DE3615447A1 - Novel E/Z isomeric, fungicidally active acrylic acid compounds, process for their preparation and intermediates for carrying out the process - Google Patents
Novel E/Z isomeric, fungicidally active acrylic acid compounds, process for their preparation and intermediates for carrying out the processInfo
- Publication number
- DE3615447A1 DE3615447A1 DE19863615447 DE3615447A DE3615447A1 DE 3615447 A1 DE3615447 A1 DE 3615447A1 DE 19863615447 DE19863615447 DE 19863615447 DE 3615447 A DE3615447 A DE 3615447A DE 3615447 A1 DE3615447 A1 DE 3615447A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- alkyl
- alkoxy
- compounds
- amino
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000543 intermediate Substances 0.000 title abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- -1 hydroxy, amino Chemical group 0.000 claims description 104
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 13
- 150000001851 cinnamic acid derivatives Chemical class 0.000 claims description 13
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 8
- 150000004662 dithiols Chemical class 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000003573 thiols Chemical class 0.000 claims description 8
- 150000003555 thioacetals Chemical class 0.000 claims description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 230000000855 fungicidal effect Effects 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 125000003830 C1- C4 alkylcarbonylamino group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004863 4-trifluoromethoxyphenyl group Chemical group [H]C1=C([H])C(OC(F)(F)F)=C([H])C([H])=C1* 0.000 claims description 3
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 3
- 150000005171 halobenzenes Chemical class 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 3
- 241000233866 Fungi Species 0.000 claims 1
- 230000003032 phytopathogenic effect Effects 0.000 claims 1
- 239000000417 fungicide Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- XYKIUTSFQGXHOW-UHFFFAOYSA-N propan-2-one;toluene Chemical compound CC(C)=O.CC1=CC=CC=C1 XYKIUTSFQGXHOW-UHFFFAOYSA-N 0.000 description 14
- SPBNQJPWGMBPPP-UHFFFAOYSA-N 3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C=CC(=O)N1CCOCC1 SPBNQJPWGMBPPP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- KBTMGSMZIKLAHN-UHFFFAOYSA-N 4-bromo-1,2-dimethoxybenzene Chemical compound COC1=CC=C(Br)C=C1OC KBTMGSMZIKLAHN-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 235000013985 cinnamic acid Nutrition 0.000 description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 5
- GWQSENYKCGJTRI-UHFFFAOYSA-N 1-chloro-4-iodobenzene Chemical compound ClC1=CC=C(I)C=C1 GWQSENYKCGJTRI-UHFFFAOYSA-N 0.000 description 4
- AXICCPYRMWRPMS-UHFFFAOYSA-N 1-morpholin-4-yl-3-phenylprop-2-en-1-one Chemical compound C1COCCN1C(=O)C=CC1=CC=CC=C1 AXICCPYRMWRPMS-UHFFFAOYSA-N 0.000 description 4
- ZJPKEPANXMIBBZ-UHFFFAOYSA-N 3-(4-chlorophenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=CC(Cl)=CC=C1C=CC(=O)N1CCOCC1 ZJPKEPANXMIBBZ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PUCISUQLWLKKJH-UHFFFAOYSA-N 4-iodo-1,2-dimethoxybenzene Chemical compound COC1=CC=C(I)C=C1OC PUCISUQLWLKKJH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007341 Heck reaction Methods 0.000 description 3
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- QNBTYORWCCMPQP-NBVRZTHBSA-N (E)-dimethomorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(Cl)=CC=1)=C\C(=O)N1CCOCC1 QNBTYORWCCMPQP-NBVRZTHBSA-N 0.000 description 2
