DE4434975A1 - New tri:cyclic cpds. - Google Patents
New tri:cyclic cpds.Info
- Publication number
- DE4434975A1 DE4434975A1 DE4434975A DE4434975A DE4434975A1 DE 4434975 A1 DE4434975 A1 DE 4434975A1 DE 4434975 A DE4434975 A DE 4434975A DE 4434975 A DE4434975 A DE 4434975A DE 4434975 A1 DE4434975 A1 DE 4434975A1
- Authority
- DE
- Germany
- Prior art keywords
- cyclopenta
- dihydro
- naphthalene example
- dimethylsila
- formula
- 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- Withdrawn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
- 125000004122 cyclic group Chemical group 0.000 title 1
- -1 cyclopropane-1,2-diyl Chemical group 0.000 claims abstract description 275
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims abstract description 7
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 claims abstract description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims abstract description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 32
- 239000004973 liquid crystal related substance Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004976 cyclobutylene group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 abstract 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract 1
- 229930188620 butyrolactone Natural products 0.000 abstract 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 8
- 239000004990 Smectic liquid crystal Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000137 polyphosphoric acid Polymers 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical class CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 150000000185 1,3-diols Chemical class 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 238000000819 phase cycle Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VCGRFBXVSFAGGA-UHFFFAOYSA-N (1,1-dioxo-1,4-thiazinan-4-yl)-[6-[[3-(4-fluorophenyl)-5-methyl-1,2-oxazol-4-yl]methoxy]pyridin-3-yl]methanone Chemical compound CC=1ON=C(C=2C=CC(F)=CC=2)C=1COC(N=C1)=CC=C1C(=O)N1CCS(=O)(=O)CC1 VCGRFBXVSFAGGA-UHFFFAOYSA-N 0.000 description 1
- MAYZWDRUFKUGGP-VIFPVBQESA-N (3s)-1-[5-tert-butyl-3-[(1-methyltetrazol-5-yl)methyl]triazolo[4,5-d]pyrimidin-7-yl]pyrrolidin-3-ol Chemical compound CN1N=NN=C1CN1C2=NC(C(C)(C)C)=NC(N3C[C@@H](O)CC3)=C2N=N1 MAYZWDRUFKUGGP-VIFPVBQESA-N 0.000 description 1
- WSZDCPGZALCPAY-UHFFFAOYSA-N (6-hexoxynaphthalen-2-yl)methanol Chemical compound C(CCCCC)OC=1C=C2C=CC(=CC2=CC=1)CO WSZDCPGZALCPAY-UHFFFAOYSA-N 0.000 description 1
- ZGYIXVSQHOKQRZ-COIATFDQSA-N (e)-n-[4-[3-chloro-4-(pyridin-2-ylmethoxy)anilino]-3-cyano-7-[(3s)-oxolan-3-yl]oxyquinolin-6-yl]-4-(dimethylamino)but-2-enamide Chemical compound N#CC1=CN=C2C=C(O[C@@H]3COCC3)C(NC(=O)/C=C/CN(C)C)=CC2=C1NC(C=C1Cl)=CC=C1OCC1=CC=CC=N1 ZGYIXVSQHOKQRZ-COIATFDQSA-N 0.000 description 1
- MOWXJLUYGFNTAL-DEOSSOPVSA-N (s)-[2-chloro-4-fluoro-5-(7-morpholin-4-ylquinazolin-4-yl)phenyl]-(6-methoxypyridazin-3-yl)methanol Chemical compound N1=NC(OC)=CC=C1[C@@H](O)C1=CC(C=2C3=CC=C(C=C3N=CN=2)N2CCOCC2)=C(F)C=C1Cl MOWXJLUYGFNTAL-DEOSSOPVSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- APWRZPQBPCAXFP-UHFFFAOYSA-N 1-(1-oxo-2H-isoquinolin-5-yl)-5-(trifluoromethyl)-N-[2-(trifluoromethyl)pyridin-4-yl]pyrazole-4-carboxamide Chemical compound O=C1NC=CC2=C(C=CC=C12)N1N=CC(=C1C(F)(F)F)C(=O)NC1=CC(=NC=C1)C(F)(F)F APWRZPQBPCAXFP-UHFFFAOYSA-N 0.000 description 1
- ABDDQTDRAHXHOC-QMMMGPOBSA-N 1-[(7s)-5,7-dihydro-4h-thieno[2,3-c]pyran-7-yl]-n-methylmethanamine Chemical compound CNC[C@@H]1OCCC2=C1SC=C2 ABDDQTDRAHXHOC-QMMMGPOBSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KXYGKDBONOVZOM-UHFFFAOYSA-N 1h-cyclopenta[a]naphthalene Chemical compound C1=CC=CC2=C3CC=CC3=CC=C21 KXYGKDBONOVZOM-UHFFFAOYSA-N 0.000 description 1
- DHABTOFDIICRRO-UHFFFAOYSA-N 2-(bromomethyl)-6-hexoxynaphthalene Chemical compound C(CCCCC)OC=1C=C2C=CC(=CC2=CC=1)CBr DHABTOFDIICRRO-UHFFFAOYSA-N 0.000 description 1
- LXVMZXDHVIVJLY-UHFFFAOYSA-N 2-[(6-hexoxynaphthalen-2-yl)methyl]decanoic acid Chemical compound C(CCCCCCC)C(C(=O)O)CC1=CC2=CC=C(C=C2C=C1)OCCCCCC LXVMZXDHVIVJLY-UHFFFAOYSA-N 0.000 description 1
- JBNWDSSVOCTJBL-UHFFFAOYSA-N 2-bromo-6-hexoxynaphthalene Chemical compound C1=C(Br)C=CC2=CC(OCCCCCC)=CC=C21 JBNWDSSVOCTJBL-UHFFFAOYSA-N 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical class C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- HCDMJFOHIXMBOV-UHFFFAOYSA-N 3-(2,6-difluoro-3,5-dimethoxyphenyl)-1-ethyl-8-(morpholin-4-ylmethyl)-4,7-dihydropyrrolo[4,5]pyrido[1,2-d]pyrimidin-2-one Chemical compound C=1C2=C3N(CC)C(=O)N(C=4C(=C(OC)C=C(OC)C=4F)F)CC3=CN=C2NC=1CN1CCOCC1 HCDMJFOHIXMBOV-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- SRVXSISGYBMIHR-UHFFFAOYSA-N 3-[3-[3-(2-amino-2-oxoethyl)phenyl]-5-chlorophenyl]-3-(5-methyl-1,3-thiazol-2-yl)propanoic acid Chemical compound S1C(C)=CN=C1C(CC(O)=O)C1=CC(Cl)=CC(C=2C=C(CC(N)=O)C=CC=2)=C1 SRVXSISGYBMIHR-UHFFFAOYSA-N 0.000 description 1
- YFCIFWOJYYFDQP-PTWZRHHISA-N 4-[3-amino-6-[(1S,3S,4S)-3-fluoro-4-hydroxycyclohexyl]pyrazin-2-yl]-N-[(1S)-1-(3-bromo-5-fluorophenyl)-2-(methylamino)ethyl]-2-fluorobenzamide Chemical compound CNC[C@@H](NC(=O)c1ccc(cc1F)-c1nc(cnc1N)[C@H]1CC[C@H](O)[C@@H](F)C1)c1cc(F)cc(Br)c1 YFCIFWOJYYFDQP-PTWZRHHISA-N 0.000 description 1
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 1
- IRPVABHDSJVBNZ-RTHVDDQRSA-N 5-[1-(cyclopropylmethyl)-5-[(1R,5S)-3-(oxetan-3-yl)-3-azabicyclo[3.1.0]hexan-6-yl]pyrazol-3-yl]-3-(trifluoromethyl)pyridin-2-amine Chemical compound C1=C(C(F)(F)F)C(N)=NC=C1C1=NN(CC2CC2)C(C2[C@@H]3CN(C[C@@H]32)C2COC2)=C1 IRPVABHDSJVBNZ-RTHVDDQRSA-N 0.000 description 1
- KCBWAFJCKVKYHO-UHFFFAOYSA-N 6-(4-cyclopropyl-6-methoxypyrimidin-5-yl)-1-[[4-[1-propan-2-yl-4-(trifluoromethyl)imidazol-2-yl]phenyl]methyl]pyrazolo[3,4-d]pyrimidine Chemical compound C1(CC1)C1=NC=NC(=C1C1=NC=C2C(=N1)N(N=C2)CC1=CC=C(C=C1)C=1N(C=C(N=1)C(F)(F)F)C(C)C)OC KCBWAFJCKVKYHO-UHFFFAOYSA-N 0.000 description 1
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 1
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZNLGHCORTDCVRX-UHFFFAOYSA-N C(CCCCC)OC=1C=C2C=CC(=CC2=CC=1)[Li] Chemical compound C(CCCCC)OC=1C=C2C=CC(=CC2=CC=1)[Li] ZNLGHCORTDCVRX-UHFFFAOYSA-N 0.000 description 1
- HWITUWILZJLILE-UHFFFAOYSA-N CCCCCCOC1CCC2=C1C3=CC=CC=C3C=C2 Chemical compound CCCCCCOC1CCC2=C1C3=CC=CC=C3C=C2 HWITUWILZJLILE-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- GISRWBROCYNDME-PELMWDNLSA-N F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C Chemical compound F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C GISRWBROCYNDME-PELMWDNLSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- AYCPARAPKDAOEN-LJQANCHMSA-N N-[(1S)-2-(dimethylamino)-1-phenylethyl]-6,6-dimethyl-3-[(2-methyl-4-thieno[3,2-d]pyrimidinyl)amino]-1,4-dihydropyrrolo[3,4-c]pyrazole-5-carboxamide Chemical compound C1([C@H](NC(=O)N2C(C=3NN=C(NC=4C=5SC=CC=5N=C(C)N=4)C=3C2)(C)C)CN(C)C)=CC=CC=C1 AYCPARAPKDAOEN-LJQANCHMSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910018954 NaNH2 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- IDRGFNPZDVBSSE-UHFFFAOYSA-N OCCN1CCN(CC1)c1ccc(Nc2ncc3cccc(-c4cccc(NC(=O)C=C)c4)c3n2)c(F)c1F Chemical compound OCCN1CCN(CC1)c1ccc(Nc2ncc3cccc(-c4cccc(NC(=O)C=C)c4)c3n2)c(F)c1F IDRGFNPZDVBSSE-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000033641 Ring chromosome 5 syndrome Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- LXRZVMYMQHNYJB-UNXOBOICSA-N [(1R,2S,4R)-4-[[5-[4-[(1R)-7-chloro-1,2,3,4-tetrahydroisoquinolin-1-yl]-5-methylthiophene-2-carbonyl]pyrimidin-4-yl]amino]-2-hydroxycyclopentyl]methyl sulfamate Chemical compound CC1=C(C=C(S1)C(=O)C1=C(N[C@H]2C[C@H](O)[C@@H](COS(N)(=O)=O)C2)N=CN=C1)[C@@H]1NCCC2=C1C=C(Cl)C=C2 LXRZVMYMQHNYJB-UNXOBOICSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical group 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- YZYBVYGISZANLI-UHFFFAOYSA-N diethyl 2-octylpropanedioate Chemical compound CCCCCCCCC(C(=O)OCC)C(=O)OCC YZYBVYGISZANLI-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000003392 indanyl group Chemical class C1(CCC2=CC=CC=C12)* 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 150000001564 phenyl benzoates Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- XIIOFHFUYBLOLW-UHFFFAOYSA-N selpercatinib Chemical compound OC(COC=1C=C(C=2N(C=1)N=CC=2C#N)C=1C=NC(=CC=1)N1CC2N(C(C1)C2)CC=1C=NC(=CC=1)OC)(C)C XIIOFHFUYBLOLW-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- XGVXKJKTISMIOW-ZDUSSCGKSA-N simurosertib Chemical compound N1N=CC(C=2SC=3C(=O)NC(=NC=3C=2)[C@H]2N3CCC(CC3)C2)=C1C XGVXKJKTISMIOW-ZDUSSCGKSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical class OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
-
- 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
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
- C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
- C07C43/168—Unsaturated ethers containing six-membered aromatic rings containing six-membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
- C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
- C07C43/1747—Unsaturated ethers containing halogen containing six-membered aromatic rings containing six membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- 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
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/16—Benz[e]indenes; Hydrogenated benz[e]indenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
Neben nematischen und cholesterischen Flüssigkristallen werden in jüngerer Zeit auch optisch aktive geneigt smektische (ferroelektrische) Flüssigkristalle in kommerziellen Displayvorrichtungen verwendet.In addition to nematic and cholesteric liquid crystals, more recently also optically active inclined smectic (ferroelectric) liquid crystals in commercial display devices used.
Clark und Lagerwall konnten zeigen, daß der Einsatz ferroelektrischer Flüssigkristalle (FLC) in sehr dünnen Zellen zu optoelektrischen Schalt- oder Anzeigeelementen führt, die im Vergleich zu den herkömmlichen TN ("twisted nematic")-Zellen um bis zu einem Faktor 1000 schnellere Schaltzeiten haben (siehe z. B. EP-A 0 032 362). Aufgrund dieser und anderer günstiger Eigenschaften, z. B. der bistabilen Schaltmöglichkeit und des nahezu blickwinkelunabhängigen Kontrasts, sind FLCs grundsätzlich für Anwendungsgebiete wie Computerdisplays gut geeignet.Clark and Lagerwall were able to show that the use of ferroelectric Liquid crystals (FLC) in very thin cells for optoelectric switching or Display elements leads, which compared to the conventional TN ("twisted nematic ") cells have switching times that are up to a factor of 1000 faster (see e.g. EP-A 0 032 362). Because of this and others cheaper Properties, e.g. B. the bistable switching option and almost angle-independent contrast, FLCs are basically for Areas of application such as computer displays are well suited.
