalze, vorzugsweise Ethyl-dimethyl-dodecyl- ammonium-4-hexyloxybenzoat, Tetrabutylammoniumtetraphenylboranat oder Komplexsalze von Kronenethern (vgl. z. B. I. Haller et al., Mol. Cryst.Such additives are known to the person skilled in the art and are detailed in the literature described. For example, electrolyte salts, preferably ethyl-dimethyl-dodecyl- ammonium 4-hexyloxybenzoate, Tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf. B. I. Haller et al., Mol. Cryst.
Liq. Cryst. Band 24, Seiten 249 - 258 (1073)) zur Verbesserung der Leitfähigkeit, dichroitische Farbstoffe oder Substanzen zur Veränderung der dielektrischen Anisotropie, der Viskosität und/oder der Orientierung der nematischen Phasen zugesetzt werden. Derartige Substanzen sind zum Beispiel in den DE-OS 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 und 29 02 177 beschrieben.Liq. Cryst. Volume 24, pages 249-258 (1073)) to improve the Conductivity, dichroic dyes or substances that change the dielectric Anisotropy, the viscosity and / or the orientation of the nematic phases added will. Such substances are for example in DE-OS 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 and 29 02 177.
Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen. In den Beispielen beideten F. den Schmelzpunkt und K. den Klärpunkt einer flüssigkristallinen Substanz. Vor- und nachstehend bedeuten Prozentangaben Gewichtsprozent; alle Temperaturen sind in Grad Celsius angegeben.The following examples are intended to illustrate the invention without limiting it limit. In the examples, F. both have the melting point and K. the clearing point of one liquid crystalline substance. Above and below, percentages are percentages by weight; all temperatures are given in degrees Celsius.
"Übliche Aufarbeitung" bedeutet: man gibt Wasser hinzu, extrahiert mit Dichlormethan oder Toluol, trennt ab, trocknet die organische Phase mit Natriumsulfat, dampft ein und reinigt das Produkt durch Destillation, Kristallisation und/oder Chromatographie.“Customary work-up” means: water is added and extraction is carried out with dichloromethane or toluene, separates, the organic phase is dried with sodium sulfate, evaporates and purifies the product by distillation, crystallization and / or Chromatography.
Beispiel 1 1. Herstellung von 8α-n-Pentyl-4aß-H-4bα-H-6aß-H-10aα-H-10bß-H-12aα-H-perhydrochrysen-2ß-ol (IIIa): a) Zu einer Lösung von 1,76 g Kalium in 100 ml t-Butanol werden 6,6 g des Ketons VI (R1 = n-Pentyl) in 10 ml t-Butanol zugegeben. Es wird 70 min. unter Stickstoff gekocht, worauf 6,5 g m-Methoxyphenylethylbromid (Kp0,5 75-82°; erhältlich durch Umsetzung von m-Methoxyphenylethylalkohol mit Triphenylphosphin Br2 in Tetrachlorkohlenstoff) gelöst in 90 ml t-Butanol innerhalb 80 min. zugetropft werden. Es wird noch eine Stunde gekocht, mit halbkonzentrierter Salzsäure angesäuert und das t-Butanol größtenteils abgedampft. Aus dem Rückstand wird nach üblicher Aufarbeitung VII (R¹ = n-Pentyl, Alkoxy = Methoxy) erhalten.Example 1 1. Preparation of 8α-n-Pentyl-4ass-H-4bα-H-6ass-H-10aα-H-10bβ-H-12aα-H-perhydrochrysen-2β-ol (IIIa): a) To a solution of 1.76 g of potassium in 100 ml of t-butanol, 6.6 g of des Ketone VI (R1 = n-pentyl) in 10 ml of t-butanol was added. It is 70 minutes under nitrogen cooked, whereupon 6.5 g of m-methoxyphenylethyl bromide (bp 0.5 75-82 °; obtainable through Conversion of m-methoxyphenylethyl alcohol with triphenylphosphine Br2 in carbon tetrachloride) dissolved in 90 ml of t-butanol are added dropwise over the course of 80 min. There will be another Boiled for an hour, acidified with half-concentrated hydrochloric acid and most of the t-butanol evaporated. After customary work-up, VII (R¹ = n-pentyl, Alkoxy = methoxy).
b) Zu 0,13 g Lithium in 150 ml Ammoniak werden 2,78 g VII in 35 ml THF getropft. Es wird noch 2,5 Stunden gerührt, der Li-Überschuß mit Ammoniumchlorid beseitigt und das Ammoniak abgedampft. Übliche Aufarbeitung liefert das gewünschte Keton. b) To 0.13 g of lithium in 150 ml of ammonia add 2.78 g of VII in 35 ml THF dripped. The mixture is stirred for a further 2.5 hours, the excess Li with ammonium chloride eliminated and the ammonia evaporated. Usual work-up supplies the desired Ketone.
c) Eine Lösung von 0,79 g dieses Ketons in 30 ml Benzol wird mit 50 mg Methansulfonsäure versetzt und 20 min. bei Raumtemperatur gerührt. Das Benzol wird abgedampft. Aus dem Rückstand wird nach üblicher Aufarbeitung VIII (R1 = n-Pentyl, Alkoxy = Methoxy) erhalten (F. 700). c) A solution of 0.79 g of this ketone in 30 ml of benzene is with 50 mg of methanesulfonic acid are added and the mixture is stirred at room temperature for 20 minutes. The benzene is evaporated. After customary work-up, VIII (R1 = n-pentyl, Alkoxy = methoxy) obtained (F. 700).