- AILMSPBSXLNSLU-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C=C(C=1C=CC(Cl)=CC=1)C(=O)N1CCOCC1 AILMSPBSXLNSLU-UHFFFAOYSA-N 0.000 description 2
- JXRYDOZRPYFBKO-UHFFFAOYSA-N 3,4-dimethoxy-cinnamic acidmethyl ester Natural products COC(=O)C=CC1=CC=C(OC)C(OC)=C1 JXRYDOZRPYFBKO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- RLZZZVKAURTHCP-UHFFFAOYSA-N phenanthrene-3,4-diol Chemical compound C1=CC=C2C3=C(O)C(O)=CC=C3C=CC2=C1 RLZZZVKAURTHCP-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- MLLIIHAKTPXMFF-UHFFFAOYSA-N (4-chlorophenyl)-(3,4-dimethoxyphenyl)methanone Chemical compound C1=C(OC)C(OC)=CC=C1C(=O)C1=CC=C(Cl)C=C1 MLLIIHAKTPXMFF-UHFFFAOYSA-N 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- ZKPHAZVFWUFOBL-DHZHZOJOSA-N (E)-1-morpholin-4-yl-3-(4-phenylphenyl)prop-2-en-1-one Chemical compound C1COCCN1C(=O)\C=C\C(C=C1)=CC=C1C1=CC=CC=C1 ZKPHAZVFWUFOBL-DHZHZOJOSA-N 0.000 description 1
- OCVGNDNRLVLPBB-LYBHJNIJSA-N (E)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-yl-3-(4-phenylphenyl)prop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(=CC=1)C=1C=CC=CC=1)=C\C(=O)N1CCOCC1 OCVGNDNRLVLPBB-LYBHJNIJSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SXHGIILHJKUXOS-CLCOLTQESA-N (Z)-3-(4-benzoylphenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C(C1=CC=CC=C1)(=O)C1=CC=C(C=C1)/C(=C/C(=O)N1CCOCC1)/C1=CC(=C(C=C1)OC)OC SXHGIILHJKUXOS-CLCOLTQESA-N 0.000 description 1
- DFJHABQTUCBCBF-PTNGSMBKSA-N (Z)-3-[4-(carboxymethyl)phenyl]-3-(3,4-dimethoxyphenyl)prop-2-enoic acid Chemical compound C1=C(OC)C(OC)=CC=C1C(=C/C(O)=O)\C1=CC=C(CC(O)=O)C=C1 DFJHABQTUCBCBF-PTNGSMBKSA-N 0.000 description 1
- QNBTYORWCCMPQP-JXAWBTAJSA-N (Z)-dimethomorph Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(Cl)=CC=1)=C/C(=O)N1CCOCC1 QNBTYORWCCMPQP-JXAWBTAJSA-N 0.000 description 1
- SXHGIILHJKUXOS-LYBHJNIJSA-N (e)-3-(4-benzoylphenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(=CC=1)C(=O)C=1C=CC=CC=1)=C\C(=O)N1CCOCC1 SXHGIILHJKUXOS-LYBHJNIJSA-N 0.000 description 1
- ZJPKEPANXMIBBZ-ZZXKWVIFSA-N (e)-3-(4-chlorophenyl)-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=CC(Cl)=CC=C1\C=C\C(=O)N1CCOCC1 ZJPKEPANXMIBBZ-ZZXKWVIFSA-N 0.000 description 1
- OCVGNDNRLVLPBB-CLCOLTQESA-N (z)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-yl-3-(4-phenylphenyl)prop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(=CC=1)C=1C=CC=CC=1)=C/C(=O)N1CCOCC1 OCVGNDNRLVLPBB-CLCOLTQESA-N 0.000 description 1
- MNJOFPIBBOODIP-SILNSSARSA-N (z)-3-(3,4-dimethoxyphenyl)-3-[4-(1,3-dioxolan-2-yl)phenyl]-1-morpholin-4-ylprop-2-en-1-one Chemical compound C1=C(OC)C(OC)=CC=C1C(\C=1C=CC(=CC=1)C1OCCO1)=C/C(=O)N1CCOCC1 MNJOFPIBBOODIP-SILNSSARSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZYIMHOWVWWHLDN-UHFFFAOYSA-N 2-(4-bromophenyl)-1,3-dioxolane Chemical compound C1=CC(Br)=CC=C1C1OCCO1 ZYIMHOWVWWHLDN-UHFFFAOYSA-N 0.000 description 1
- JTTPIFRYHSJHOY-UHFFFAOYSA-N 2-(4-bromophenyl)-1,3-dithiane Chemical compound C1=CC(Br)=CC=C1C1SCCCS1 JTTPIFRYHSJHOY-UHFFFAOYSA-N 0.000 description 1
- JIFLGTDRQPNZQC-UHFFFAOYSA-N 2-(4-bromophenyl)-4-propyl-1,3-dioxolane Chemical compound O1C(CCC)COC1C1=CC=C(Br)C=C1 JIFLGTDRQPNZQC-UHFFFAOYSA-N 0.000 description 1