Für die Verwendung von FLCs in elektrooptischen oder vollständig optischen Bauelementen benötigt man entweder Verbindungen, die geneigte bzw. orthogonale smektische Phasen ausbilden und selbst optisch aktiv sind, oder man kann durch Dotierung von Verbindungen, die zwar solche smektischen Phasen ausbilden, selbst aber nicht optisch aktiv sind, mit optisch aktiven Verbindungen ferroelektrische smektische Phasen induzieren. Die gewünschte Phase soll dabei über einen möglichst großen Temperaturbereich stabil sein.For the use of FLCs in electro-optical or completely optical Components either require connections that are inclined or form orthogonal smectic phases and are themselves optically active, or one can by doping compounds that are smectic Form phases, but are not optically active themselves, with optically active ones Compounds induce ferroelectric smectic phases. The desired The phase should be stable over the largest possible temperature range.
Zur Erzielung eines guten Kontrastverhältnisses in elektrooptischen Bauelementen ist eine einheitliche planare Orientierung der Flüssigkristalle nötig. Eine gute Orientierung in der SA und S* C-Phase läßt sich z. B. erreichen, wenn die Phasenfolge der Flüssigkristallmischung mit abnehmender Temperatur lautet:A uniform planar orientation of the liquid crystals is necessary to achieve a good contrast ratio in electro-optical components. A good orientation in the S A and S * C phase can e.g. B. achieve if the phase sequence of the liquid crystal mixture with decreasing temperature is:
Isotrop → N* → SA → S*C Isotropic → N * → S A → S * C
Voraussetzung ist, daß der Pitch (Ganghöhe der Helix) in der N*-Phase sehr groß (größer 10 µm) oder, noch besser, völlig kompensiert ist (siehe z. B. T. Matsumoto et al., p. 468-470, Proc. of the 6th Int. Display Research Conf., Japan Display, Sept. 30-Okto. 2, 1986, Tokyo, Japan; M. Murakami et al., ibid. S. 344-S. 347). Dies erreicht man, z. B. indem man zu der chiralen Flüssigkristallmischung, die in der N*-Phase z. B. eine linksdrehende Helix aufweist, einen oder mehrere optisch aktive Dotierstoffe, die eine rechtsdrehende Helix induzieren, in solchen Mengen hinzugibt, daß die Helix kompensiert wird.The prerequisite is that the pitch (pitch of the helix) is very high in the N * phase large (larger than 10 µm) or, even better, completely compensated (see e.g. T. Matsumoto et al., P. 468-470, Proc. of the 6th Int. Display Research Conf., Japan Display, Sept. 30-Octo. 2, 1986, Tokyo, Japan; M. Murakami et al., ibid. P. 344-p. 347). This is achieved e.g. B. by going to the chiral Liquid crystal mixture which in the N * phase z. B. a left-turning helix has one or more optically active dopants, the one induce clockwise helix in such amounts that the helix is compensated.
Für die Verwendung des SSFLCD-Effektes (Surface Stabilized Ferroelectric Liquid Crystal Display) von Clark und Lagerwall zur einheitlichen, planaren Orientierung ist ferner Voraussetzung, daß der Pitch in der smektischen C* Phase wesentlich größer ist als die Dicke des Anzeigeelementes (Mol. Cryst. Liq. Cryst. 94 (1983) 213-134 und 114 (1984) 151-187). Dies erreicht man, wie im Fall des cholesterischen Pitches, durch Verwendung von Dotierstoffen mit entgegengesetztem Drehsinn der Helix.For the use of the SSFLCD effect (Surface Stabilized Ferroelectric Liquid Crystal Display) from Clark and Lagerwall for uniform, planar Orientation is also a prerequisite that the pitch in the smectic C * Phase is significantly greater than the thickness of the display element (Mol. Cryst. Liq. Cryst. 94 (1983) 213-134 and 114 (1984) 151-187). This is achieved, as in the Case of cholesteric pitch, by using dopants with opposite direction of rotation of the helix.
Die optische Schaltzeit τ [µs] ferroelektrischer Flüssigkristallsysteme, die möglichst kurz sein soll, hängt von der Rotationsviskosität des Systems γ [mPas], der spontanen Polarisation Ps[nC/cm²] und der elektrischen Feldstärke E[V/m] ab nach der BeziehungThe optical switching time τ [µs] of ferroelectric liquid crystal systems, which should be as short as possible, depends on the rotational viscosity of the system γ [mPas], the spontaneous polarization P s [nC / cm²] and the electric field strength E [V / m] according to relationship
Da die Feldstärke E durch den Elektrodenabstand im elektrooptischen Bauteil und durch die angelegte Spannung festgelegt ist, muß das ferroelektrische Anzeigemedium niedrigviskos sein und eine hohe spontane Polarisation aufweisen, damit eine kurze Schaltzeit erreicht wird. Since the field strength E is due to the electrode spacing in the electro-optical component and is determined by the applied voltage, the ferroelectric Display medium be low viscosity and high spontaneous polarization have so that a short switching time is achieved.
Schließlich wird neben thermischer, chemischer und photochemischer Stabilität eine kleine optische Anisotropie Δn, vorzugsweise ≈ 0,13, und eine geringe positive oder vorzugsweise negative dielektrische Anisotropie Δε verlangt (siehe z. B. S.T. Lagerwall et al., "Ferroelectric Liquid Crystals for Displays" SID Symposium, ect. Meeting 1985, San Diego, Ca, USA).Finally, in addition to thermal, chemical and photochemical stability a small optical anisotropy Δn, preferably ≈ 0.13, and a small one requires positive or preferably negative dielectric anisotropy Δε (see e.g. B. S.T. Lagerwall et al., "Ferroelectric Liquid Crystals for Displays" SID Symposium, ect. Meeting 1985, San Diego, CA, USA).
Die Gesamtheit dieser Forderungen ist nur mit Mischungen aus mehreren Komponenten zu erfüllen. Als Basis (oder Matrix) dienen dabei bevorzugt Verbindungen, die möglichst selbst bereits die gewünschte Phasenfolge I→N→SA→SC aufweisen. Weitere Komponenten der Mischung werden oftmals zur Schmelzpunktserniedrigung und zur Verbreiterung der SC- und meist auch N-Phase, zum Induzieren der optischen Aktivität, zur Pitch-Kompensation und zur Anpassung der optischen und dielektrischen Anisotropie zugesetzt, wobei aber beispielsweise die Rotationsviskosität möglichst nicht vergrößert werden soll.All of these requirements can only be met with mixtures of several components. The basis (or matrix) used is preferably compounds which, if possible, already have the desired phase sequence I → N → S A → S C. Other components of the mixture are often added to lower the melting point and broaden the S C - and usually also the N phase, to induce optical activity, to compensate for pitch and to adjust the optical and dielectric anisotropy, but, for example, do not increase the rotational viscosity if possible shall be.
Ferroelektrische Flüssigkristallanzeigen lassen sich auch durch Nutzung des DHF (Distorted Helix Formation)-Effektes oder des PSFLCD-Effektes (Pitch Stabilized Ferroelectric Liquid Crystal Display, auch SBF = Short pitch Bistable Ferroelektric Effekt genannt) betreiben. Der DHF-Effekt wurde von B.I. Ostrovski in Advances in Liquid Crystal Research and Applications, Oxford/Budapest 1980, 469 ff. beschrieben, der PSFLCD-Effekt ist in DE-A 39 20 625 bzw. EP-A 0 405 346 beschrieben. Zur Nutzung dieser Effekte wird im Gegensatz zum SSFLCD-Effekt ein flüssigkristallines Material mit einem kurzen SC-Pitch benötigt.Ferroelectric liquid crystal displays can also be operated by using the DHF (Distorted Helix Formation) effect or the PSFLCD effect (Pitch Stabilized Ferroelectric Liquid Crystal Display, also called SBF = Short pitch Bistable Ferroelectric Effect). The DHF effect was described by BI Ostrovski in Advances in Liquid Crystal Research and Applications, Oxford / Budapest 1980, 469 ff., The PSFLCD effect is described in DE-A 39 20 625 and EP-A 0 405 346. In contrast to the SSFLCD effect, a liquid crystal material with a short S C pitch is required to use these effects.
Derivate des Indans (EP-A 546 338) sowie Kondensierte-6-Ring-5-Ring- Verbindungen (EP-A 555 843) sind bereits als Flüssigkristalle oder als Komponenten flüssigkristalliner Mischungen beschrieben.Derivatives of indane (EP-A 546 338) and condensed-6-ring-5-ring Compounds (EP-A 555 843) are already in the form of liquid crystals or as Components of liquid-crystalline mixtures described.
Da die Entwicklung, insbesondere von ferroelektrischen Flüssigkristallmischungen, noch in keiner Weise als abgeschlossen betrachtet werden kann, sind die Hersteller von Displays an den unterschiedlichsten Komponenten für Mischungen interessiert. Dieses u. a. auch deshalb, weil erst das Zusammenwirken der flüssigkristallinen Mischungen mit den einzelnen Bauteilen der Anzeigevorrichtung bzw. der Zellen (z. B. der Orientierungsschicht) Rückschlüsse auf die Qualität auch der flüssigkristallinen Mischungen zuläßt.Because the development, especially of ferroelectric Liquid crystal mixtures, in no way considered complete the manufacturers of displays are on the most varied Components for mixtures interested. This u. a. also because only the interaction of the liquid crystalline mixtures with the individual Components of the display device or the cells (e.g. the orientation layer) Allows conclusions to be drawn about the quality of the liquid-crystalline mixtures.
Aufgabe der vorliegenden Erfindung war es daher, neue Verbindungen bereitzustellen, die in flüssigkristallinen Mischungen geeignet sind, das Eigenschaftsprofil dieser Mischungen zu verbessern.The object of the present invention was therefore to create new compounds To provide, which are suitable in liquid crystalline mixtures, the To improve the property profile of these mixtures.
Es wurde nun gefunden, daß tricyclische Verbindungen der Formel I in besonderer Weise zum Einsatz in Flüssigkristallmischungen geeignet sind.It has now been found that tricyclic compounds of the formula I in are particularly suitable for use in liquid crystal mixtures.
Der aromatische Grundkörper selbst (siehe z. B. J. Chem. Soc. 1933, 1098) und auch wenige mono-substituierte Derivate (siehe z. B. Ber. Dtsch. Chem. Ges. 60, 1835) sind bekannt; über eine generelle Eignung dieser tricyclischen Verbindungen als Komponenten in Flüssigkristallmischungen liegen jedoch keine Veröffentlichungen vor.The aromatic base body itself (see, for example, J. Chem. Soc. 1933, 1098) and also a few mono-substituted derivatives (see e.g. Ber. Dtsch. Chem. Ges. 60, 1835) are known; about the general suitability of these tricyclic However, there are no compounds as components in liquid crystal mixtures Publications.
Gegenstand der Erfindung sind daher Verbindungen der Formel I,The invention therefore relates to compounds of the formula I
in der die Symbole und Indizes folgende Bedeutungen haben:
R¹ ist -F, -CN, -Cl, CF₃ oder hat, unabhängig von R², eine der bei R²
aufgeführten Bedeutungen;
R² H oder ein geradkettiger oder verzweigter Alkylrest mit 1 bis 20 C-
Atomen (mit oder ohne asymmetrisches C-Atom), wobei auch eine oder
mehrere -CH₂-Gruppen (jedoch nicht die unmittelbar an den Fünfring
gebundene) durch -O-, -S-, CH=CH-, -C≡C-, Cyclopropan-1,2-diyl,
-Si(CH₃)₂-, 1,4-Phenylen, 1,4-Cyclohexylen, 1,3-Cyclopentylen, 1,3
Cyclobutylen, 1,3-Dioxan-2,5-diyl ersetzt sein können, mit der Maßgabe,
daß Sauerstoffatome und Schwefelatome nicht unmittelbar verbunden
sein dürfen, und wobei auch ein oder mehrere H-Atome des Alkylrestes
durch F, Cl, Br oder OR³ substituiert sein können, oder eine der
nachfolgenden Gruppen (optisch aktiv oder racemisch):in which the symbols and indices have the following meanings:
R¹ is -F, -CN, -Cl, CF₃ or, independently of R², has one of the meanings listed for R²;
R² H or a straight-chain or branched alkyl radical with 1 to 20 C atoms (with or without asymmetrical C atom), with one or more -CH₂ groups (but not the one bonded directly to the five-membered ring) by -O-, - S-, CH = CH-, -C≡C-, cyclopropane-1,2-diyl, -Si (CH₃) ₂-, 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentylene, 1, 3 cyclobutylene, 1,3-dioxane-2,5-diyl can be replaced, with the proviso that oxygen atoms and sulfur atoms must not be directly connected, and also one or more H atoms of the alkyl radical by F, Cl, Br or OR³ may be substituted, or one of the following groups (optically active or racemic):
R³ ist H oder ein geradkettiger Alkylrest mit 1 bis 6 C-Atomen;
R⁴, R⁵, R⁶ sind gleich-oder verschieden Wasserstoff oder ein geradkettiger oder
verzweigter Alkylrest mit 1-16 C-Atomen, wobei auch eine oder zwei
CH₂-Gruppen durch -O- und/oder -CH = CH- ersetzt sein können, mit der
Maßgabe, daß Sauerstoffatome nicht unmittelbar miteinander gebunden
sein dürfen, R⁴ und R⁵ können zusammen auch -(CH₂)₄- oder -(CH₂)₅-
sein, wenn sie an ein Oxiran-, Dioxolan-, Tetrahydrofuran-,
Tetrahydropropyran-, Bytorolacton- oder Valerolacton-System gebunden
sind;
Q¹ ist eine Einfachbindung, -CO-O- oder -CH₂-O-;
Ring B istR³ is H or a straight-chain alkyl radical with 1 to 6 C atoms;
R⁴, R⁵, R⁶ are identical or different hydrogen or a straight-chain or branched alkyl radical having 1-16 C atoms, it also being possible for one or two CH₂ groups to be replaced by -O- and / or -CH = CH- with the proviso that oxygen atoms must not be bonded directly to one another, R⁴ and R⁵ together can also be - (CH₂) ₄- or - (CH₂) ₅- if they are an oxirane, dioxolane, tetrahydrofuran, tetrahydropropyran, bytorolactone - or valerolactone system are bound;
Q¹ is a single bond, -CO-O- or -CH₂-O-;
Ring B is
A¹ ist 1,4-Phenylen, 1,4-Cyclohexylen, Pyridin-2,5-diyl, Pyrimidin-2,5-diyl,
(1,3,4)Thiadiazol-2,5-diyl, (1,3)-Thiazol-2,5-diyl, (1,3)-Thiazol-2,4-diyl,
wobei auch jeweils ein oder mehrere Wasserstoffatome durch F
substituiert sein können, (1,3,4)Thiadiazol-2,5-diyl;
M¹ ist eine Einfachbindung, -C-C-, -CH₂CH₂-, -O-CO-, -CO-O-, -CO-,
-OCH₂-, -CH₂O-, -O-CO-O-;
m ist Null oder Eins.A¹ is 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, (1,3,4) thiadiazole-2,5-diyl, (1,3) -Thiazol-2,5-diyl, (1,3) -Thiazol-2,4-diyl, where one or more hydrogen atoms can be substituted by F, (1,3,4) thiadiazole-2,5-diyl ;
M¹ is a single bond, -CC-, -CH₂CH₂-, -O-CO-, -CO-O-, -CO-, -OCH₂-, -CH₂O-, -O-CO-O-;
m is zero or one.