d) Eine Lösung von 0,42 g VIII in 15 ml THF und 1,2 ml Ethanol wird zu 0,17 g Lithium in 100 ml flüssigem Ammoniak getropft. Nach zwei Stunden Rühren wird das überschüssige Lithium mit Methanol beseitigt und das Ammoniak abgedampft. Übliche Aufarbeitung des Rückstandes liefert IX (R 1 = n-Pentyl, Alkoxy = Methoxy) (F. 820). d) A solution of 0.42 g of VIII in 15 ml of THF and 1.2 ml of ethanol becomes added dropwise to 0.17 g of lithium in 100 ml of liquid ammonia. After stirring for two hours the excess lithium is removed with methanol and the ammonia evaporated. Customary work-up of the residue gives IX (R 1 = n-pentyl, alkoxy = methoxy) (F. 820).
e) Eine Lösung von 0,30 g IX in 50 ml Ethanol wird mit 15 ml halbhonzentrierter Salzsäure versetzt, 20 min. gekocht und nach Abkühlen mit gesättigter Natriumbicarbonatlösung neutralisiert. Übliche Aufarbeitung liefert II (R1 = n-Pentyl) (F. 1170). e) A solution of 0.30 g of IX in 50 ml of ethanol is half-concentrated with 15 ml Hydrochloric acid is added, the mixture is boiled for 20 minutes and, after cooling, with saturated sodium bicarbonate solution neutralized. Customary work-up gives II (R1 = n-pentyl) (F. 1170).
f) Eine Lösung von 0,26 g dieser Verbindung in 15 ml THF und 2,4 g Ethanol wird zu 0,22 g Lithium in 100 ml flüssigem Ammoniak getropft. Nachdem die blaue Farbe verschwunden ist, wird das Ammoniak abgedampft. Übliche Aufarbeitung liefert IIIa (F. 1720). f) A solution of 0.26 g of this compound in 15 ml of THF and 2.4 g of ethanol is added dropwise to 0.22 g of lithium in 100 ml of liquid ammonia. After this the blue color has disappeared, the ammonia is evaporated. Usual work-up provides IIIa (F. 1720).
2. Herstellung von 8«,n-Pentyl-2ß-butyryloxy-4aß-H-6aß-H-4bα-H-10aα-H-10bß-H-12aα-H-perhydrochrysen (Ib): Ein Gemisch von 30 mg IIIa und 100 mg Buttersäurechlorid wird mit 50 mg Kaliumcarbonat versetzt und bis zur beendeten Gasentwicklung gerührt. Nach Zugabe won 2 ml 20°Óiger Kaliumcarbonatlösung und üblicher ufarbeitung erhält man Ib, F. 1450, K. 2000 (Ethanol,.2. Preparation of 8 ″, n-pentyl-2β-butyryloxy-4ass-H-6ass-H-4bα-H-10aα-H-10bβ-H-12aα-H-perhydrochrysene (Ib): A mixture of 30 mg IIIa and 100 mg butyric acid chloride is made with 50 mg potassium carbonate added and stirred until the evolution of gas has ceased. After adding 2 ml 20 ° Óiger Potassium carbonate solution and customary work-up are obtained Ib, F. 1450, K. 2000 (ethanol ,.
In den nachstehenden Beispielen wird 4aß-H-4bqAH-6aß-H-10aH-10bß-H-l2a-H-Perhydrochrysen kurz als "Perhydrochrysen" bezeichnet. In the examples below, 4ass-H-4bqAH-6ass-H-10aH-10bβ-H-l2a-H-Perhydrochrysen briefly referred to as "Perhydrochrysen".
Beispiele 2 bis 18 Analog Beispiel 1 erhält man aus den entsprechenden 8X-Rl-perhydrochrysen-2-olen: 2. 8«-Pentyl-2ß-acetoxy-perhydrochrysen. Examples 2 to 18 Analogously to Example 1, one obtains from the corresponding 8X-R1-perhydrochrysen-2-ols: 2. 8 "-pentyl-2ß-acetoxy-perhydrochrysenic.
3. 8α-Pentyl-2ß-propionyloxy-perhydrochrysen. 3. 8α-Pentyl-2β-propionyloxy-perhydrochrysenic.
4. 8α-Pentyl-2ß-pentanoyloxy-perhydrochrysen. 4. 8α-Pentyl-2β-pentanoyloxy-perhydrochrysenic.
5. 8α-Pentyl-2ß-hexanoyloxy-perhydrochrysen. 5. 8α-Pentyl-2β-hexanoyloxy-perhydrochrysenic.
6. 8α-Pentyl-2ß-heptanoyloxy-perhydrochrysen. 6. 8α-Pentyl-2β-heptanoyloxy-perhydrochrysenic.
7. 8α-Pentyl-2ß-octanoyloxy-perhydrochrysen. 7. 8α-Pentyl-2β-octanoyloxy-perhydrochrysene.