- MFHFWRBXPQDZSA-UHFFFAOYSA-N 2-(4-bromophenyl)acetonitrile Chemical compound BrC1=CC=C(CC#N)C=C1 MFHFWRBXPQDZSA-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000006268 biphenyl-3-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C(*)=C([H])C([H])=C1[H] 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 230000008030 elimination Effects 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XPYGGHVSFMUHLH-UUSULHAXSA-N falecalcitriol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@@H](CCCC(O)(C(F)(F)F)C(F)(F)F)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C XPYGGHVSFMUHLH-UUSULHAXSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
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- 150000008424 iodobenzenes Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- YUUCWHZGZYKOQV-RVDMUPIBSA-N methyl (e)-3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)prop-2-enoate Chemical compound C=1C=C(OC)C(OC)=CC=1C(=C/C(=O)OC)/C1=CC=C(Cl)C=C1 YUUCWHZGZYKOQV-RVDMUPIBSA-N 0.000 description 1
- IIBXQGYKZKOORG-UHFFFAOYSA-N methyl 3-(4-chlorophenyl)prop-2-enoate Chemical compound COC(=O)C=CC1=CC=C(Cl)C=C1 IIBXQGYKZKOORG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical class OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
- C07D207/327—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
Description
Die Erfindung betrifft neue isomere Verbindungen, Verfahren zu deren Herstellung sowie Zwischenprodukte zur Durchführung dieses Verfahrens.The invention relates to new isomeric compounds, processes for their Manufacture and intermediates to carry out this process.
Aus der europäischen Patentanmeldung EP-A-1 20 321 sind 3,3-Diphenylacrylsäureamide bekannt geworden, welche eine neue Klasse wertvoller fungizider Wirkstoffe sind.From European patent application EP-A-1 20 321 3,3-Diphenylacrylsäureamide known, which is a new class are valuable fungicidal active ingredients.
Als Verfahren zur Synthese dieser Wirkstoffe wird u. a. der Aufbau des 3,3-Diphenylacrylsäuregerüsts ausgehend von entsprechend substituierten Benzophenonen und Phosphonsäurederivaten nach der Methode von Wittig und Horner vorgeschlagen.As a method for the synthesis of these active ingredients u. a. the structure of the 3,3-Diphenylacrylsäuretrüsts starting from appropriately substituted Benzophenones and phosphonic acid derivatives according to the Wittig and Horner suggested.
Dabei entstehen als Produkte Mischungen der Z und E-Isomere. Es wird vorgeschlagen, die Isomeren mittels üblicher Verfahren wie fraktionierte Kristallisation oder chromatographischer Methoden zu trennen.Mixtures of the Z and E isomers are formed as products. It will proposed the isomers by conventional methods such as fractional Separate crystallization or chromatographic methods.
Es wird nun ein Verfahren zur Synthese von Acrylsäurederivaten vorgeschlagen, mit welchem gezielt die Z und E-Isomere hergestellt werden können. Darüber hinaus können mit dem erfindungsgemäßen Verfahren auch Acrylsäurederivate hergestellt werden, welche durch Hydroxy-, Carboxy-, Carbonyl-, oder sonstige Radikale substituiert sind, die bei dem Wittig-Horner-Verfahren Nebenreaktionen eingehen können.There now becomes a process for the synthesis of acrylic acid derivatives proposed with which the Z and E isomers are specifically produced can. In addition, with the method according to the invention Acrylic acid derivatives are produced, which by hydroxy, carboxy, Carbonyl, or other radicals are substituted, which in the Wittig-Horner process can undergo side reactions.