Bevorzugte Verbindungen der Formel (I) sind solche der Formel (Ia),Preferred compounds of the formula (I) are those of the formula (Ia)
wobei die Symbole und Indizes die in der Formel (I) angegebenen Bedeutungen haben. where the symbols and indices have the meanings given in the formula (I) to have.
Darunter besonders bevorzugt sind die Verbindungen der Formeln (Ia bis Ia 11),Among these, particular preference is given to the compounds of the formulas (Ia to Ia 11),
wobei R¹ und R² die in Formel (I) angegebenen Bedeutungen haben. Weitere bevorzugte Teilbereiche der Formel (Ia) sind die Verbindungen der Formeln (Iaa 1) bis (Iaa 14),wherein R¹ and R² have the meanings given in formula (I). Further preferred subsections of the formula (Ia) are the compounds of Formulas (Iaa 1) to (Iaa 14),
wobei R² die in Formel (I) angegebenen Bedeutungen hat. where R² has the meanings given in formula (I).
Eine weitere bevorzugte Ausführungsform der Formel (Ia) sind die Verbindungen der Formeln (Iab 1),Another preferred embodiment of the formula (Ia) are the compounds of the formulas (Iab 1),
wobei R¹ und R² die in Formel (I) angegebenen Bedeutungen haben. Darunter ganz besonders bevorzugt sind die Verbindungen der Formeln (Iab 1a) bis (Iab 1d),wherein R¹ and R² have the meanings given in formula (I). Among these, the compounds of the formulas (Iab 1a) are very particularly preferred to (Iab 1d),
wobei
p eine natürliche Zahl von 1 bis 20;
q eine natürliche Zahl von 1 bis 19;
s, t eine natürliche Zahl von 1 bis 18 und
y eine natürliche Zahl von 1 bis 17 bedeutet und t + y 18 sein muß.
in which
p is a natural number from 1 to 20;
q is a natural number from 1 to 19;
s, t is a natural number from 1 to 18 and
y is a natural number from 1 to 17 and t + y must be 18.
Die Herstellung der erfindungsgemäßen Verbindungen erfolgt nach an sich literaturbekannten Methoden, wie sie in Standardwerken zur Organischen Synthese, z. B. Houben-Weyl, Methoden der Organischen Chemie, Georg- Thieme-Verlag, Stuttgart, beschrieben werden.The compounds according to the invention are prepared per se methods known from the literature, as used in standard works on organic matter Synthesis, e.g. B. Houben-Weyl, Methods of Organic Chemistry, Georg- Thieme-Verlag, Stuttgart.
Die Herstellung erfolgt dabei unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The production takes place under reaction conditions for the above Implementations are known and suitable. It can also by itself make use of known variants not mentioned here.
Die Ausgangsstoffe können gewünschtenfalls auch in situ gebildet werden, und zwar 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, and in such a way that they are not isolated from the reaction mixture, but rather immediately continues to react to the compounds of formula (I).
So ist im Schema 1 beispielhaft die Synthese des Typs (Iab 1) aufgeführt, deren Grundzüge jedoch auch für die anderen Typen der erfindungsgemäßen Verbindungen (I) gelten. Ausgangspunkt ist die bifunktionelle 6-Hydroxy-2- naphthol-säure, die nach Blockierung der phenolischen Gruppe - entweder durch den angestrebten Rest R, der sich aus R¹ ableitet, oder durch eine Schutzgruppe für Phenole, die im weiteren Verlauf der Synthese wieder entfernt wird, um einen gewünschten Substituenten einzubringen - nach Veresterung der Carboxylfunktion zu einem 6-substituierten Naphthalin-2-yl-methanol reduziert wird. Dieser wird entweder in die entsprechende Brommethylverbindung oder das Tosylat (Mesylat) überführt, um alkylierend mit mono-substituierten Malonsäuredialkylestern zu einem disubstituierten Malonester umgesetzt werden zu können; dabei entspricht auf der Stufe des mono-substituierten Malonesters der Substituent dem späteren Substituenten R² in (I). Dieser disubstituierte Malonester wird nach gängigen Methoden verseift und zur 2,3-substituierten Propionsäure decarboxyliert. Durch Ringschlußreaktion, z. B. in Polyphosphorsäure oder unter Einfluß von Lewissäuren, wird ein tricyclisches Keton erhalten. Durch geeignete Reduktionsmittel, z. B. Triethylsilan in Trifluoressigsäure, wird die Zielstruktur (Iab 1) erhalten. For example, in Scheme 1 the synthesis of type (Iab 1) is listed, the Basics, however, also for the other types of the invention Compounds (I) apply. The starting point is the bifunctional 6-hydroxy-2- naphtholic acid after blocking the phenolic group - either by the desired radical R, which is derived from R¹, or by a protective group for phenols, which is removed in the further course of the synthesis in order to introduce a desired substituent - after esterification of the Carboxylfunction reduced to a 6-substituted naphthalin-2-yl-methanol becomes. This is either in the corresponding bromomethyl compound or the tosylate (mesylate) is converted to alkylating with mono-substituted Malonic acid dialkyl esters can be converted into a disubstituted malonic ester to be able to; corresponds to the level of the mono-substituted malonic ester the substituent is the later substituent R² in (I). This disubstituted Malonic ester is saponified according to common methods and becomes 2,3-substituted Decarboxylated propionic acid. By ring closure reaction, e.g. B. in Polyphosphoric acid or under the influence of Lewis acids becomes a tricyclic Get ketone. By suitable reducing agents, e.g. B. triethylsilane in Trifluoroacetic acid, the target structure (Iab 1) is obtained.
Schema 2 nimmt wesentliche Grundzüge des Schema 1 auf, vor allem hinsichtlich der Ausbildung des Rings B. Spezifisch ist die vorgeschaltete regioselektive Anknüpfung des Restes R¹-A¹- durch Pd-katalysierte Boronsäurekupplung mit einem bifunktionellen Naphthalin-2,6-diyl-derivat.Scheme 2 outlines key features of Scheme 1, especially with regard to the formation of the ring B. The upstream is specific regioselective attachment of the radical R¹-A¹- by Pd-catalyzed Boronic acid coupling with a bifunctional naphthalene-2,6-diyl derivative.
Schema 3 zeigt, wie das tricyclische Keton - das nach Schema 1 erhalten wird - z. B. mit DAST(Diethylamino-schwefeltrifluorid) in die Verbindungen (Ib) bzw. (Ic) überführt werden kann. Das Verhältnis von (Ib) zu (Ic) kann in Grenzen durch die Reaktionsbedingungen gesteuert werden.Scheme 3 shows how the tricyclic ketone - obtained according to Scheme 1 - e.g. B. with DAST (diethylamino-sulfur trifluoride) in the compounds (Ib) or (Ic) can be transferred. The ratio of (Ib) to (Ic) can be limited by the Reaction conditions can be controlled.
Reduktion des tricyclischen Ketons, z. B. mit LiAIH₄ oder NaBH₄, und sauer katalysierte Dehydratisierung des so erhaltenen Benzylalkohols liefert die Verbindungen (Id); Umsetzung dieses Benzylalkohols mit DAST resultiert in den Verbindungen (Ie). Reduction of the tricyclic ketone, e.g. B. with LiAIH₄ or NaBH₄, and acidic Catalyzed dehydration of the benzyl alcohol thus obtained provides the Connections (Id); Implementation of this benzyl alcohol with DAST results in Connections (Ie).
a) z. B. mit RX/KOH/EtOH/H₂O;
b) z. B. mit R′OH/DCC;
c) mit LiAlH;
d) 1. Überführung in das Tosylat 2. Umsetzung mit CH(R′′)(CO₂Et)₂/Alkoholat,
(analog EP-A 546 338);
e) 1. NaOH/H₂O 2. H₃O+ 3. Δ, (analog EP-A 546 338);
f) mit Polyphosphorsäure, (analog EP-A 546 338);
g) mit Et₃SiH/TFA, (analog EP-A 546 338).
a) z. B. with RX / KOH / EtOH / H₂O;
b) z. B. with R'OH / DCC;
c) with LiAlH;
d) 1. Conversion to tosylate 2. Reaction with CH (R ′ ′) (CO₂Et) ₂ / alcoholate, (analogous to EP-A 546 338);
e) 1. NaOH / H₂O 2. H₃O + 3. Δ, (analog EP-A 546 338);
f) with polyphosphoric acid (analogous to EP-A 546 338);
g) with Et₃SiH / TFA, (analog EP-A 546 338).
a, b) 1. Überführung in das Triflat 2. Kupplung mit R¹-A¹-B(OH)₂; beides in
Analogie zu Mol. Cryst. 1991, 204, 91;
c) 1. Mg 2. H₂CO;
d) 1. Überführung in das Tosylat 2. Umsetzung mit CH(R′′)(CO₂Et)₂/Alkoholat
(beides analog EP-A 546 338);
e) 1. NaOH/H₂O 2. H₃O+ 3. Δ (analog EP-A 546 338);
f) mit Polyphosphorsäure (analog EP-A 546 338);
g) mit Et₃SiH/TFA (analog EP-A 546 338).
a, b) 1. Conversion to the triflate 2. Coupling with R¹-A¹-B (OH) ₂; both in analogy to Mol. Cryst. 1991, 204, 91;
c) 1. Mg 2. H₂CO;
d) 1. Conversion to tosylate 2. Reaction with CH (R ′ ′) (CO₂Et) ₂ / alcoholate (both analogous to EP-A 546 338);
e) 1. NaOH / H₂O 2. H₃O + 3. Δ (analogous to EP-A 546 338);
f) with polyphosphoric acid (analogous to EP-A 546 338);
g) with Et₃SiH / TFA (analog EP-A 546 338).
a) mit DAST; vgl. M. Hudlicky, Org. Reactions 35, 513;
b) z. B. LiAlH₄;
c) H⁺/Δ.a) with DAST; see. M. Hudlicky, Org. Reactions 35, 513;
b) z. B. LiAlH₄;
c) H⁺ / Δ.
Die Synthese der Reste R¹-(A¹)-(-M¹) und R² oder geeigneter reaktiver Derivate davon oder auch anderer geeigneter Vorläufer dieser Gruppierungen erfolgt nach an sich bekannten, dem Fachmann geläufigen Methoden.The synthesis of the residues R¹- (A¹) - (- M¹) and R² or suitable reactive derivatives of these or other suitable precursors of these groups follows known methods known to those skilled in the art.
Die Herstellung erfolgt dabei unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The production takes place under reaction conditions for the above Implementations are known and suitable. It can also by itself make use of known variants not mentioned here.
Beispielsweise sei verwiesen auf DE-A 23 44 732, 24 50 088, 24 29 093, 25 02 94, 26 36 684, 27 01 591 und 27 52 975 für Verbindungen mit 1,4- Cyclohexylen und 1,4-Phenylen-Gruppen; DE-A 26 41 724 für Verbindungen mit Pyrimidin-2,5-diyl-Gruppen; DE-A 40 26 223 und EP-A 03 91 203 für Verbindungen mit Pyridin-2,5-diyl-Gruppen; EP-A 309 514 für Verbindungen mit (1,3,4)-Thiadiazol-2-5-diyl-Gruppen.For example, reference is made to DE-A 23 44 732, 24 50 088, 24 29 093, 25 02 94, 26 36 684, 27 01 591 and 27 52 975 for connections with 1,4- Cyclohexylene and 1,4-phenylene groups; DE-A 26 41 724 for connections with Pyrimidine-2,5-diyl groups; DE-A 40 26 223 and EP-A 03 91 203 for Compounds with pyridine-2,5-diyl groups; EP-A 309 514 for connections with (1,3,4) -Thiadiazole-2-5-diyl groups.
Die Herstellung disubstituierter Pyridine und disubstituierter Pyrimidine findet sich beispielsweise auch in den entsprechenden Bänden der Serie "The Chemistry of Heterocyclic Compounds" von A. Weissberger und E.C. Taylor (Herausgeber).The production of disubstituted pyridines and disubstituted pyrimidines takes place can also be found, for example, in the corresponding volumes of the series "The Chemistry of Heterocyclic Compounds "by A. Weissberger and E.C. Taylor (Editor).