8. 8α-Pentyl-2ß-nonanoyloxy-perhydrochrysen. 8. 8α-Pentyl-2β-nonanoyloxy-perhydrochrysene.
9. 8α-Pentyl-2ß-decanoyloxy-perhydrochrysen. 9. 8α-Pentyl-2β-decanoyloxy-perhydrochrysenic.
10. 8α-Propyl-2ß-acetoxy-perhydrochrysen.10. 8α-Propyl-2β-acetoxy-perhydrochrysenic.
11. 8α-Propyl-2ß-propionyloxy-perhydrochrysen.11. 8α-Propyl-2β-propionyloxy-perhydrochrysenic.
12. 8α-Propyl-2ß-butyryloxy-perhydrochrysen.12. 8α-Propyl-2β-butyryloxy-perhydrochrysenic.
13. 8α-Propyl-2ß-pentanoyloxy-perhydrochrysen.13. 8α-Propyl-2β-pentanoyloxy-perhydrochrysenic.
14. 8α-Propyl-2ß-hexanoyloxy-perhydrochrysen.14. 8α-Propyl-2β-hexanoyloxy-perhydrochrysenic.
15. 8α-Propyl-2ß-heptanoyloxy-perhydrochrysen.15. 8α-Propyl-2β-heptanoyloxy-perhydrochrysenic.
16. 8α-Propyl-2ß-octanoyloxy-perhydrochrysen.16. 8α-Propyl-2β-octanoyloxy-perhydrochrysene.
17. 8α-Propyl-2ß-nonanoyloxy-perhydrochrysen.17. 8α-Propyl-2β-nonanoyloxy-perhydrochrysenic.
18. 8α-Propyl-2ß-decanoyloxy-perhydrochrysen.18. 8α-Propyl-2β-decanoyloxy-perhydrochrysene.
18a. BOGHexyl-2ß-acetoxy-perhydrochrysen.18a. BOGHexyl-2ß-acetoxy-perhydrochrysenic.
18b. 8α-Hexyl-2ß-propionyloxy-perhydrochrysen.18b. 8α-hexyl-2β-propionyloxy-perhydrochrysenic.
18c. 8α-Hexyl-2ß-butyryloxy-perhydrochrysen, F. 131,70, K. 194,90.18c. 8α-Hexyl-2β-butyryloxy-perhydrochrysenic, m.p. 131.70, K. 194.90.
18d. 8α-Hexyl-2ß-pentanoyloxy-perhydrochrysen.18d. 8α-hexyl-2β-pentanoyloxy-perhydrochrysenic.
18e. 8α-Hexyl-2ß-hexanoyloxy-perhydrochrysen.18e. 8α-hexyl-2β-hexanoyloxy-perhydrochrysenic.
18f. 8α-Hexyl-2ß-heptanoyloxy-perhydrochrysen.18f. 8α-hexyl-2β-heptanoyloxy-perhydrochrysenic.
18g. 8α-Hexyl-2ß-octanoyloxy-perhydrochrysen.18g. 8α-hexyl-2β-octanoyloxy-perhydrochrysene.
18h. 8α-Hexyl-2ß-nonanoyloxy-perhydrochrysen.18h. 8α-hexyl-2β-nonanoyloxy-perhydrochrysenic.
18i. 8α-Hexyl-2ß-decanoyloxy-perhydrochrysen.18i. 8α-hexyl-2β-decanoyloxy-perhydrochrysenic.
Beispiel 19 Eine Lösung von 2,1 g 80-Hexylperhydrochrysen-2ß-ol und 0,3 g p-Toluolsulfonsäure in 30 ml Toluol wird 2 Std. am Wasserabscheider gekocht. Man läßt abkühlen, filtriert über A1203 und dampft ein. Der Rückstand wird in 30 ml THF an 0,5 g 5 aÓigem Pd-C bei 600 und 6 bar bis zum Stillstand hydriert. Nach dem Filtrieren und Eindampfen erhält man 8α-Hexylperhydrochrysen, F.1780.Example 19 A solution of 2.1 g of 80-hexylperhydrochrysen-2β-ol and 0.3 g of p-toluenesulfonic acid in 30 ml of toluene is boiled on a water separator for 2 hours. It is allowed to cool, filtered through A1203 and evaporated. The residue is in 30 ml of THF hydrogenated to a standstill on 0.5 g of 5-aqueous Pd-C at 600 and 6 bar. To filtration and evaporation give 8α-Hexylperhydrochrysen, F.1780.
Beispiele 20 bis 28 Analog Beispiel 19 erhält man aus dem entsprechenden 1 1 8«-R -perhydrochrysen-2ß-ol: 20. 8cC-Methyl-perhydrochrysen.Examples 20 to 28 Example 19 is obtained from the corresponding example 1 1 8 "-R -perhydrochrysen-2ß-ol: 20. 8cC-methyl-perhydrochrysen.
21. Bd-Ethyl-perhydrochrysen.21. Bd-ethyl perhydrochrysene.
22. 8α-Propyl-perhydrochrysen.22. 8α-propyl perhydrochrysene.
23. 8α-Butyl-perhydrochrysen.23. 8α-butyl perhydrochrysene.