Die Erfindung betrifft isomere Verbindungen der FormelThe invention relates to isomeric compounds of the formula
und/oderand or
in der
R1 für OH, OR2 oder NR3R4
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
R3 und R4 unabhängig voneinander fürin the
R 1 for OH, OR 2 or NR 3 R 4
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
R 3 and R 4 are independently for
- a) Wasserstoffa) hydrogen
- b) C1-C6-Alkyl gewünschtenfalls ein- oder mehrfach substituiert durch Halogen, C1-C4 Alkoxy, Hydroxyb) C 1 -C 6 alkyl optionally substituted one or more times by halogen, C 1 -C 4 alkoxy, hydroxy
oder
R3 und R4 gemeinsam mit dem Stickstoffatom ein ganz oder teilweise
gesättigtes oder ungesättigtes heterocyclisches 4 bis 7gliedriges
Ringsystem bilden, welches bis zu 3 Heteroatome enthalten kann und
welches gewünschtenfalls ein oder mehrfach durchor
R 3 and R 4 together with the nitrogen atom form a fully or partially saturated or unsaturated heterocyclic 4 to 7-membered ring system which can contain up to 3 heteroatoms and which, if desired, can be carried out one or more times
- a) C1-C4-Alkyla) C 1 -C 4 alkyl
- b) C1-C4-Alkoxyb) C 1 -C 4 alkoxy
- d) Hydroxy und/oderd) hydroxy and / or
- e) Oxo substituiert iste) oxo is substituted
A fürA for
B fürB for
die Substituenten R5 bis R9 unabhängig voneinander fürthe substituents R 5 to R 9 independently of one another for
- a) Wasserstoff, Halogen, Amino, Mono- oder Di-C1-C4-Alkylamino C1-C4-Alkyl-CO-NH, Cyano oder Nitroa) hydrogen, halogen, amino, mono- or di-C 1 -C 4 alkylamino C 1 -C 4 alkyl-CO-NH, cyano or nitro
- b) C1-C4-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlorb) C 1 -C 4 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C1-C6-Alkyl, gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Hydroxy, Amino, Cyano, Carboxy, C1-C6-Alkylthio C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoylc) C 1 -C 6 -alkyl, if desired mono- or polysubstituted by fluorine, chlorine, hydroxyl, amino, cyano, carboxy, C 1 -C 6 -alkylthio C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 - Alkylcarbonyl, benzoyl
- d) C1-C4-Alkylthiod) C 1 -C 4 alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor, C1-C4-Alkyl, Hydroxy, Cyano, Carboxy, Amino, C1-C4-Alkoxye) phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl, hydroxy, cyano, carboxy, amino, C 1 -C 4 alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiertf) phenoxy, if desired substituted as above under e)
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiertg) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituierth) Benzoyl, if desired substituted as above under e)
- i) C1-C4-Alkylcarbonylamino, gewünschtenfalls wie vorstehend unter c) substituierti) C 1 -C 4 alkylcarbonylamino, if desired substituted as above under c)
- j) CHO oder C1-C4-Alkyl CHO sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C4-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- oder Arylhydrazone und -Oxime.j) CHO or C 1 -C 4 alkyl CHO and, if desired, their acetals or thioacetals with C 1 -C 4 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl or aryl hydrazones and -Oxime.
Insbesondere betrifft die Erfindung Verbindungen der FormelIn particular, the invention relates to compounds of the formula
in der
R1 für OH, OR2 oder Morpholin
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
A fürin the
R 1 for OH, OR 2 or morpholine
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
A for
B fürB for
R5, R6 und R7 unabhängig voneinander für Wasserstoff, C1-C4- Alkyl, Amino, Chlor, Brom oder C1-C4-Niederalkoxy, Acetamido, C1-C4-Alkylthio, C1-C4-Alkylthio-C1-C6-alkyl R 5 , R 6 and R 7 independently of one another are hydrogen, C 1 -C 4 alkyl, amino, chlorine, bromine or C 1 -C 4 lower alkoxy, acetamido, C 1 -C 4 alkylthio, C 1 -C 4 -Alkylthio-C 1 -C 6 alkyl
Die Substituenten R8 und R9 unabhängig voneinander fürThe substituents R 8 and R 9 independently of one another for
- a) Wasserstoff, Fluor, Chlor, Cyano, Nitro, Amino, Acetamido, Broma) hydrogen, fluorine, chlorine, cyano, nitro, amino, acetamido, bromine
- b) C1-C6-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlorb) C 1 -C 6 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C1-C6-Alkyl, gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Hydroxy, Amino, C1-C4-Alkoxy, Phenyl, Carboxy, Cyano, Phenoxy, C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoylc) C 1 -C 6 alkyl, optionally substituted one or more times by fluorine, chlorine, hydroxy, amino, C 1 -C 4 alkoxy, phenyl, carboxy, cyano, phenoxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, benzoyl
- d) C1-C4-Alkylthiod) C 1 -C 4 alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor, C1-C4-Alkyl, Hydroxy, Cyano, Carboxy, Amino, C1-C4-Alkoxye) phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl, hydroxy, cyano, carboxy, amino, C 1 -C 4 alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiertf) phenoxy, if desired substituted as above under e)
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiertg) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituierth) Benzoyl, if desired substituted as above under e)
- i) CHO oder C1-C4-Alkyl-CHO sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C6-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- und Arylhydrazone und -Oximei) CHO or C 1 -C 4 alkyl CHO and, if desired, their acetals or thioacetals with C 1 -C 6 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl and aryl hydrazones and -Oxime
steht.stands.