Dioxanderivate werden zweckmäßig durch Reaktion eines entsprechenden Aldehyds (oder eines seiner reaktionsfähigen Derivate) mit einem entsprechenden 1,3-Diol (oder einem seiner reaktionsfähigen Derivate) hergestellt, vorzugsweise in Gegenwart eines inerten Lösungsmittels, wie Benzol oder Toluol, und/oder eines Katalysators, z. B. einer starken Säure, wie Schwefelsäure, Benzol- oder p-Toluolsulfonsäure, bei Temperaturen zwischen etwa 20°C und etwa 150°C, vorzugsweise zwischen 80°C und 120°C. Als reaktionsfähige Derivate der Ausgangsstoffe eignen sich in erster Linie Acetale.Dioxane derivatives are useful by reacting an appropriate one Aldehyde (or one of its reactive derivatives) with a corresponding 1,3-diol (or one of its reactive derivatives) prepared, preferably in the presence of an inert solvent such as benzene or toluene, and / or a catalyst, e.g. B. a strong acid, such as Sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° C and about 150 ° C, preferably between 80 ° C and 120 ° C. As reactive derivatives of the starting materials are primarily suitable for acetals.
Die genannten Aldehyde und 1,3-Diole sowie ihre reaktionsfähigen Derivate sind zum Teil bekannt, zum Teil können sie ohne Schwierigkeiten nach Standardverfahren der Organischen Chemie aus literaturbekannten Verbindungen hergestellt werden. Beispielsweise sind die Aldehyde durch Oxydation entsprechender Alkohole oder durch Reduktion von Nitrilen oder entsprechenden Carbonsäuren oder ihrer Derivate, die Diole durch Reduktion entsprechender Diester erhältlich.The aldehydes and 1,3-diols mentioned and their reactive derivatives are partly known, partly they can be followed without difficulty Standard methods of organic chemistry from literature Connections are made. For example, the aldehydes are through Oxidation of appropriate alcohols or by reduction of nitriles or corresponding carboxylic acids or their derivatives, the diols by reduction corresponding diester available.
Verbindungen, worin ein aromatischer Ring durch mindestens ein F-Atom substituiert ist, können auch aus den entsprechenden Diazoniumsalzen durch Austausch der Diazoniumgruppe gegen ein Fluoratom, z. B. nach den Methoden von Balz und Schiemann, erhalten werden. Compounds in which an aromatic ring has at least one F atom is substituted, can also from the corresponding diazonium salts Exchange of the diazonium group for a fluorine atom, e.g. B. according to the methods from Balz and Schiemann.
Ester der Formel (I) können auch durch Veresterung entsprechender Carbonsäuren (oder ihrer reaktionsfähigen Derivate) mit Alkoholen bzw. Phenolen (oder ihren reaktionsfähigen Derivaten) oder nach der DCCl-Methode (DCCl = Dicyclohexylcarbodiimid) erhalten werden.Esters of the formula (I) can also be correspondingly esterified Carboxylic acids (or their reactive derivatives) with alcohols or Phenols (or their reactive derivatives) or by the DCCl method (DCCl = dicyclohexylcarbodiimide) can be obtained.
Die entsprechenden Carbonsäuren und Alkohole bzw. Phenole sind bekannt und können in Analogie zu bekannten Verfahren hergestellt werden.The corresponding carboxylic acids and alcohols or phenols are known and can be produced in analogy to known processes.
Als reaktionsfähige Derivate der genannten Carbonsäuren eignen sich insbesondere die Säurehalogenide, vor allem die Chloride und Bromide, ferner die Anhydride, z. B. auch gemischte Anhydride, Azide oder Ester, insbesondere Alkylester mit 1-4 C-Atomen in der Alkylgruppe.Suitable reactive derivatives of the carboxylic acids mentioned are especially the acid halides, especially the chlorides and bromides the anhydrides, e.g. B. also mixed anhydrides, azides or esters, in particular Alkyl esters with 1-4 C atoms in the alkyl group.
Als reaktionsfähige Derivate der genannten Alkohole bzw. Phenole kommen insbesondere die entsprechenden Metallalkoholate bzw. Phenolate, vorzugsweise eines Alkalimetalls, wie Natrium oder Kalium, in Betracht.Coming as reactive derivatives of the alcohols or phenols mentioned in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal such as sodium or potassium.
Die Veresterung wird vorteilhaft in Gegenwart eines inerten Lösungsmittels durchgeführt. Gut geeignet sind insbesondere Ether, wie Diethylether, Di-n- butylether, THF, Dioxan oder Anisol, Ketone, wie Aceton, Butanon oder Cyclohexanon, Amide, wie DMF oder Phosphorsäurehexamethyltriamid, Kohlenwasserstoffe, wie Benzol, Toluol oder Xylol, Halogenkohlenwasserstoffe, wie Tetrachlorkohlenstoff, Dichlormethan oder Tetrachlorethylen und Sulfoxide, wie Dimethylsulfoxid oder Sulfolan.The esterification is advantageous in the presence of an inert solvent carried out. Particularly suitable are ethers, such as diethyl ether, di-n- butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or Cyclohexanone, amides, such as DMF or phosphoric acid hexamethyltriamide, Hydrocarbons, such as benzene, toluene or xylene, halogenated hydrocarbons, such as carbon tetrachloride, dichloromethane or tetrachlorethylene and sulfoxides, such as dimethyl sulfoxide or sulfolane.
Ether der Formel (I) sind durch Veretherung entsprechender Hydroxyverbindungen, vorzugsweise entsprechender Phenole, erhältlich, wobei die Hydroxyverbindung zweckmäßig zunächst in ein entsprechendes Metallderivat, z. B. durch Behandeln mit NaH, NaNH₂, NaOH, KOH, Na₂CO₃ oder K₂CO₃ in das entsprechende Alkalimetallalkoholat oder Alkalimetallphenolat übergeführt wird. Dieses kann dann mit dem entsprechenden Alkylhalogenid, Sulfonat oder Dialkylsulfat umgesetzt werden, zweckmäßig in einem inerten Lösungsmittel, wie Aceton, 1,2-Dimethoxyethan, DMF oder Dimethylsulfoxid, oder auch mit einem Überschuß an wäßriger oder wäßrig-alkoholischer NaOH oder KOH bei Temperaturen zwischen etwa 200 und 100°C.Ethers of the formula (I) are more appropriate by etherification Hydroxy compounds, preferably corresponding phenols, are available, where the hydroxy compound expediently first in a corresponding Metal derivative, e.g. B. by treatment with NaH, NaNH₂, NaOH, KOH, Na₂CO₃ or K₂CO₃ in the corresponding alkali metal alcoholate or alkali metal phenolate is transferred. This can then be combined with the corresponding alkyl halide, Sulfonate or dialkyl sulfate are implemented, advantageously in an inert Solvents such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide, or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 200 and 100 ° C.
Was die Synthese spezieller Reste R¹ und R² angeht, sei zusätzlich beispielsweise verwiesen auf EP-A 0 355 008 für Verbindungen mit siliziumhaltigen Seitenketten und EP-A 0 292 954 und EP-A 0 398 155 für Verbindungen mit Cyclopropylgruppen in der Seitenkette.Regarding the synthesis of special R¹ and R² residues, is additional for example, refer to EP-A 0 355 008 for compounds with silicon-containing side chains and EP-A 0 292 954 and EP-A 0 398 155 for Compounds with cyclopropyl groups in the side chain.
Die Verbindungen der Formel (I) bilden im allgemeinen flüssigkristalline Mesophasen in einem für die elektrooptische Verwendung günstig gelegenen Temperaturbereich. Chemisch, thermisch und gegen Licht sind sie stabil.The compounds of formula (I) generally form liquid crystalline Mesophases in one conveniently located for electro-optical use Temperature range. They are stable chemically, thermally and against light.
Mit der Bereitstellung von Verbindungen der Formel (I) wird ganz allgemein die Palette der flüssigkristallinen Substanzen, die sich unter verschiedenen anwendungstechnischen Gesichtspunkten zur Herstellung flüssigkristalliner Gemische eignen, erheblich verbreitert.With the provision of compounds of formula (I), the Range of liquid crystalline substances, which are among different technical aspects for the production of liquid crystalline Mixtures are suitable, considerably widened.
In diesem Zusammenhang besitzen die Verbindungen der Formel (I) einen breiten Anwendungsbereich. In Abhängigkeit von der Auswahl der Substituenten können diese Verbindungen als Basismaterialien dienen, aus denen flüssigkristalline smektische, insbesondere ferroelektrische Phasen zum überwiegenden Teil zusammengesetzt sind; es können aber auch Verbindungen der Formel (I) flüssigkristallinen Basismaterialien aus anderen Verbindungsklassen zugesetzt werden, um beispielsweise die dielektrische und/oder optische Anisotropie und/oder die Viskosität und/oder die spontane Polarisation und/oder den Phasenbereiche und/oder den Tiltwinkel und/oder den Pitch eines solchen Dielektrikums zu variieren.In this connection, the compounds of formula (I) have a wide range Scope of application. Depending on the choice of substituents these compounds can serve as base materials from which liquid-crystalline smectic, especially ferroelectric phases for the majority are composed; but connections can also be made of the formula (I) liquid-crystalline base materials from others Classes of compound are added, for example the dielectric and / or optical anisotropy and / or the viscosity and / or the spontaneous Polarization and / or the phase ranges and / or the tilt angle and / or the To vary the pitch of such a dielectric.
Gegenstand der Erfindung ist auch die Verwendung von Verbindungen der Formel (I) in Flüssigkristallmischungen, vorzugsweise ferroelektrischen, antiferroelektrischen und nematischen, insbesondere ferroelektrischen. The invention also relates to the use of compounds of Formula (I) in liquid crystal mixtures, preferably ferroelectric, antiferroelectric and nematic, especially ferroelectric.
Weiterhin Gegenstand der Erfindung sind Flüssigkristallmischungen, vorzugsweise ferroelektrische, antiferroelektrische und nematische, insbesondere ferroelektrische, enthaltend eine oder mehrere Verbindungen der Formel (I), vorzugsweise der Formel (Ia).The invention furthermore relates to liquid crystal mixtures, preferably ferroelectric, antiferroelectric and nematic, in particular ferroelectric, containing one or more compounds of the Formula (I), preferably of formula (Ia).
Insbesondere sind auch nematische Flüssigkristallmischungen, vorzugsweise zur Anwendung in TN-, TFT-TN- und STN-Displays, enthaltend eine oder mehrere Verbindungen der Formel (Iaa).In particular, nematic liquid crystal mixtures are also preferred Use in TN, TFT-TN and STN displays containing one or more Compounds of formula (Iaa).
Die erfindungsgemäßen Flüssigkristallmischungen enthalten im allgemeinen 2 bis 35, vorzugsweise 2 bis 25, besonders bevorzugt 2 bis 20 Komponenten.The liquid crystal mixtures according to the invention generally contain 2 to 35, preferably 2 to 25, particularly preferably 2 to 20 components.
Sie enthalten im allgemeinen 0,01 bis 80 Gew.-%, vorzugsweise 0,1 bis 60 Gew.-%, besonders bevorzugt 0,1 bis 30 Gew.-%, an einer oder mehreren, vorzugsweise 1 bis 10, besonders bevorzugt 1 bis 5, ganz besonders bevorzugt 1 bis 3, der erfindungsgemäßen Verbindungen der Formel (I).They generally contain 0.01 to 80 wt .-%, preferably 0.1 to 60 % By weight, particularly preferably 0.1 to 30% by weight, of one or more, preferably 1 to 10, particularly preferably 1 to 5, very particularly preferably 1 to 3, the compounds of formula (I) according to the invention.
Weitere Komponenten von Flüssigkristallmischungen, die erfindungsgemäße Verbindungen der Formel (I) enthalten, werden vorzugsweise ausgewählt aus den bekannten Verbindungen mit smektischen und/oder nematischen und/oder cholesterischen Phasen.Other components of liquid crystal mixtures, the invention Compounds of formula (I) are preferably selected from the known compounds with smectic and / or nematic and / or cholesteric phases.
- - Derivate des Phenylpyrimidins, wie beispielsweise in WO 86/06401, US-A 4 874 542 beschrieben,Derivatives of phenylpyrimidine, as for example in WO 86/06401, US-A 4 874 542,
- - metasubstituierte Sechsringaromaten, wie beispielsweise in EP-A 0 578 054 beschrieben,- Meta-substituted six-ring aromatics, such as in EP-A 0 578 054,
- - Siliziumverbindungen, wie beispielsweise in EP-A 0 355 008 beschrieben,Silicon compounds, as described for example in EP-A 0 355 008,
- - mesogene Verbindungen mit nur einer Seitenkette, wie in EP-A 0 541 081 beschrieben,- mesogenic connections with only one side chain, as in EP-A 0 541 081,
- - Hydrochinonderivate, wie beispielsweise in EP-A 0 603 786 beschrieben,- Hydroquinone derivatives, such as in EP-A 0 603 786,
- - Pyridylpyrimidine, wie beispielsweise in WO 92/12974 beschrieben, Pyridylpyrimidines, as described for example in WO 92/12974,
- - Phenylbenzoate, wie beispielsweise bei P. Keller, Ferroelectrics 58 (1984), 3 und J. W. Goodby et al., Liquid Crystals and Ordered Fluids, Bd. 4, New York 1984 beschrieben und- Phenylbenzoates, such as from P. Keller, Ferroelectrics 58 (1984), 3 and J.W. Goodby et al., Liquid Crystals and Ordered Fluids, 4, New York 1984 and
- - Thiadiazole, wie beispielsweise in EP-B 309 514 beschrieben.Thiadiazoles, as described for example in EP-B 309 514.