24. 80C-Pentyl-perhydrochrysen.24. 80C-pentyl perhydrochrysene.
25. 8«-Heptyl-perhydrochrysen.25. 8 "-Heptyl-perhydrochrysenic.
26. 8α-Octyl-perhydrochrysen.26. 8α-octyl perhydrochrysene.
27. 8α-Nonyl-perhydrochrysen.27. 8α-Nonyl-perhydrochrysene.
28. 80dDecyl-perhydrochrysen.28. 80d decyl perhydrochrysene.
Beispiel 29 Zu einer aus 85 g Hexylbromid und 13 g Magnesium in 400 ml Ether bereiteten Grignard-Lösung tropft man unter Rühren und Kühlen eine Lösung von 168 g 8;X-Hexylperhydrochrysen-2-on in 200 ml Ether. Nach einstündigem Kochen gießt man auf verdünnte Salzsäure Eis, extrahiert mehrfach mit Ether, wäscht die Extrakte neutral, trocknet über Natriumsulfat und dampft ein.Example 29 For one made from 85 g of hexyl bromide and 13 g of magnesium in 400 ml of Grignard solution prepared in ether are added dropwise to a solution with stirring and cooling of 168 g of 8; X-hexylperhydrochrysen-2-one in 200 ml of ether. After boiling for an hour it is poured onto dilute hydrochloric acid ice, extracted several times with ether, the washes Extracts neutral, dried over sodium sulfate and evaporated.
Das erhaltene rohe Gemisch aus 2oW8«-Dihexyl-perhydrochrysen-2ß-ol und 2ß,8α-Dihexyl-perhydrochrysen-2α-ol wird in 400 ml Toluol gelöst. Nach Zugabe von 10 g p-Toluolsulfonsäure kocht man 3 Std. am Wasserabscheider, läßt abkühlen, filtriert über Al 203 und dampft ein. Das erhaltene rohe Gemisch von 2,8o(-Dihexylhexadekahydrochrysenen wird in 1 1 Tetrahydrofuran mit 50 g 5igem Pd-C bei 60C und 6 bar bis zum Stillstand hydriert. Nach dem Filtrieren und Eindampfen erhält man ein Gemisch aus 2α,8α- und 2ß,8akDihexyl-perhydrochrysen, das durch HPLC getrennt werden kann.The crude mixture obtained from 2oW8 «-dihexyl-perhydrochrysen-2ß-ol and 2β, 8α-dihexyl-perhydrochrysen-2α-ol is dissolved in 400 ml of toluene. After adding 10 g p-Toluenesulfonic acid is boiled for 3 hours on a water separator, allowed to cool, filtered through Al 203 and evaporated. The crude mixture obtained of 2,8o (-Dihexylhexadekahydrochrysenen is in 1 1 of tetrahydrofuran with 50 g of 5igem Pd-C hydrogenated to a standstill at 60C and 6 bar. After filtering and evaporation a mixture of 2α, 8α- and 2β, 8akDihexyl-perhydrochrysen is obtained, which can be separated by HPLC.
Beispiele 30 bis 59 Analog Beispiel 29 erhält man aus den entsprechenden -perhydrochrysen-2-onen: 30. 2ß,8α-Dimethyl-perhydrochrysen.Examples 30 to 59 Analogously to Example 29 are obtained from the corresponding -perhydrochrysen-2-ones: 30. 2β, 8α-dimethyl-perhydrochrysen.
31. 2ß,8α-Diethyl-perhydrochrysen.31. 2β, 8α-diethyl perhydrochrysenic.
32. 2ß,8α-Dipropyl-perhydrochrysen.32. 2 [beta], 8 [alpha] -dipropyl-perhydrochrysenic.
33. 2ß,8α-Dibutyl-perhydrochrysen.33. 2 [beta], 8 [alpha] -dibutyl-perhydrochrysenic.
34. 2ß,8α-Dipenthyl-perhydrochrysen.34. 2β, 8α-dipenthyl-perhydrochrysenic.
35. 2ß,8dDiheptyl-perhydrochrysen.35.2β, 8d-diheptyl-perhydrochrysenic.
36. 2ß,8α-Dioctyl-perhydrochrysen.36. 2β, 8α-dioctyl-perhydrochrysenic.
37. 2ß,8α-Dinonyl-perhydrochrysen.37. 2β, 8α-dinonyl-perhydrochrysenic.
38. 2ß,8α-Didecyl-perhydrochrysen.38. 2β, 8α-didecyl-perhydrochrysenic.
39. 2ß-Propyl-8α-methyl-perhydrochrysen.39. 2β-propyl-8α-methyl-perhydrochrysenic.
40. 2ß-Propyl-8α-ethyl-perhydrochrysen.40. 2β-propyl-8α-ethyl-perhydrochrysenic.
41. 2ß-Propyl-8α-propyl-perhydrochrysen.41. 2β-propyl-8α-propyl-perhydrochrysenic.
42. 2ß-Propyl-8α-butyl-perhydrochrysen.42. 2β-propyl-8α-butyl-perhydrochrysenic.
43. 2ß-Propyl-8α-pentyl-perhydrochrysen.43. 2β-propyl-8α-pentyl-perhydrochrysenic.