Besonders bevorzugt sind folgende Bedeutungskombinationen für den Ring A
der Formel I:
3,4-Dimethoxyphenyl, 3-Methyl-4-methoxyphenyl, 3-Chlor-4-methoxyphenyl,
4-Methyl-3-methoxyphenyl, 3-Ethyl-4-methoxyphenyl, 3-Ethoxy-4-
methoxyphenyl, 4-Ethoxy-3-methoxyphenyl, 4-Amino-3,5-dichlorphenyl,
4-Amino-3-methylphenyl, 3-Amino-4-methoxyphenyl,
3-Acetamido-4-methoxyphenyl, 3-n-Propyl-4-methoxyphenyl,
3,5-Dichlorphenyl, 3-Methylthiomethyl-4-methoxyphenyl, 3,4-Dimethylphenyl.
The following combinations of meanings for ring A of formula I are particularly preferred:
3,4-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3-chloro-4-methoxyphenyl, 4-methyl-3-methoxyphenyl, 3-ethyl-4-methoxyphenyl, 3-ethoxy-4-methoxyphenyl, 4-ethoxy- 3-methoxyphenyl, 4-amino-3,5-dichlorophenyl, 4-amino-3-methylphenyl, 3-amino-4-methoxyphenyl, 3-acetamido-4-methoxyphenyl, 3-n-propyl-4-methoxyphenyl, 3, 5-dichlorophenyl, 3-methylthiomethyl-4-methoxyphenyl, 3,4-dimethylphenyl.
Und für den Ring B in Formel I:
4-Chlorphenyl, 4-Biphenyl, 4-Trifluormethylphenyl, 4-Hydroxyphenyl,
4-Aminophenyl, 4-Trifluormethoxyphenyl; 3-Biphenyl, 4-Acetylphenyl,
4-Benzoylphenyl, 4-Difluormethoxyphenyl, 4-Ethylphenyl, 4-n-Propylphenyl,
4-n-Butylphenyl, 4-Formylphenyl, 4-(1,3-Dioxolan-2-yl)-phenyl,
4-(4-n-Propyl-1,3-dioxan-2-yl)-phenyl, 4-(1,3-Dithian-2-yl)-phenyl,
4-Bromphenyl.And for ring B in Formula I:
4-chlorophenyl, 4-biphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-aminophenyl, 4-trifluoromethoxyphenyl; 3-biphenyl, 4-acetylphenyl, 4-benzoylphenyl, 4-difluoromethoxyphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-n-butylphenyl, 4-formylphenyl, 4- (1,3-dioxolan-2-yl) - phenyl, 4- (4-n-propyl-1,3-dioxan-2-yl) phenyl, 4- (1,3-dithian-2-yl) phenyl, 4-bromophenyl.
Des weiteren wurde gefunden, daß die E/Z-Isomeren durch Lichteinwirkung durch Lewissäure-Katalyse, thermisch oder durch Basenkatalyse bei erhöhter Temperatur in einem Gleichgewicht stehen.Furthermore, it was found that the E / Z isomers by exposure to light by Lewis acid catalysis, thermally or by base catalysis are in equilibrium at elevated temperatures.
Die Verbindungen der Formel Ia sind daher als wertvolle Vorstufen für die eigentlich fungizid wirksame Form Ib anzusehen. Insbesondere unter Freilandbedingungen können die per se unwirksamen Verbindungen Ia über das Gleichgewicht Ia Ib die wirksame Form Ib zur Verfügung stellen. Die Erfindung betrifft somit auch Verbindungen der Formel Ia, in der die Substituenten A, B und R1 die gleiche Bedeutung haben können wie die vorstehend als bevorzugt und besonders bevorzugt genannten Verbindungen der Formel Ib. The compounds of the formula Ia are therefore to be regarded as valuable precursors for the actually fungicidally active form Ib. Particularly under field conditions, the compounds Ia which are ineffective per se can provide the active form Ib via the equilibrium Ia Ib. The invention thus also relates to compounds of the formula Ia in which the substituents A, B and R 1 can have the same meaning as the compounds of the formula Ib mentioned above as preferred and particularly preferred.