Als chirale, nicht racemische Dotierstoffe kommen beispielsweise in Frage:Examples of chiral, non-racemic dopants are:
- - optisch aktive Phenylbenzoate, wie beispielsweise bei P. Keller, Ferroelectrics 58 (1984), 3 und J. W. Goodby et al., Liquid Crystals and Ordered Fluids, Bd. 4, New York 1984 beschrieben,optically active phenylbenzoates, such as, for example, P. Keller, Ferroelectrics 58 (1984), 3 and J.W. Goodby et al., Liquid Crystals and Ordered Fluids, Vol. 4, New York 1984,
- - optisch aktive Oxiranether, wie beispielsweise in EP-A 0 263 437 und WO-A 93/13093 beschrieben,- Optically active oxirane ethers, such as in EP-A 0 263 437 and WO-A 93/13093,
- - optisch aktive Oxiranester, wie beispielsweise in EP-A 0 292 954 beschrieben,- Optically active oxirane esters, as for example in EP-A 0 292 954 described
- - optisch aktive Dioxolanether, wie beispielsweise in EP-A 0 351 746 beschrieben,optically active dioxolane ethers, such as, for example, in EP-A 0 351 746 described
- - optisch aktive Dioxolanester, wie beispielsweise in EP-A 0 361 272 beschrieben, und- Optically active dioxolane esters, such as, for example, in EP-A 0 361 272 described, and
- - optisch aktive Tetrahydrofuran-2-carbonsäureester, wie beispielsweise in EP-A 0 355 561 beschrieben.- Optically active tetrahydrofuran-2-carboxylic acid esters, such as in EP-A 0 355 561.
Die Mischungen wiederum können Anwendung finden in elektrooptischen oder vollständig optischen Elementen, z. B. Anzeigeelementen, Schaltelementen, Lichtmodulatoren, Elementen zur Bildbearbeitung und/oder Signalverarbeitung oder allgemein im Bereich der nichtlinearen Optik.The mixtures in turn can be used in electro-optical or completely optical elements, e.g. B. display elements, switching elements, Light modulators, elements for image processing and / or signal processing or generally in the field of nonlinear optics.
Flüssigkristalline Mischungen, die Verbindungen der allgemeinen Formel (I) enthalten, sind besonders für die Verwendung in elektrooptischen Schalt- und Anzeigevorrichtungen (Displays) geeignet. Diese Displays sind üblicherweise so aufgebaut, daß eine Flüssigkristallschicht beiderseitig von Schichten eingeschlossen ist, die üblicherweise, in dieser Reihenfolge ausgehend von der LC-Schicht, mindestens eine Orientierungsschicht, Elektroden und eine Begrenzungsscheibe (z. B. aus Glas) sind. Darüberhinaus enthalten sie Abstandshalter, Kleberahmen, Polarisatoren sowie für Farbdisplays dünne Farbfilterschichten. Weitere mögliche Komponenten sind Antireflex-, Passivierungs-, Ausgleichs- und Sperrschichten sowie elektrisch-nichtlineare Elemente, wie Dünnschichttransistoren (TFT) und Metall-Isolator-Metall-(MIM)- Elemente. Im Detail ist der Aufbau von Flüssigkristalldisplays bereits in einschlägigen Monographien beschrieben (siehe z. B. E. Kaneko, "Liquid Crystal TV Displays: Principles and Applications of Liquid Crystal Displays", KTK Scientific Publishers 1987).Liquid-crystalline mixtures, the compounds of the general formula (I) included, are especially for use in electro-optical switching and Suitable display devices. These displays are usually like this built that a liquid crystal layer on both sides of layers is included, which is usually in that order starting from the LC layer, at least one orientation layer, electrodes and one Boundary disk (e.g. made of glass). They also contain Spacers, adhesive frames, polarizers and thin ones for color displays Color filter layers. Other possible components are anti-reflective, Passivation, compensation and barrier layers as well as non-linear electrical Elements such as thin film transistors (TFT) and metal insulator metal (MIM) - Elements. The structure of liquid crystal displays is already in detail relevant monographs (see, for example, E. Kaneko, "Liquid Crystal TV Displays: Principles and Applications of Liquid Crystal Displays ", KTK Scientific Publishers 1987).
Ferner sind die Mischungen für Feldbehandlung, d. h. zum Betrieb in der Quasi- Bookshelf-Geometrie (QBG), (siehe z. B. H. Rieger et al., SID 91 Digest (Anaheim) 1991, 396), geeignet.Furthermore, the mixtures for field treatment, i.e. H. for operation in the quasi Bookshelf geometry (QBG), (see e.g. H. Rieger et al., SID 91 Digest (Anaheim) 1991, 396).
Ebenso sind die erfindungsgemäßen Mischungen geeignet für die Verwendung in ferroelektrischen Flüssigkristallanzeigen, die auf Nutzung des DHF-Effekts oder des PSFLCD-Effekts (Pitch Stabilized Ferroelectric Liquid Crystal Display, auch SBF = Short Pitch Bistable Ferroelectric Effect genannt) beruhen.The mixtures according to the invention are also suitable for use in ferroelectric liquid crystal displays based on the use of the DHF effect or the PSFLCD effect (Pitch Stabilized Ferroelectric Liquid Crystal Display, too SBF = Short Pitch Bistable Ferroelectric Effect).
Die Erfindung wird durch die nachfolgenden Beispiele weiter erläutert, ohne sie dadurch beschränken zu wollen.The invention is further illustrated by the following examples without it wanting to restrict it.
In eine Lösung von 6-Hexyloxy-naphthalin-2-yl-lithium (erhalten durch Umsetzung von Butyllithium bei -78°C mit 6-Hexyloxy-2-brom-naphthalin, das seinerseits durch Williamson-Ethersynthese aus 6-Hydroxy-2-brom-naphthalin hergestellt wurde) wird bei -78°C sowie unter langsamen Auftauen Formaldehydgas eingeleitet. Nach üblicher wäßrig-saurer Aufarbeitung wird das Rohprodukt (6-Hexyloxy-2-hydroxymethyl-naphthalin) in Tetrachlormethan mittels Triphenylphin/Brom in die entsprechende Brommethylverbindung überführt.In a solution of 6-hexyloxy-naphthalin-2-yl lithium (obtained from Reaction of butyllithium at -78 ° C with 6-hexyloxy-2-bromo-naphthalene, the in turn by Williamson ether synthesis from 6-hydroxy-2-bromo-naphthalene was produced) at -78 ° C and with slow thawing Formaldehyde gas introduced. After the usual aqueous-acidic workup, the Crude product (6-hexyloxy-2-hydroxymethyl-naphthalene) in carbon tetrachloride using triphenylphin / bromine in the corresponding bromomethyl compound transferred.
Zu einer Lösung von 1,4 g Natrium in 70 ml Ethanol werden bei 45°C 13.3 g 2- Octyl-malonsäurediethylester getropft. Nach 1 h werden 16.5 g 6-Hexyloxy-2- brommethyl-naphthalin (erhalten wie oben beschrieben) zugegeben und 22 h auf Siedetemperatur erhitzt.13.3 g of 2- to a solution of 1.4 g of sodium in 70 ml of ethanol are added at 45 ° C. Dropped octyl malonic acid diethyl ester. After 1 h, 16.5 g of 6-hexyloxy-2- Bromomethyl-naphthalene (obtained as described above) was added and left for 22 h Boiling temperature heated.
Nach Erkalten wird im Vakuum zur Trockene gebracht und der erhaltene halbfeste Rückstand zwischen Wasser und tert.-Butylmethylether verteilt. Das nach Abdestillation des Lösungsmittels erhaltene Rohprodukt [2-Octyl-2-(6- hexyloxy-naphthin-2-yl)methyl-naphthalin-malonsäurediethylester] wird in 100 ml Methanol gelöst, mit 24 g 50 gew.-%iger wäßriger Kaliumhydroxid-Lösung versetzt und 5 h auf Siedetemperatur erhitzt. Nach Erkalten wird mit Salzsäure auf pH 1 gestellt, dreimal mit jeweils 300 ml tert.-Butylmethylether extrahiert und die vereinigten Extrakte für 6 h auf 160°C erhitzt. Die so erhaltene rohe 2-Octyl-3-(6-hexyloxy-naphthalin-2-yl)propionsäure wird in 100 g Polyphosphorsäure 7 h bei 140°C gerührt. Die noch 90°C warme Lösung wird in 500 ml eines Eis-Wasser-Gemisches gegossen und 1 h gerührt. Es wird zweimal mit je 100 ml Toluol und zweimal mit 100 ml Dichlormethan extrahiert, die vereinigten Extrakte im Vakuum eingedampft und der Rückstand an Kieselgel mit Dichlormethan chromatographiert. Man erhält 2.7 g 2-Octyl-7-hexyloxy-2,3- dihydro-cyclopenta[a]naphthalin-1-on.After cooling, it is brought to dryness in vacuo and the resultant semi-solid residue between water and tert-butyl methyl ether. The crude product obtained after distilling off the solvent [2-octyl-2- (6- hexyloxy-naphthin-2-yl) methyl-naphthalene-malonic acid diethyl ester] is in 100 ml of methanol dissolved, with 24 g of 50 wt .-% aqueous potassium hydroxide solution added and heated to boiling temperature for 5 h. After cooling, use hydrochloric acid adjusted to pH 1, extracted three times with 300 ml of tert-butyl methyl ether each time and the combined extracts heated to 160 ° C for 6 h. The raw so obtained 2-Octyl-3- (6-hexyloxy-naphthalin-2-yl) propionic acid is dissolved in 100 g Polyphosphoric acid stirred at 140 ° C for 7 h. The solution is still 90 ° C warm poured into 500 ml of an ice-water mixture and stirred for 1 h. It will extracted twice with 100 ml toluene and twice with 100 ml dichloromethane, the combined extracts evaporated in vacuo and the residue on silica gel chromatographed with dichloromethane. 2.7 g of 2-octyl-7-hexyloxy-2,3- are obtained. dihydro-cyclopenta [a] naphthalin-1-one.
Eine Lösung des obigen Produktes (1.35 g) in 25 ml Trifluoressigsäure wird mit 2.3 g Triethylsilan versetzt und 6 h zum Sieden erhitzt. Nach Erkalten wird in 150 ml Wasser gegossen, dreimal mit 100 ml Toluol extrahiert, die Extrakte vereinigt und nach Abdampfen des Lösungsmittels an Kiesegel mit Dichlormethan/Heptan 9 : 1 chromatographiert. Man erhält 1.8 g 2-Octyl-7- hexyloxy-2,3-dihydro-1H-cyclopenta[a]naphthalin.A solution of the above product (1.35 g) in 25 ml of trifluoroacetic acid is mixed with 2.3 g of triethylsilane are added and the mixture is heated to boiling for 6 h. After cooling in Poured 150 ml of water, extracted three times with 100 ml of toluene, the extracts combined and after evaporation of the solvent on silica gel with Dichloromethane / heptane 9: 1 chromatographed. 1.8 g of 2-octyl-7- are obtained. hexyloxy-2,3-dihydro-1H-cyclopenta [a] naphthalene.