44. 2ß-Propyl-8«-hexyl-perhydrochrysen.44. 2β-Propyl-8'-hexyl-perhydrochrysenic.
45. 2ß-Propyl-8α-heptyl-perhydrochrysen.45. 2β-propyl-8α-heptyl-perhydrochrysenic.
46. 2ß-Propyl-8α-octyl-perhydrochrysen.46. 2β-Propyl-8α-octyl-perhydrochrysenic.
47. 2ß-Propyl-80Gnonyl-perhydrochrysen.47. 2β-Propyl-80Gnonyl-perhydrochrysenic.
48. 2ß-Propyl-8α-decyl-perhydrochrysen.48. 2β-propyl-8α-decyl-perhydrochrysenic.
49. 2ß-Butyl-8α-methyl-perhydrochrysen.49. 2β-Butyl-8α-methyl-perhydrochrysenic.
50. 2ß-Butyl-8dethyl-perhydrochrysen, 51. 2ß-Butyl-8α-propyl-perhydrochrysen.50. 2β-butyl-8dethyl-perhydrochrysenic, 51. 2β-butyl-8α-propyl-perhydrochrysenic.
52. 2ß-Butyl-8α-butyl-perhydrochrysen.52. 2β-Butyl-8α-butyl-perhydrochrysenic.
53. 2ß-Butyl-8α-pentyl-perhydrochrysen.53. 2β-Butyl-8α-pentyl-perhydrochrysenic.
54. 2ß-Butyl-8Z-hexyl-perhydrochrysen.54. 2β-Butyl-8Z-hexyl-perhydrochrysenic.
55. 2ß-Butyl-8α-heptyl-perhydrochrysen.55. 2β-Butyl-8α-heptyl-perhydrochrysenic.
56. 2ß-Butyl-8oLoctyl-perhydrochrysen.56. 2β-Butyl-8oLoctyl-perhydrochrysen.
57. 2ß-Butyl-8oC-nonyl-perhydrochrysen.57. 2β-Butyl-8oC-nonyl-perhydrochrysenic.
58. 2ß-Butyl-8oWdecyl-perhydrochrysen.58. 2β-Butyl-8oWdecyl-perhydrochrysenic.
59. 2ß-Pentyl-8α-methyl-perhydrochrysen.59. 2β-Pentyl-8α-methyl-perhydrochrysenic.
60. 2ß-Pentyl-8α-ethyl-perhydrochrysen.60. 2β-Pentyl-8α-ethyl-perhydrochrysenic.
61. 2ß-Pentyl-8α-propyl-perhydrochrysen.61. 2β-Pentyl-8α-propyl-perhydrochrysenic.
62. 2ß-Pentyl-806butyl-perhydrochrysen.62. 2β-Pentyl-806butyl-perhydrochrysenic.
63. 2ß-Pentyl-8α-pentyl-perhydrochrysen.63. 2β-pentyl-8α-pentyl-perhydrochrysenic.
64. 2ß-Pentyl-8α-hexyl-perhydrochrysen.64. 2β-Pentyl-8α-hexyl-perhydrochrysenic.
65. 2ß-Pentyl-8α-heptyl-perhydrochrysen.65. 2β-Pentyl-8α-heptyl-perhydrochrysenic.
66. 2ß-Pentyl-8α-octyl-perhydrochrysen.66. 2β-Pentyl-8α-octyl-perhydrochrysenic.
67. 2ß-Pentyl-8α-nonyl-perhydrochrysen.67. 2β-Pentyl-8α-nonyl-perhydrochrysenic.
68. 2ß-Pentyl-8α-decyl-perhydrochrysen.68. 2β-Pentyl-8α-decyl-perhydrochrysenic.
Beispiel 69 Zu einer Lösung von 25 mg 8K-Pentyl-perhydrochrysen-2ß-ol in 10 ml THF gibt man 15 mg 35ige KH-Dispersion zu und rührt zwei Stunden unter Rückfluß. Dann wird 0,5 ml n-Jodpentan zugegeben und zwei Stunden bei Raumtemperatur gerührt. Übliche Aufarbeitung (Kieselgel; Ether:Petrolether = 1:20) liefert 8Z-Pentyl-2ß-pentyloxy-perhydrochrysen, F. 1150, K. 1650 (aus Methanol).Example 69 To a solution of 25 mg of 8K-pentyl-perhydrochrysen-2ß-ol 15 mg of 35% KH dispersion in 10 ml of THF are added and the mixture is stirred for two hours Reflux. Then 0.5 ml of n-iodopentane is added and two hours at room temperature touched. Customary work-up (silica gel; ether: petroleum ether = 1:20) gives 8Z-pentyl-2ß-pentyloxy-perhydrochrysenic, F. 1150, K. 1650 (from methanol).
Beispiele 70 bis 98 Analog Beispiel 69 erhält man durch Veretherung: 70. 8α-Ethyl-2ß-propyloxy-perhydrochrysen.Examples 70 to 98 Analogously to Example 69, etherification gives: 70. 8α-Ethyl-2β-propyloxy-perhydrochrysene.
71. 2ß-Butyloxy-8α-ethyl-perhydrochrysen.71. 2β-Butyloxy-8α-ethyl-perhydrochrysenic.