Die Benennung der Isomeren wird nach der E/Z-Nomenklatur vorgenommen, wobei die vier Substituenten dem Cahn-Ingold-Prelog-System gemäß in der Reihenfolge sinkender Priorität angeordnet werden, (Angewandte Chemie 71 (1966) 413; J. Chem. Soc. 1951 612; Experimenta 12 (1956), 81; Bayer/Walter, Lehrbuch der organischen Chemie 19. Aufl. S. Hirzel Verlag Stuttgart, S. 69; Pure-Appl. Chem, 45 11-30 (1976); J. Org. Chem. 1970 2849).The isomers are named according to the E / Z nomenclature, the four substituents according to the Cahn-Ingold-Prelog system in the Order of decreasing priority, (Angewandte Chemie 71 (1966) 413; J. Chem. Soc. 1951 612; Experimenta 12 (1956), 81; Bayer / Walter, textbook of organic chemistry 19th ed. S. Hirzel Verlag Stuttgart, p. 69; Pure appl. Chem, 45, 11-30 (1976); J. Org. Chem. 1970 2849).
Im einzelnen bedeuten die einzelnen Substituenten für sich allein oder in Kombination mit weiteren Radikalen oder funktionellen Gruppen:Specifically, the individual substituents stand alone or in Combination with other radicals or functional groups:
- - C1-C4-Alkyl die Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, sek-Butyl-, iso-Butyl- oder tert-Butylradikale- C 1 -C 4 alkyl, the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl radicals
- - mit C1-C6-Alkyl sind außerdem noch die isomeren Pentyl- und Hexylradikale gemeint.- C 1 -C 6 alkyl also means the isomeric pentyl and hexyl radicals.
- - Halogen ist Fluor, Chlor, Brom oder Jod.- Halogen is fluorine, chlorine, bromine or iodine.
- - gesättigte heterocyclische Systeme sind Morpholin, Piperidin, Piperazin Pyrazolidin, Oxazolidin, Perhydroazepin- Saturated heterocyclic systems are morpholine, piperidine, piperazine Pyrazolidine, oxazolidine, perhydroazepine
- - teilweise gesättigte heterocyclische Systeme sind Imidazolin, Pyrazolin, Tetrahydropyridinpartially saturated heterocyclic systems are imidazoline, Pyrazoline, tetrahydropyridine
- - ungesättigte heterocyclische Systeme sind Pyrazol, Imidazo, 1,2,4- Triazol, 1,2,3-Triazol, Oxazol- Unsaturated heterocyclic systems are pyrazole, imidazo, 1,2,4- Triazole, 1,2,3-triazole, oxazole
- - Heteroatome sind Stickstoff und Sauerstoff - Heteroatoms are nitrogen and oxygen
- - Acetale bzw. Thioacetale sind offenkettige oder cyclische funktionelle Derivate der zugrunde liegenden Aldehyde mit Alkoholen, Thiolen, Diolen oder Dithiolen. Als Alkohole sind zu nennen: Methanol, Ethanol, Propanol u. a.; Diole sind: Ethylenglycol; Propandiol-1,2, Propandiol-1,3, 2-Hydroxymethyl-pentanol-1 u. a.; Thiole sind: Methylthiol, Ethylthiol, Propylthiol u. a.; Dithiole sind: Thioethylenglycol, 1,3-Propandithiol u. a.;- Acetals or thioacetals are open-chain or cyclic functional Derivatives of the underlying aldehydes with alcohols, thiols, diols or dithiols. The following can be mentioned as alcohols: methanol, ethanol, propanol u. a .; Diols are: ethylene glycol; 1,2-propanediol, 1,3-propanediol, 2-hydroxymethyl-pentanol-1 u. a .; Thiols are: methylthiol, ethylthiol, Propylthiol u. a .; Dithiols are: thioethylene glycol, 1,3-propanedithiol u. a .;
- - Hydrazone sind funktionelle Derivate von Aldehyden mit C1-C6-Alkyldrazinen oder Phenylhydrazinen oder mit Hydrazin allein- Hydrazones are functional derivatives of aldehydes with C 1 -C 6 -alkyldrazines or phenylhydrazines or with hydrazine alone
- -Oxime sind funktionelle Derivate des Aldehydes und können an der Sauerstoffunktion C1-C6-Alkyl oder arylsubstituiert sein.-Oximes are functional derivatives of the aldehyde and can be substituted on the oxygen function C 1 -C 6 alkyl or aryl.