Analog Beispiel 1 werden nach den Schemata 1, 2 und 3 erhalten:
Beispiel 2:
7-Octyloxy-2-heptyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 3:
7-Heptyl-2-heptyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 4:
7-(6-Cyclopropylhexyloxy)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 5:
7-(9-Dimethylsila)tetradecyl-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 6:
7-(1-Hexansäureester)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 7:
7-(5-Oxa-nonyloxy)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 8:
7-(5-Oxa-undecyl)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 9:
7-(6-Dimethylsila)decyloxy-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 10:
7-Octyloxy-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-cyclopenta
[a]naphthalin
Beispiel 11:
7-Heptyl-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 12:
7-(6-Cyclopropylhexyloxy)-2-(9-dimethylsiIa)tetradecyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 1 3:
7-(9-Dimethylsila)tetradecyl-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 14:
7-(1-Hexansäureester)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 15:
7-(5-Oxa-nonyloxy)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 16:
7-(5-Oxa-undecyl)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 17:
7-(6-Dimethylsila)decyloxy-2-(9-dimethylsila)tetradecyl-2,3-dihydin
1H-cyclopenta[a]naphthalin
Beispiel 18:
7-Octyloxy-2-(9-cycIopropylnonyl)-2,3-dihydrn-1H-cyclopenta[a]
naphthalin
Beispiel 19:
7-Heptyl-2-(9-cycIopropylnonyl)-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 20:
7-(6-CycIopropylhexyloxy)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 21:
7-(9-Dimethylsila)tetradecyl-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 22:
7-(1-Hexansäureester)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 23:
7-(5-Oxa-nonyloxy)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 24:
7-(5-Oxa-undecyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 25:
7-(6-Dimethylsila)decyloxy-2-(9-cycIopropylnonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 26:
7-Octyloxy-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 27:
7-Heptyl-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 28:
7-(6-Cyclopropylhexyloxy)-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 29:
7-(9-Dimethylsila)tetradecyl-2-(5-oxa-undecyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 30:
7-( 1 -Hexansäureester)-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 31:
7-(5-Oxa-nonyloxy)-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclopenta
[a]naphthalin
Beispiel 32:
7-(5-Oxa-undecyl)-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 33:
7-(6-Dimethylsila)decyloxy-2-(5-oxa-undecyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 34:
7-(4-Octyloxy-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 35:
7-(4-Octyloxy-2,3-difluoro-phenyl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 36:
7-(4-Octyloxy-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta
[a]naphthalin
Beispiel 37:
7-(4-Heptyl-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 38:
7-(4-Heptyl-2,3-difluoro-phenyl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 39:
7-(4-Heptyl-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 40:
7-(4-(6-CycIopropylhexyloxy)-phenyl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 41:
7-(4-(6-Cyclopropylhexyloxy)-2,3-difluoro-phenyl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 42:
7-(4-(6-Cyclopropylhexyloxy)-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 43:
7-(4-(9-Dimethylsila)tetradecyl-phenyl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 44:
7-(4-(9-Dimethylsila)tetradecyl-2,3-difluoro-phenyl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 45:
7-(4-(9-Dimethylsila)tetradecyl-3-fluoro-phenyl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 46:
7-(4-(1-Hexansäureester)-phenyl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 47:
7-(4-(1-Hexansäureester)-2,3-difluoro-phenyl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 48:
7-(4-(1-Hexansäureester)-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 49:
7-(4-(5-Oxa-nonyloxy)-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta
[a]naphthalin
Beispiel 50:
7.(4-(5-Oxa-nonyloxy)-2,3-difluoro-phenyl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 51:
7-(4-(5-Oxa-nonyloxy)-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 52:
7-(4-(5-Oxa-undecyl)-phenyl)-2-heptyl-2,3-dihydro-1H-cyclopenta
[a]naphthalin
Beispiel 53:
7-(4-(5-Oxa-undecyl)-2,3-difluoro-phenyl)-2-heptyl-2,3-dihydro1H-
cyclopenta[a]naphthalin
Beispiel 54:
7-(4-(5-Oxa-undecyl)-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-1H-
cycIopenta[a]naphthalin
Beispiel 55:
7-(4-(6-Dimethylsila)decyloxy-phenyl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 56:
7-(4-(6-Dimethylsila)decyloxy-2,3-difluoro-phenyl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 57:
7-(4-(6-Dimethylsila)decyloxy-3-fluoro-phenyl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 58:
7-(4-Octyloxy-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 59:
7-(4-Octyloxy-2,3-difluoro-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 60:
7-(4-Octyloxy-3-fluoro-phenyl)-2-(9-dimethylsiIa)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 61:
7-(4-Heptyl-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 62:
7-(4-Heptyl-2,3-difluoro-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-di-
hydro-1H-cyclopenta[a]naphthalin
Beispiel 63:
7-(4-Heptyl-3-fluoro-phenyl)-2-(9-dimethylsiIa)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 64:
7-(4-(6-CycIopropylhexyloxy)-phenyl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 65:
7-(4-(6-Cyclopropylhexyloxy)-2,3-difluoro-phenyl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 66:
7-(4-(6-Cyclopropylhexyloxy)-3-fluoro-phenyl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 67:
7-(4-(9-Dimethylsila)tetradecyl-phenyl)-2-(9-dimethylsila)tetradecyl-
2,3 dihydro1H cyclopenta[a]naphthalin
Beispiel 68:
7-(4-(9-Dimethylsila)tetradecyl-2,3-difluoro-phenyl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 69:
7-(4-(9-Dimethylsila)tetradecyl-3-fluoro-phenyl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 70:
7-(4-(1-Hexansäureester)-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 71:
7-(4-(1-Hexansäureester)-2,3-difluoro-phenyl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 72:
7-(4-(1-Hexansäureester)-3-fluoro-phenyl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 73:
7-(4-(5-Oxa-nonyloxy)-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 74:
7-(4-(5-Oxa-nonyloxy)-2,3-difluoro-phenyl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 75:
7-(4-(5-Oxa-nonyloxy)-3-fluoro-phenyl)-2-(9-dimethylsila)tetradecyl--
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 76:
7-(4-(5-Oxa-undecyl)-phenyl)-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 77:
7-(4-(5-Oxa-undecyl)-2,3-difluoro-phenyl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 78:
7-(4-(5-Oxa-undecyl)-3-fluoro-phenyl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 79:
7-(4-(6-Dimethylsila)decyloxy-phenyl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 80:
7-(4-(6-Dimethylsila)decyloxy-2,3-difluoro-phenyl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 81:
7-(4-(6-Dimethylsila)decyloxy-3-fluoro-phenyl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 82:
7-(4-Octyloxy-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 83:
7-(4-Octyloxy-2,3-difluoro-phenyl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 84:
7-(4-Octyloxy-3-fluoro-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 85:
7-(4-Heptyl-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 86:
7-(4-Heptyl-2,3-difluoro-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro--
1H-cyclopenta[a]naphthalin
Beispiel 87:
7-(4-Heptyl-3-fluoro-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 88:
7-(4-(6-CycIopropylhexyloxy)-phenyl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 89:
7-(4-(6-Cyclopropylhexyloxy)-2,3-difluoro-phenyl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 90:
7-(4-(6-Cyclopropylhexyloxy)-3-fluoro-phenyl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 91:
7-(4-(9-Dimethylsila)tetradecyl-phenyl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 92:
7-(4-(9-Dimethylsila)tetradecyl-2,3-difluoro-phenyl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 93:
7-(4-(9-Dimethylsila)tetradecyl-3-fluoro-phenyl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 94:
7-(4-(1-Hexansäureester)-phenyl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 95:
7-(4-(1-Hexansäureester)-2,3-difluoro-phenyl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 96:
7-(4-(1-Hexansäureester)-3-fluoro-phenyl)-2-(9-cyclopropylnonyl)-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 97:
7-(4-(5-Oxa-nonyloxy)-phenyl)-2-(9-cyclopropylnonyl)-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 98:
7-(4-(5-Oxa-nonyloxy)-2,3-difluoro-phenyl)-2-(9-cyclopropylnonyl)-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 99.
7-(4-(5-Oxa-nonyloxy)-3-fluoro-phenyl)-2-(9-cyclopropylnoflyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 100:
7-(4-(5-Oxa-undecyl)-phenyl)-2-(9 cyclopropylnonyl)-2,3-dihydro
1H-cyclopenta[a]naphthalin
Beispiel 101:
7-(4-(5-Oxa-undecyl)-2,3-difluoro-phenyl)-2-(9-cyclopropylnonyl)-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 102:
7-(4-(5-Oxa-undecyl)-3-fluoro-phenyl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 103:
7-(4-(6-Dimethylsila)decyloxy-phenyl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 104:
7-(4-(6-Dimethylsila)decyloxy-2,3-difluoro-phenyl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 105:
7-(4-(6-Dimethylsila)decyloxy-3-fluoro-phenyl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 106:
7-(5-Octyloxy-pyrimidin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 107:
7-(5-Heptyl-pyrimidin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclopenta-
[a]naphthalin
Beispiel 108:
7-(5-(6-Cyclopropylhexyloxy)-pyrimidin-2-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 109:
7-(5-(9-Dimethylsila)tetradecyl-pyrimidin-2-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 110:
7-(5-(1-Hexansäureester)-pyrimidin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 111:
7-(5-(5-Oxa-nonyloxy)-pyrimidin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 112:
7-(5-(5-Oxa-undecyl)-pyrimidin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 113:
7-(5-(6-Dimethylsila)decyloxy-pyrimidin-2-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 114:
7-(5-Octyloxy-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclopenta-
[a]naphthalin
Beispiel 115:
7-(5-Heptyl-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclopenta[a]
naphthalin
Beispiel 116:
7-(5-(6-Cyclopropylhexyloxy)-pyridin-2-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 117:
7-(5-(9-Dimethylsila)tetradecyl-pyridin-2-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 118:
7-(5-(1Hexansäureester)-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a] naphthalin
Beispiel 119:
7-(5-(5-Oxa-nonyloxy)-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 120:
7-(5-(5-Oxa-undecyl)-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 1 21:
7-(5-(6-Dimethylsila)decyloxy-pyridin-2-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 122:
7-(6-0ctyloxy-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 123:
7-(6-Heptyl-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 124:
7-(6-(6-Cyclopropylhexyloxy)-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 125:
7-(6-(9-Dimethylsila)tetradecyl-2-fluoro-pyridin-2-yl)-2-heptyl-2,3--
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 126:
7-(6-(1-Hexansäureester)-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 127:
7-(6-(5-Oxa-nonyloxy)-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 128:
7-(6-(5-Oxa-undecyl)-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 129:
7-(6-(6-Dimethylsila)decyloxy-2-fluoro-pyridin-2-yl)-2-heptyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 130:
7-(2-Octyloxy-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-dihydro-1H-
cycIopenta[a]naphthalin
Beispiel 131:
7-(2-Heptyl-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-dihydro-1H-cyclo
penta[a]naphthalin
Beispiel 132:
7-(2-(6-Cyclopropylhexyloxy)-[ 1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 133:
7-(2-(9-Dimethylsila)tetradecyl-[1,3,4]thiadiazol-5-yl)-2-heptyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 134:
7-(2-(1-Hexansäureester)-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 135:
7-(2-(5-Oxa-nonyloxy)-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 136:
7-(2-(5-Oxa-undecyl)-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 137:
7-(2-(6-Dimethylsila)decyloxy-[1,3,4]thiadiazol-5-yl)-2-heptyl-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 138:
7-(5-Octyloxy-pyrimidin-2-yl)-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 139:
7-(5-Heptyl-pyrimidin-2-yl)-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 140:
7-(5-(6-Cyclopropylhexyloxy)-pyrimidin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 141:
7-(5-(9-Dimethylsila)tetradecyl-pyrimidin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 142:
7-(5-(1-Hexansäureester)-pyrimidin-2-yl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 143:
7-(5-(5-Oxa-nonyloxy)-pyrimidin-2-yl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 144:
7-(5-(5-Oxa-undecyl)-pyrimidin-2-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cycIopenta[a]naphthalin
Beispiel 145:
7-(5-(6-Dimethylsila)decyloxy-pyrimidin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 146:
7-(5-Octyloxy-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 147:
7-(5-Heptyl-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 148:
7-(5-(6-Cyclopropylhexyloxy)-pyridin-2-yl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 149:
7-(5-(9-Dimethylsila)tetradecyl-pyridin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 150:
7-(5-(1-Hexansäureester)-pyridin-2-yl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 151:
7-(5-(5-Oxa-nonyloxy)-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 152:
7-(5-(5-Oxa-undecyl)-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 153:
7-(5-(6-Dimethylsila)decyloxy-pyridin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 154:
7-(6-Octyloxy-2-fluoro-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 155:
7-(6-Heptyl-2-fluoro-pyridin-2-yl)-2-(9-dimethylsila)tetradecyl-2,3--
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 156:
7-(6-(6-Cyclopropylhexyloxy)-2-fluoro-pyridin-2-yl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 157:
7-(6-(9-Dimethylsila)tetradecyl-2-fluoro-pyridin-2-yl)-2-(9-di
methylsila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 158:
7-(6-(1-Hexansäureester)-2-fluoro-pyridin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 159:
7-(6-(5-Oxa-nonyloxy)-2-fluoro-pyridin-2-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 160:
7-(6-(5-Oxa-undecyl)-2-fluoro-pyridin-2-yl)-2-(9-dimethylsila)tetra
decyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 161:
7-(6-(6-Dimethylsila)decyloxy-2-fluoro-pyridin-2-yl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 162:
7-(2-Octyloxy-[1,3,4]thiadiazol-5-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 163:
7-(2-Heptyl-[1,3,4]thiadiazol-5-yl)-2-(9-dimethylsila)tetradecyl-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 164:
7-(2-(6-Cyclopropylhexyloxy)-[1,3,4]thiadiazol-5-yl)-2-(9-di
methylsila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 165:
7-(2-(9-Dimethylsila)tetradecyl-[1,3,4]thiadiazol-5-yl)-2-(9-di
methylsila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 166:
7-(2-(1-Hexansäureester)-[1,3,4]thiadiazol-5-yl)-2-(9-dimethyl
sila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 167:
7-(2-(5-Oxa-nonyloxy)-[1,3,4]thiadiazol-5-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 168:
7-(2-(5-Oxa-undecyl)-[1,3,4]thiadiazol-5-yl)-2-(9-dimethylsila)
tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 169:
7-(2-(6-Dimethylsila)decyloxy-[1,3,4]thiadiazol-5-yl)-2-(9-di
methylsila)tetradecyl-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 170:
7-(5-Octyloxy-pyrimidin-2-yl)-2-(9-cyclopropylnonyl)-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 171:
7-(5-Heptyl-pyrimidin-2-yl)-2-(9-cyclopropylnonyl)-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 172:
7-(5-(6-Cyclopropylhexyloxy)-pyrimidin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 173:
7-(5-(9-Dimethylsila)tetradecyl-pyrimidin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 174:
7-(5-(1-Hexansäureester)-pyrimidin-2-yl)-2-(9-cyclopropylnonyl)-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 175:
7-(5-(5-Oxa-nonyloxy)-pyrimidin-2-yl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 176:
7-(5-(5-Oxa-undecyl)-pyrimidin-2-yl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 177:
7-(5-(6-Dimethylsila)decyloxy-pyrimidin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 178:
7-(5-Octyloxy-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-dihydro-
1H-cyclopenta[a]naphthalin
Beispiel 179:
7-(5-Heptyl-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalin
Beispiel 180:
7-(5-(6-Cyclopropylhexyloxy)-pyridin-2-yl)-2-(9-cyclopropylnonyl)-
2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 181:
7-(5-(9-Dimethylsila)tetradecyl-pyridin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 182:
7-(5-(1-Hexansäureester)-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 183:
7-(5-(5-Oxa-nonyloxy)-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 184:
7-(5-(5-Oxa-undecyl)-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 185:
7-(5-(6-Dimethylsila)decyloxy-pyridin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 186:
7-(6-Octyloxy-2-fluoropyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 187:
7-(6-Heptyl-2-fluoro-pyridin-2-yl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 188:
7-(6-(6-CycIopropylhexyloxy)-2-fluoro-pyridin-2-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 189:
7-(6-(9-Dimethylsila)tetradecyl-2-fluoro-pyridin-2-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 190:
7-(6-(1Hexansäureester)-2-fluoro-pyridin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 191:
7-(6-(5-Oxa-nonyloxy)-2-fluoro-pyridin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 192:
7-(6-(5-Oxa-undecyl)-2-fluoro-pyridin-2-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 193:
7-(6-(6-Dimethylsila)decyloxy-2-fluoro-pyridin-2-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 194:
7-(2-Octyloxy-[1,3,4]thiadiazol-5-yl)-2-(9-cyclopropylnonyl)-2,3-
dihydro-1H-cyclopenta[a]naphthalin
Beispiel 195:
7-(2-Heptyl-[1,3,4]thiadiazol-5-yl)-2-(9-cyclopropylnonyl)-2,3-di
hydro-1H-cyclopenta[a]naphthalin
Beispiel 196:
7-(2-(6-Cyclopropylhexyloxy)-[1,3,4]thiadiazol-5-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 197:
7-(2-(9-Dimethylsila)tetradecyl-[1,3,4]thiadiazol-5-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 198:
7-(2-(1-Hexansäureester)-[1,3,4]thiadiazol-5-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 199:
7-(2-(5-Oxa-nonyloxy)-[1,3,4]thiadiazol-5-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 200:
7-(2-(5-Oxa-undecyl)-[1,3,4]thiadiazol-5-yl)-2-(9-cyclopropyl
nonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalin
Beispiel 201:
7-(2-(6-Dimethylsila)decyloxy-[1,3,4]thiadiazol-5-yl)-2-(9-cyclo
propylnonyl)-2,3-dihydro-1H-cyclopenta[a]naphthalinAnalogously to example 1, the following are obtained according to schemes 1, 2 and 3:
Example 2:
7-octyloxy-2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 3:
7-heptyl-2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 4:
7- (6-Cyclopropylhexyloxy) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 5:
7- (9-Dimethylsila) tetradecyl-2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 6:
7- (1-Hexanoic acid ester) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 7:
7- (5-Oxa-nonyloxy) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 8:
7- (5-Oxa-undecyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 9:
7- (6-Dimethylsila) decyloxy-2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 10:
7-octyloxy-2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 11:
7-heptyl-2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 12:
7- (6-Cyclopropylhexyloxy) -2- (9-dimethylsiIa) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 1 3:
7- (9-Dimethylsila) tetradecyl-2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 14:
7- (1-Hexanoic acid ester) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 15:
7- (5-Oxa-nonyloxy) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 16:
7- (5-Oxa-undecyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 17:
7- (6-Dimethylsila) decyloxy-2- (9-dimethylsila) tetradecyl-2,3-dihydine 1H-cyclopenta [a] naphthalene
Example 18:
7-octyloxy-2- (9-cyclopropylnonyl) -2,3-dihydrn-1H-cyclopenta [a] naphthalene
Example 19:
7-heptyl-2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 20:
7- (6-Cyclopropylhexyloxy) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 21:
7- (9-Dimethylsila) tetradecyl-2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 22:
7- (1-Hexanoic acid ester) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 23:
7- (5-Oxa nonyloxy) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 24:
7- (5-Oxa-undecyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 25:
7- (6-Dimethylsila) decyloxy-2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 26:
7-octyloxy-2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 27:
7-heptyl-2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 28:
7- (6-Cyclopropylhexyloxy) -2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 29:
7- (9-Dimethylsila) tetradecyl-2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 30:
7- (1-Hexanoic acid ester) -2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 31:
7- (5-Oxa-nonyloxy) -2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 32:
7- (5-oxa-undecyl) -2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 33:
7- (6-Dimethylsila) decyloxy-2- (5-oxa-undecyl) -2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 34:
7- (4-Octyloxyphenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 35:
7- (4-Octyloxy-2,3-difluorophenyl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 36:
7- (4-Octyloxy-3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 37:
7- (4-heptylphenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 38:
7- (4-heptyl-2,3-difluorophenyl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 39:
7- (4-heptyl-3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 40:
7- (4- (6-Cyclopropylhexyloxy) phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 41:
7- (4- (6-Cyclopropylhexyloxy) -2,3-difluorophenyl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 42:
7- (4- (6-Cyclopropylhexyloxy) -3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 43:
7- (4- (9-Dimethylsila) tetradecylphenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 44:
7- (4- (9-Dimethylsila) tetradecyl-2,3-difluorophenyl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 45:
7- (4- (9-Dimethylsila) tetradecyl-3-fluoro-phenyl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 46:
7- (4- (1-Hexanoic acid ester) phenyl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 47:
7- (4- (1-Hexanoic acid ester) -2,3-difluorophenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 48:
7- (4- (1-Hexanoic acid ester) -3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 49:
7- (4- (5-Oxa-nonyloxy) phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 50:
7. (4- (5-Oxa-nonyloxy) -2,3-difluorophenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 51:
7- (4- (5-Oxa-nonyloxy) -3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 52:
7- (4- (5-Oxa-undecyl) phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 53:
7- (4- (5-Oxa-undecyl) -2,3-difluorophenyl) -2-heptyl-2,3-dihydro1H-cyclopenta [a] naphthalene
Example 54:
7- (4- (5-Oxa-undecyl) -3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 55:
7- (4- (6-Dimethylsila) decyloxyphenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 56:
7- (4- (6-Dimethylsila) decyloxy-2,3-difluorophenyl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 57:
7- (4- (6-Dimethylsila) decyloxy-3-fluoro-phenyl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 58:
7- (4-Octyloxy-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 59:
7- (4-Octyloxy-2,3-difluorophenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 60:
7- (4-Octyloxy-3-fluoro-phenyl) -2- (9-dimethylsiIa) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 61:
7- (4-Heptylphenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 62:
7- (4-Heptyl-2,3-difluorophenyl) -2- (9-dimethylsila) tetradecyl-2,3-di-hydro-1H-cyclopenta [a] naphthalene
Example 63:
7- (4-Heptyl-3-fluoro-phenyl) -2- (9-dimethylsiIa) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 64:
7- (4- (6-Cyclopropylhexyloxy) phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 65:
7- (4- (6-Cyclopropylhexyloxy) -2,3-difluorophenyl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 66:
7- (4- (6-Cyclopropylhexyloxy) -3-fluoro-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 67:
7- (4- (9-Dimethylsila) tetradecylphenyl) -2- (9-dimethylsila) tetradecyl-2,3 dihydro1H cyclopenta [a] naphthalene
Example 68:
7- (4- (9-Dimethylsila) tetradecyl-2,3-difluorophenyl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 69:
7- (4- (9-Dimethylsila) tetradecyl-3-fluoro-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 70:
7- (4- (1-Hexanoic acid ester) phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 71:
7- (4- (1-Hexanoic acid ester) -2,3-difluorophenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 72:
7- (4- (1-Hexanoic acid ester) -3-fluoro-phenyl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 73:
7- (4- (5-Oxa-nonyloxy) phenyl) -2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 74:
7- (4- (5-Oxa-nonyloxy) -2,3-difluorophenyl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 75:
7- (4- (5-Oxa-nonyloxy) -3-fluoro-phenyl) -2- (9-dimethylsila) tetradecyl-- 2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 76:
7- (4- (5-Oxa-undecyl) phenyl) -2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 77:
7- (4- (5-Oxa-undecyl) -2,3-difluorophenyl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 78:
7- (4- (5-Oxa-undecyl) -3-fluoro-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 79:
7- (4- (6-Dimethylsila) decyloxy-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 80:
7- (4- (6-Dimethylsila) decyloxy-2,3-difluorophenyl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 81:
7- (4- (6-Dimethylsila) decyloxy-3-fluoro-phenyl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 82:
7- (4-Octyloxyphenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 83
7- (4-Octyloxy-2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 84:
7- (4-Octyloxy-3-fluoro-phenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 85:
7- (4-heptylphenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 86:
7- (4-Heptyl-2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-- 1H-cyclopenta [a] naphthalene
Example 87:
7- (4-Heptyl-3-fluoro-phenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 88:
7- (4- (6-Cyclopropylhexyloxy) phenyl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 89:
7- (4- (6-Cyclopropylhexyloxy) -2,3-difluorophenyl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 90:
7- (4- (6-Cyclopropylhexyloxy) -3-fluoro-phenyl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 91
7- (4- (9-Dimethylsila) tetradecylphenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 92:
7- (4- (9-Dimethylsila) tetradecyl-2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 93:
7- (4- (9-Dimethylsila) tetradecyl-3-fluoro-phenyl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 94:
7- (4- (1-Hexanoic acid ester) phenyl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 95:
7- (4- (1-Hexanoic acid ester) -2,3-difluorophenyl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 96:
7- (4- (1-Hexanoic acid ester) -3-fluoro-phenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 97:
7- (4- (5-Oxa-nonyloxy) phenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 98
7- (4- (5-Oxa-nonyloxy) -2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 99.
7- (4- (5-Oxa-nonyloxy) -3-fluoro-phenyl) -2- (9-cyclopropylnoflyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 100:
7- (4- (5-Oxa-undecyl) phenyl) -2- (9 cyclopropylnonyl) -2,3-dihydro 1H-cyclopenta [a] naphthalene
Example 101:
7- (4- (5-Oxa-undecyl) -2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 102:
7- (4- (5-Oxa-undecyl) -3-fluoro-phenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 103:
7- (4- (6-Dimethylsila) decyloxyphenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 104:
7- (4- (6-Dimethylsila) decyloxy-2,3-difluorophenyl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 105:
7- (4- (6-Dimethylsila) decyloxy-3-fluoro-phenyl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 106:
7- (5-Octyloxypyrimidin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 107:
7- (5-heptyl-pyrimidin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta- [a] naphthalene
Example 108:
7- (5- (6-Cyclopropylhexyloxy) pyrimidin-2-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 109:
7- (5- (9-Dimethylsila) tetradecyl-pyrimidin-2-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 110:
7- (5- (1-Hexanoic acid ester) pyrimidin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 111:
7- (5- (5-Oxa-nonyloxy) pyrimidin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 112:
7- (5- (5-Oxa-undecyl) pyrimidin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 113:
7- (5- (6-Dimethylsila) decyloxypyrimidin-2-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 114:
7- (5-Octyloxypyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta- [a] naphthalene
Example 115:
7- (5-heptyl-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 116:
7- (5- (6-Cyclopropylhexyloxy) pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 117:
7- (5- (9-Dimethylsila) tetradecyl-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 118:
7- (5- (1-hexanoic acid ester) pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 119:
7- (5- (5-Oxa-nonyloxy) pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 120:
7- (5- (5-Oxa-undecyl) pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 1 21:
7- (5- (6-Dimethylsila) decyloxypyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 122:
7- (6-0ctyloxy-2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 123:
7- (6-heptyl-2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 124:
7- (6- (6-Cyclopropylhexyloxy) -2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 125:
7- (6- (9-Dimethylsila) tetradecyl-2-fluoro-pyridin-2-yl) -2-heptyl-2,3-- dihydro-1H-cyclopenta [a] naphthalene
Example 126:
7- (6- (1-Hexanoic acid ester) -2-fluoro-pyridin-2-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 127:
7- (6- (5-Oxa-nonyloxy) -2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 128:
7- (6- (5-Oxa-undecyl) -2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 129:
7- (6- (6-Dimethylsila) decyloxy-2-fluoro-pyridin-2-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 130:
7- (2-Octyloxy- [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 131:
7- (2-heptyl- [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclo penta [a] naphthalene
Example 132:
7- (2- (6-Cyclopropylhexyloxy) - [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 133:
7- (2- (9-Dimethylsila) tetradecyl- [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 134:
7- (2- (1-Hexanoic acid ester) - [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 135:
7- (2- (5-Oxa-nonyloxy) - [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 136:
7- (2- (5-Oxa-undecyl) - [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 137:
7- (2- (6-Dimethylsila) decyloxy- [1,3,4] thiadiazol-5-yl) -2-heptyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 138:
7- (5-Octyloxypyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 139:
7- (5-Heptyl-pyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 140:
7- (5- (6-Cyclopropylhexyloxy) pyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 141:
7- (5- (9-Dimethylsila) tetradecyl-pyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 142:
7- (5- (1-Hexanoic acid ester) pyrimidin-2-yl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 143:
7- (5- (5-Oxa-nonyloxy) pyrimidin-2-yl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 144:
7- (5- (5-Oxa-undecyl) pyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 145:
7- (5- (6-Dimethylsila) decyloxypyrimidin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 146:
7- (5-Octyloxypyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 147:
7- (5-Heptyl-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 148:
7- (5- (6-Cyclopropylhexyloxy) pyridin-2-yl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 149:
7- (5- (9-Dimethylsila) tetradecyl-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 150:
7- (5- (1-Hexanoic acid ester) pyridin-2-yl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 151:
7- (5- (5-Oxa-nonyloxy) pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 152:
7- (5- (5-Oxa-undecyl) pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 153:
7- (5- (6-Dimethylsila) decyloxypyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 154:
7- (6-Octyloxy-2-fluoro-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 155:
7- (6-Heptyl-2-fluoro-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-- dihydro-1H-cyclopenta [a] naphthalene
Example 156:
7- (6- (6-Cyclopropylhexyloxy) -2-fluoro-pyridin-2-yl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 157:
7- (6- (9-Dimethylsila) tetradecyl-2-fluoro-pyridin-2-yl) -2- (9-di methylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 158:
7- (6- (1-Hexanoic acid ester) -2-fluoro-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 159:
7- (6- (5-Oxa-nonyloxy) -2-fluoro-pyridin-2-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 160:
7- (6- (5-Oxa-undecyl) -2-fluoro-pyridin-2-yl) -2- (9-dimethylsila) tetra decyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 161:
7- (6- (6-Dimethylsila) decyloxy-2-fluoro-pyridin-2-yl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 162:
7- (2-Octyloxy- [1,3,4] thiadiazol-5-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 163:
7- (2-Heptyl- [1,3,4] thiadiazol-5-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 164:
7- (2- (6-Cyclopropylhexyloxy) - [1,3,4] thiadiazol-5-yl) -2- (9-di methylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 165:
7- (2- (9-Dimethylsila) tetradecyl- [1,3,4] thiadiazol-5-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 166:
7- (2- (1-Hexanoic acid ester) - [1,3,4] thiadiazol-5-yl) -2- (9-dimethyl sila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 167:
7- (2- (5-Oxa-nonyloxy) - [1,3,4] thiadiazol-5-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 168:
7- (2- (5-Oxa-undecyl) - [1,3,4] thiadiazol-5-yl) -2- (9-dimethylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 169:
7- (2- (6-Dimethylsila) decyloxy- [1,3,4] thiadiazol-5-yl) -2- (9-di methylsila) tetradecyl-2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 170:
7- (5-Octyloxypyrimidin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 171:
7- (5-Heptyl-pyrimidin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 172:
7- (5- (6-Cyclopropylhexyloxy) pyrimidin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 173:
7- (5- (9-Dimethylsila) tetradecyl-pyrimidin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 174:
7- (5- (1-Hexanoic acid ester) pyrimidin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 175:
7- (5- (5-Oxa-nonyloxy) pyrimidin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 176:
7- (5- (5-Oxa-undecyl) pyrimidin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 177:
7- (5- (6-Dimethylsila) decyloxypyrimidin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 178:
7- (5-Octyloxypyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 179:
7- (5-heptyl-pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 180:
7- (5- (6-Cyclopropylhexyloxy) pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 181:
7- (5- (9-Dimethylsila) tetradecyl-pyridin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 182:
7- (5- (1-Hexanoic acid ester) pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 183:
7- (5- (5-Oxa-nonyloxy) pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 184:
7- (5- (5-Oxa-undecyl) pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 185:
7- (5- (6-Dimethylsila) decyloxypyridin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 186:
7- (6-Octyloxy-2-fluoropyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 187
7- (6-Heptyl-2-fluoro-pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 188:
7- (6- (6-Cyclopropylhexyloxy) -2-fluoro-pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 189:
7- (6- (9-Dimethylsila) tetradecyl-2-fluoro-pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 190:
7- (6- (1-hexanoic acid ester) -2-fluoro-pyridin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 191
7- (6- (5-Oxa-nonyloxy) -2-fluoro-pyridin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 192:
7- (6- (5-Oxa-undecyl) -2-fluoro-pyridin-2-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 193
7- (6- (6-Dimethylsila) decyloxy-2-fluoro-pyridin-2-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 194
7- (2-Octyloxy- [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 195
7- (2-Heptyl- [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropylnonyl) -2,3-di hydro-1H-cyclopenta [a] naphthalene
Example 196:
7- (2- (6-Cyclopropylhexyloxy) - [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 197:
7- (2- (9-Dimethylsila) tetradecyl- [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 198:
7- (2- (1-Hexanoic acid ester) - [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 199:
7- (2- (5-Oxa-nonyloxy) - [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 200:
7- (2- (5-Oxa-undecyl) - [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropyl nonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Example 201:
7- (2- (6-Dimethylsila) decyloxy- [1,3,4] thiadiazol-5-yl) -2- (9-cyclopropylnonyl) -2,3-dihydro-1H-cyclopenta [a] naphthalene
Claims (10)
R¹ ist -F, -CN, -Cl, CF₃ oder hat, unabhängig von R², eine der bei R² aufgeführten Bedeutungen;
R² H oder ein geradkettiger oder verzweigter Alkylrest mit 1 bis 20 C- Atomen (mit oder ohne asymmetrisches C-Atom), wobei auch eine oder mehrere -CH₂-Gruppen (jedoch nicht die direkt an den Fünfring gebundene) durch -O-, -S-, -CH=CH-, -C-C-, Cyclopropan-1,2-diyl, -Si(CH₃)₂-, 1,4-Phenylen, 1,4-Cyclohexylen, 1,3-Cyclopentylen, 1,3 Cyclobutylen, 1,3-Dioxan-2,5-diyl ersetzt sein können, mit der Maßgabe, daß Sauerstoffatome und Schwefelatome nicht unmittelbar verbunden sein dürfen, und wobei auch ein oder mehrere H-Atome des Alkylrestes durch F, Cl, Br oder OR³ substituiert sein können, oder eine der nachfolgenden Gruppen (optisch aktiv oder racemisch): R³ ist H oder ein geradkettiger Alkylrest mit 1 bis 6 C-Atomen;
R⁴, R⁵, R⁶ sind gleich oder verschieden Wasserstoff oder ein geradkettiger oder verzweigter Alkylrest mit 1-16 C-Atomen, wobei auch eine oder zwei CH₂-Gruppen durch -O- und/oder -CH = CH- ersetzt sein können, mit der Maßgabe, daß Sauerstoffatome nicht unmittelbar miteinander gebunden sein dürfen, R⁴ und R⁵ können zusammen auch -(CH₂)₄- oder -(CH₂)₅- sein, wenn sie an ein Oxiran-, Dioxolan-, Tetrahydrofuran-, Tetrahydropropyran-, Bytorolacton- oder Valerolacton-System gebunden sind;
Q¹ ist eine Einfachbindung, -CO-O- oder -CH₂-O-;
Ring B ist A¹ ist 1,4-Phenylen, 1,4-Cyclohexylen, Pyridin-2,5-diyl, Pyrimidin-2,5-diyl, (1,3)-Thiazol-2,5-diyl, (1,3)-Thiazol-2,4-diyl, wobei auch ein oder mehrere Wasserstoffe durch F substituiert sein können, (1,3,4)Thiadiazol-2,5-diyl;
M¹ ist eine Einfachbindung, -C ≡ C-, -CH₂CH₂-, -O-CO-, -CO-O-, -CO-, -OCH₂-, -CH₂O-, -O-CO-O-;
m Null oder Eins.1. tricyclic compounds of the general formula (1), in which the symbols and indices have the following meanings:
R¹ is -F, -CN, -Cl, CF₃ or, independently of R², has one of the meanings listed for R²;
R² H or a straight-chain or branched alkyl radical with 1 to 20 C atoms (with or without asymmetrical C atom), one or more -CH₂ groups (but not the one bonded directly to the five-membered ring) by -O-, - S-, -CH = CH-, -CC-, cyclopropane-1,2-diyl, -Si (CH₃) ₂-, 1,4-phenylene, 1,4-cyclohexylene, 1,3-cyclopentylene, 1,3 Cyclobutylene, 1,3-dioxane-2,5-diyl can be replaced, with the proviso that oxygen atoms and sulfur atoms must not be directly connected, and also one or more H atoms of the alkyl radical by F, Cl, Br or OR³ may be substituted, or one of the following groups (optically active or racemic): R³ is H or a straight-chain alkyl radical with 1 to 6 C atoms;
R⁴, R⁵, R⁶ are the same or different hydrogen or a straight-chain or branched alkyl radical having 1-16 C atoms, where one or two CH₂ groups can be replaced by -O- and / or -CH = CH- with which Provided that oxygen atoms must not be bonded directly to one another, R⁴ and R⁵ together can also be - (CH₂) ₄- or - (CH₂) ₅- if they are attached to an oxirane, dioxolane, tetrahydrofuran, tetrahydropropyran, bytorolactone or valerolactone system are bound;
Q¹ is a single bond, -CO-O- or -CH₂-O-;
Ring B is A¹ is 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, (1,3) -thiazole-2,5-diyl, (1,3) - Thiazole-2,4-diyl, where one or more hydrogens may also be substituted by F, (1,3,4) thiadiazole-2,5-diyl;
M¹ is a single bond, -C ≡ C-, -CH₂CH₂-, -O-CO-, -CO-O-, -CO-, -OCH₂-, -CH₂O-, -O-CO-O-;
m zero or one.
p eine natürliche Zahl von 1 bis 20;
q eine natürliche Zahl von 1 bis 19;
s, t eine natürliche Zahl von 1 bis 18 und
y eine natürliche Zahl von 1 bis 17 bedeutet und t + y 18 sein muß, und
R² die in Formel (I) in Anspruch 1 angegebenen Bedeutungen hat.4. Tricyclic compounds according to one or more of claims 1 to 3, characterized by the formulas (Iaa 1) to (Iaa 14) and (Iab 1a) to (Iab Id), in which
p is a natural number from 1 to 20;
q is a natural number from 1 to 19;
s, t is a natural number from 1 to 18 and
y is a natural number from 1 to 17 and t + y must be 18, and
R² has the meanings given in formula (I) in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4434975A DE4434975A1 (en) | 1994-09-30 | 1994-09-30 | New tri:cyclic cpds. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4434975A DE4434975A1 (en) | 1994-09-30 | 1994-09-30 | New tri:cyclic cpds. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4434975A1 true DE4434975A1 (en) | 1996-04-04 |
Family
ID=6529610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4434975A Withdrawn DE4434975A1 (en) | 1994-09-30 | 1994-09-30 | New tri:cyclic cpds. |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4434975A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021682A1 (en) * | 2003-08-22 | 2005-03-10 | Merck Patent Gmbh | Cyclopenta[a]naphthaline derivatives |
| DE10145780B4 (en) * | 2001-09-17 | 2012-10-04 | Merck Patent Gmbh | Fluorinated cyclopenta [a] naphthalenes and their use in liquid crystal mixtures and displays |
| WO2018107911A1 (en) * | 2016-12-16 | 2018-06-21 | 江苏和成显示科技有限公司 | Liquid crystal compound having negative dielectric anisotropy, and application therefor |
-
1994
- 1994-09-30 DE DE4434975A patent/DE4434975A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10145780B4 (en) * | 2001-09-17 | 2012-10-04 | Merck Patent Gmbh | Fluorinated cyclopenta [a] naphthalenes and their use in liquid crystal mixtures and displays |
| WO2005021682A1 (en) * | 2003-08-22 | 2005-03-10 | Merck Patent Gmbh | Cyclopenta[a]naphthaline derivatives |
| US7575785B2 (en) | 2003-08-22 | 2009-08-18 | Merck Patent Gmbh | Cyclopenta[a]naphthaline derivatives |
| WO2018107911A1 (en) * | 2016-12-16 | 2018-06-21 | 江苏和成显示科技有限公司 | Liquid crystal compound having negative dielectric anisotropy, and application therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0825987B1 (en) | 1-fluorisoquinoline derivatives and the use thereof in liquid crystalline mixtures | |
| DE19522195A1 (en) | Stable 3,4,5-tri:fluoro-naphthalene derivs. useful in liquid crystal mixt. | |
| EP0824522B1 (en) | 1,8-difluorisoquinoline derivatives and the use thereof in liquid crystalline mixtures | |
| DE19500768C2 (en) | Phenanthrene derivatives and their use in liquid crystalline mixtures | |
| EP0828716B1 (en) | Trifluortetrahydro-isoquinoline derivatives and the use thereof in liquid crystalline mixtures | |
| EP0824520B1 (en) | 1-fluor-5,6,7,8-tetrahydroisoquinoline derivatives and their use in liquid crystal mixtures | |
| EP0824521B1 (en) | 1-fluor-6,7-dihydro-5h-isoquinoline-8-one-derivatives and the use thereof in liquid crystalline mixtures | |
| DE4423044A1 (en) | Alkyl-oxiranyl-alkyl ester(s) of mesogenic carboxylic acids useful in liquid crystal mixts. | |
| DE19522167B4 (en) | 1,2-Difluoronaphthalene derivatives and their use in liquid crystalline mixtures | |
| DE19522145B4 (en) | 7,8-Difluorotetralin derivatives and their use in liquid crystalline mixtures | |
| DE4434974A1 (en) | New tri:cyclic cpds. for liq. crystal mixts. | |
| DE19522152A1 (en) | Stable 1,1,7,8-tetra:fluoro-tetralin derivs. useful in liquid crystal mixt. | |
| EP0743971B1 (en) | Phenanthridine derivatives and their use in liquid crystal mixtures | |
| DE4434975A1 (en) | New tri:cyclic cpds. | |
| DE4432970A1 (en) | New tetra:cyclic cpds., e.g. cyclo:alkyl:phenanthrene derivs. | |
| DE19652247A1 (en) | 5,7-difluoro-1,2,3,4-tetrahydronaphthalene derivatives and their use in liquid-crystalline mixtures | |
| DE19652250A1 (en) | 1,1,5,7-tetrafluoro-1,2,3,4-tetrahydronaphthalene derivatives and their use in liquid-crystalline mixtures | |
| DE19627899A1 (en) | Cpds. for improving properties of pref. ferroelectric LC mixts. | |
| DE19653010A1 (en) | 9,9-difluoro-9,10-dihydrophenanthrene derivatives and their use in liquid-crystalline mixtures | |
| DE19522175A1 (en) | Stable 7,8-di:fluoro-3,4-di:hydro-2H-naphthalen-1-one derivs. useful in liquid crystal mixt. | |
| DE19652249A1 (en) | 1,3,5-trifluoronaphthalene derivatives and their use in liquid crystalline mixtures | |
| DE19652246A1 (en) | 5,7-difluoro-3,4-dihydro-2H-naphthalin-1-one derivatives and their use in liquid-crystalline mixtures | |
| DE4446880A1 (en) | Pyridazinone(s) improving property profile of liquid crystal mixts. | |
| DE19748433A1 (en) | 1-Fluoro-isoquinoline-8-carbonitrile derivatives, used as components of liquid crystal mixtures | |
| DE19648171A1 (en) | Di:fluoro-phenyl-pyrimidyl-pyridine compounds used in liquid crystal mixtures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8127 | New person/name/address of the applicant |
Owner name: AVENTIS RESEARCH & TECHNOLOGIES GMBH & CO KG, 6592 |
|
| 8141 | Disposal/no request for examination |