72. 8α-Ethyl-2ß-pentyloxy-perhydrochrysen.72. 8α-Ethyl-2β-pentyloxy-perhydrochrysenic.
73. BdEthyl-2u-hexyloxy-perhydrochrysen.73. BdEthyl-2u-hexyloxy-perhydrochrysenic.
74. BdEthyl-2ß-heptyloxy-perhydrochrysen.74. BdEthyl-2ß-heptyloxy-perhydrochrysenic.
75. 8α-Propyl-2ß-ethoxy-perhydrochrysen.75. 8α-propyl-2β-ethoxy-perhydrochrysenic.
76. 2ß-Butyloxy-8α-propyl-perhydrochrysen.76. 2β-Butyloxy-8α-propyl-perhydrochrysenic.
77. 2ß-Pentyloxy-8α-propyl-perhydrochrysen.77. 2β-pentyloxy-8α-propyl-perhydrochrysenic.
78. 2ß-Hexyloxy-8α-propyl-perhydrochrysen.78. 2β-Hexyloxy-8α-propyl-perhydrochrysenic.
79. 2ß-Heptyloxy-8α-propyl-perhydrochrysen.79. 2β-Heptyloxy-8α-propyl-perhydrochrysenic.
80. 8α-Butyl-2ß-propyloxy-perhydrochrysen.80. 8α-Butyl-2β-propyloxy-perhydrochrysenic.
81. 8Z-Butyl-2ß-butyloxy-perhydrochrysen.81. 8Z-butyl-2β-butyloxy-perhydrochrysenic.
82. 8α-Butyl-2ß-pentyloxy-perhydrochrysen.82. 8α-Butyl-2β-pentyloxy-perhydrochrysene.
83. 8Z-Butyl-2ß-hexyloxy-perhydrochrysen.83. 8Z-Butyl-2ß-hexyloxy-perhydrochrysenic.
84. 8α-Butyl-2ß-heptyloxy-perhydrochrysen.84. 8α-Butyl-2β-heptyloxy-perhydrochrysene.
85. 8α-Pentyl-2ß-propyloxy-perhydrochrysen.85. 8α-Pentyl-2β-propyloxy-perhydrochrysenic.
F. 137,60, K. 1820. F. 137.60, K. 1820.
85a.8X-Pentyl-2ß-methoxy-perhydrochrysen, F. 102,50, K. 168,60.85a.8X-pentyl-2β-methoxy-perhydrochrysenic, m.p. 102.50, K. 168.60.
85b. 8α-Pentyl-2ß-ethoxy-perhydrochrysen.85b. 8α-pentyl-2β-ethoxy-perhydrochrysenic.
85c.8X-Pentyl-2ß-butyloxy-perhydrochrysen, F. 135,20, K. 1820.85c.8X-pentyl-2β-butyloxy-perhydrochrysenic, F. 135.20, K. 1820.
86. 2ß-Butyloxy-8«-pentyl-perhydrochrysen.86. 2β-Butyloxy-8'-pentyl-perhydrochrysene.
87. 8α-Pentyl-2ß-hexyloxy-perhydrochrysen.87. 8α-Pentyl-2β-hexyloxy-perhydrochrysenic.
88. 2ß-Hexyloxy-8α-pentyl-perhydrochrysen.88. 2β-hexyloxy-8α-pentyl-perhydrochrysene.
89. 2ß-Heptyloxy-8α-pentyl-perhydrochrysen.89. 2β-heptyloxy-8α-pentyl-perhydrochrysenic.
90. 8α-Hexyl-2ß-propyloxy-perhydrochrysen, F. 116,50, K. 176.8°.90. 8α-Hexyl-2β-propyloxy-perhydrochrysenic, m.p. 116.50, K. 176.8 °.
90a.8K-Hexyl-2ß-butyloxy-perhydrochrysen, F. 118,50, K. 171,70.90a.8K-hexyl-2β-butyloxy-perhydrochrysenic, m.p. 118.50, K. 171.70.
90b. 8α-Hexyl-2ß-pentyloxy-perhydrochrysen, F. 119,30, K. 169,40.90b. 8α-hexyl-2β-pentyloxy-perhydrochrysenic, m. 119.30, k. 169.40.
90. 8α-Hexyl-2ß-propyloxy-perhydrochrysen.90. 8α-Hexyl-2β-propyloxy-perhydrochrysenic.
91. 2ß-Butyloxy-8dhexyl-perhydrochrysen.91. 2β-Butyloxy-8dhexyl-perhydrochrysenic.
92. 8Z-Hexyl-2ß-hexyloxy-perhydrochrysen.92. 8Z-Hexyl-2ß-hexyloxy-perhydrochrysenic.
93. 8α-Hexyl-2ß-heptyloxy-perhydrochrysen.93. 8α-Hexyl-2β-heptyloxy-perhydrochrysene.
94. 8α-Heptyl-2ß-propyloxy-perhydrochrysen.94. 8α-heptyl-2β-propyloxy-perhydrochrysene.
95. 2ß-Butyloxy-8α-heptyl-perhydrochrysen.95. 2β-Butyloxy-8α-heptyl-perhydrochrysenic.
96. 8α-Heptyl-2ß-pentyloxy-perhydrochrysen.96. 8α-heptyl-2β-pentyloxy-perhydrochrysenic.
97. 2ß-Hexyloxy-8α-heptyl-perhydrochrysen.97. 2β-Hexyloxy-8α-heptyl-perhydrochrysene.
98. 8α-Heptyl-2ß-heptyloxy-perhydrochrysen.98. 8α-heptyl-2β-heptyloxy-perhydrochrysene.
Beispiel 99 Zu einer Lösung von 1,19 g N-Bromsuccinimid in 5 ml THF tropft man unter Stickstoff eine Lösung von 1,74 g Triphenylphosphin in 5 ml THF. Dazu wird eine Lösung von Hexyl-perhydrochrysen-2Z-ol (erhältlich aus 8aSHexylperhydrochrysen-2-on und Kalium-tris-sek. -butylborhydrid in THF) in 5 ml THF gegeben. Es wird 4 Std. gekocht, danach über Nacht bei 200 nachgerührt und wie üblich aufgearbeitet. (Kieselgel 60; n-Hexan). Man erhält 2ß-Brom-8d-hexyl-perhydrochrysen.Example 99 To a solution of 1.19 g of N-bromosuccinimide in 5 ml of THF a solution of 1.74 g of triphenylphosphine in 5 ml of THF is added dropwise under nitrogen. A solution of hexyl perhydrochrysen-2Z-ol (obtainable from 8aSHexylperhydrochrysen-2-one and potassium-tris-sec. -butylborohydride in THF) in 5 ml of THF. It will be 4 hours boiled, then stirred overnight at 200 and worked up as usual. (Silica gel 60; n-hexane). 2ß-Bromo-8d-hexyl-perhydrochrysenic is obtained.
Beispiele 100 bis 118 Analog Beispiel 99 erhält man aus den entsprechenden Alkoholen mit N-Chlorsuccinimid oder N-Bromsuccinimid: 100. 2ß-Chlor-8α-methyl-perhydrochrysen 101. 2ß-Chlor-8α-ethyl-perhydrochrysen.Examples 100 to 118 Analogously to Example 99 are obtained from the corresponding Alcohols with N-chlorosuccinimide or N-bromosuccinimide: 100. 2β-chloro-8α-methyl-perhydrochrysenic 101. 2β-chloro-8α-ethyl-perhydrochrysenic.
102. 2ß-Chlor-8α-propyl-perhydrochrysen.102. 2β-chloro-8α-propyl-perhydrochrysenic.
103. 8α-Butyl-2ß-chlor-perhydrochrysen.103. 8α-Butyl-2β-chloroperhydrochrysenic.
104. 2ß-Chlor-8α-pentyl-perhydrochrysen.104. 2β-chloro-8α-pentyl-perhydrochrysenic.
105. 2ß-Chlor-8α-hexyl-perhydrochrysen.105. 2β-chloro-8α-hexyl-perhydrochrysenic.
106. 2ß-Chlor-8α-heptylperhydrochrysen.106. 2β-chloro-8α-heptyl perhydrochrysene.
107. 2ß-Chlor-8α-octyl-perhydrochrysen.107. 2β-chloro-8α-octyl-perhydrochrysenic.
108. 2ß-Chlor-8α-nonyl-perhydrochrysen.108. 2β-chloro-8α-nonyl-perhydrochrysenic.
109. 2ß-Chlor-8α-decyl-perhydrochrysen.109. 2β-chloro-8α-decyl-perhydrochrysenic.
110. 2ß-Brom-8α-methyl-perhydrochrysen.110. 2β-Bromo-8α-methyl-perhydrochrysenic.
111. 2ß-Brom-8q-ethyl-perhydrochrysen.111. 2β-Bromo-8q-ethyl-perhydrochrysenic.
112. 2ß-Brom-8α-propyl-perhydrochrysen.112. 2β-Bromo-8α-propyl-perhydrochrysenic.
113. 2ß-Brom-8O(-butyl-perhydrochrysen.113. 2β-Bromo-8O (-butyl-perhydrochrysenic.
114. 2ß-Brom-8α-pentyl-perhydrochrysen.114. 2β-Bromo-8α-pentyl-perhydrochrysenic.
115. 2ß-Brom-8d-heptyl-perhydrochrysen.115. 2β-Bromo-8d-heptyl-perhydrochrysenic.
116. 2ß-Brom-8i-octyl-perhydrochrysen.116. 2β-Bromo-8i-octyl-perhydrochrysenic.
117. 2ß-Brom-8i-nonyl-perhydrochrysen.117. 2β-Bromo-8i-nonyl-perhydrochrysenic.
118. 2ß-Brom-84-decylperhydrochrysen.118. 2β-Bromo-84-decylperhydrochrysenic.
Beispiel 119 Eine Lösung von 470 mg 8Z-Hexyl-2ß-p-toluolsulfonyloxyperhydrochrysen und 724 mg Natriumcyanid in 50 ml N-Methylpyrrolidon wird 20 Stunden bei 900 gerührt.Example 119 A solution of 470 mg of 8Z-hexyl-2β-p-toluenesulfonyloxyperhydrochrysene and 724 mg of sodium cyanide in 50 ml of N-methylpyrrolidone is stirred at 900 for 20 hours.
Nach dem Abkühlen verdünnt man mit Wasser und arbeitet wie üblich auf (Kieselgel 60; Petrolether:Ether = 95:5).After cooling, dilute with water and work as usual on (silica gel 60; petroleum ether: ether = 95: 5).
Man erhält 2ß-Cyan-8K-hexyl-perhydrochrysen.2ß-cyano-8K-hexyl-perhydrochrysenic is obtained.
Beispiele 120 bis 129 Analog Beispiel 119 erhält man aus den entsprechenden Chloriden, Bromiden oder p-Toluolsulfonaten mit NaCN: 120. 2ß-Cyan-8α-methyl-perhydrochrysen.Examples 120 to 129 Analogously to example 119 are obtained from the corresponding Chlorides, bromides or p-toluenesulfonates with NaCN: 120. 2β-cyano-8α-methyl-perhydrochrysene.
121. 2ß-Cyan-8α-ethyl-perhydrochrysen.121. 2β-cyano-8α-ethyl-perhydrochrysenic.
122. 2ß-Cyan-8α-propyl-perhydrochrysen.122. 2β-cyano-8α-propyl-perhydrochrysenic.
123. 8K-Butyl-2ß-cyan-perhydrochrysen.123. 8K-butyl-2ß-cyano-perhydrochrysenic.
124. 2ß-Cyan-8α-pentyl-perhydrochrysen.124. 2β-cyano-8α-pentyl-perhydrochrysenic.
125. 2ß-Cyan-8d-hexyl-perhydrochrysen.125. 2β-cyano-8d-hexyl-perhydrochrysenic.
126. 2ß-Cyan-8α-heptyl-perhydrochrysen.126. 2β-cyano-8α-heptyl-perhydrochrysene.
127. 2ß-Cyan-8z-octyl-perhydrochrysen.127. 2β-cyano-8z-octyl-perhydrochrysenic.
128. 2ß-Cyan-8s-nonyl-perhydrochrysen.128. 2β-cyano-8s-nonyl-perhydrochrysenic.
129. 2ß-Cyan-8i-decyl-perhydrochrysen.129. 2β-cyano-8i-decyl-perhydrochrysenic.
Die folgenden Beispiele betreffen Gemische von Verbindungen der Formel I mit anderen flüssig-kristallinen Substanzen, die erfindungsgemäß als Dielektrika verwendet werden könne.The following examples relate to mixtures of compounds of the formula I with other liquid-crystalline substances which, according to the invention, are used as dielectrics can be used.
8eispiel A Ein Gemisch aus 26 % trans,trans-4-Ethylcyclohexylcyclohexan-4'-carbonitril 17 % trans,trans-4-Propylcyclohexylcyclohexan-4'-carbonitril 21 % trans,trans-4-Butylcyclohexylcyclohexan-4'-carbonitril 26 % trans,trans-4-Heptylcyclohexylcyclohexan-4'-carbonitril und 10 % 8α-Propyl-2ß-pentanoyloxyperhydrochrysen zeigt K. 850.Example A A mixture of 26% trans, trans-4-ethylcyclohexylcyclohexane-4'-carbonitrile 17% trans, trans-4-propylcyclohexylcyclohexane-4'-carbonitrile 21% trans, trans-4-butylcyclohexylcyclohexane-4'-carbonitrile 26% trans, trans-4-heptylcyclohexylcyclohexane-4'-carbonitrile and 10% 8α-propyl-2β-pentanoyloxyperhydrochrysene shows K. 850.
Beispiel B Ein Gemisch aus 30 % r-1-Cyan-cis-4-(trans-4-pentylcyclohexyl)-1-pentyl-cyclohexan, 27 % r-1-Cyan-cis-4-(trans-4-butylcyclohexyl)-1 heptyl-cyclohexan, 28 % r-1-Cyan-cis-4-(trans-4-pentylcyclohexyl)-1 heptyl-cyclohexan und 15 % 8α-Propyl-2ß-ethoxy-perhydrochrysen zeigt K. 810. Example B A mixture of 30% r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1-pentyl-cyclohexane, 27% r-1-cyano-cis-4- (trans-4-butylcyclohexyl) -1 heptyl-cyclohexane, 28% r-1-cyano-cis-4- (trans-4-pentylcyclohexyl) -1 K. 810 shows heptyl-cyclohexane and 15% 8α-propyl-2β-ethoxy-perhydrochrysenic.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853522023 DE3522023A1 (en) | 1984-07-14 | 1985-06-20 | Perhydrochrysene derivatives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3426039 | 1984-07-14 | ||
| DE19853522023 DE3522023A1 (en) | 1984-07-14 | 1985-06-20 | Perhydrochrysene derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3522023A1 true DE3522023A1 (en) | 1986-01-16 |
Family
ID=25822960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19853522023 Withdrawn DE3522023A1 (en) | 1984-07-14 | 1985-06-20 | Perhydrochrysene derivatives |
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| Country | Link |
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| DE (1) | DE3522023A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4693841A (en) * | 1984-12-01 | 1987-09-15 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Carbonitriles |
-
1985
- 1985-06-20 DE DE19853522023 patent/DE3522023A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4693841A (en) * | 1984-12-01 | 1987-09-15 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Carbonitriles |
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