Die erfindungsgemäßen E/Z-isomeren Verbindungen können in einfacher Weise aus den entsprechenden Zimtsäurederivaten der Formel IIa bzw. IIb durch Umsetzung der Halogenide IIIa bzw. IIIb unter Pd-(0)-Katalyse unter Halogenwasserstoffeliminierung hergestellt werden. Es wurde gefunden, daß der neu eintretende Substituent IIIa bzw. IIIb im Produkt überwiegend trans zur Carboxylgruppe der Säurefunktion steht. Es kann daher gemäß nachstehendem Schema jeweils durch Auswahl geeigneter Ausgangsverbindungen der Formel II die Stereochemie des Produktes I gesteuert werden:The E / Z isomeric compounds according to the invention can be used in a simple manner from the corresponding cinnamic acid derivatives of the formula IIa or IIb Implementation of the halides IIIa and IIIb under Pd (0) catalysis Hydrogen halide elimination are produced. It was found that the newly entering substituent IIIa or IIIb in Product is predominantly trans to the carboxyl group of the acid function. It can therefore be selected according to the following scheme by selecting more suitable Starting compounds of formula II the stereochemistry of product I to be controlled:
Die Erfindung betrifft somit ein Verfahren zur Synthese isomerer Verbindungen der FormelThe invention thus relates to a process for the synthesis of isomers Compounds of the formula
undand
in der
R1 für OH, OR2 oder NR3R4
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
R3 und R4 unabhängig voneinander fürin the
R 1 for OH, OR 2 or NR 3 R 4
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
R 3 and R 4 are independently for
- a) Wasserstoffa) hydrogen
- b) C1-C6-Alkyl gewünschtenfalls ein- oder mehrfach substituiert durch Halogen, C1-C4-Alkoxy, Hydroxyb) C 1 -C 6 alkyl optionally substituted one or more times by halogen, C 1 -C 4 alkoxy, hydroxy
oder
R3 und R4 gemeinsam mit dem Stickstoffatom ein gesättigtes heterocyclisches
4 bis 7gliedriges Ringsystem bilden, welches bis zu 3
Heteroatome enthalten kann und welches gewünschtenfalls ein oder
mehrfach durchor
R 3 and R 4 together with the nitrogen atom form a saturated heterocyclic 4 to 7-membered ring system which can contain up to 3 heteroatoms and which, if desired, can be carried out one or more times
- a) C1-C4-Alkyla) C 1 -C 4 alkyl
- b) C1-C4-Alkoxyb) C 1 -C 4 alkoxy
- d) Hydroxy und/oderd) hydroxy and / or
- e) Oxo substituiert iste) oxo is substituted
A fürA for
B fürB for
die Substituenten R5 bis R9 unabhängig voneinander fürthe substituents R 5 to R 9 independently of one another for
- a) Wasserstoff, Halogen, Amino, Mono- oder Di-C1-C4- Alkylamino, C1-C4-Alkyl-CO-NH Cyano oder Nitroa) hydrogen, halogen, amino, mono- or di-C 1 -C 4 - alkylamino, C 1 -C 4 alkyl-CO-NH cyano or nitro
- b) C1-C6-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlorb) C 1 -C 6 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C1-C6-Alkyl, gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Brom, Hydroxy, Amino, Cyano, Carboxy, C1-C4-Alkoxy, C1-C4-Alkylthio C1-C4-Alkoxy, Phenyl, Carboxy, Cyano, Phenoxy, C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoylc) C 1 -C 6 alkyl, optionally substituted one or more times by fluorine, chlorine, bromine, hydroxy, amino, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio C 1 -C 4 alkoxy, phenyl, carboxy, cyano, phenoxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, benzoyl
- d) C1-C4-Alkylthiod) C 1 -C 4 alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor, C1-C4-Alkyl, Hydroxy, Cyano, Carboxy, Amino C1-C4-Alkoxye) phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl, hydroxy, cyano, carboxy, amino C 1 -C 4 alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiertf) phenoxy, if desired substituted as above under e)
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiertg) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituierth) Benzoyl, if desired substituted as above under e)
- i) C1-C4-Alkylcarbonylamino, gewünschtenfalls wie vorstehend unter c) substituierti) C 1 -C 4 alkylcarbonylamino, if desired substituted as above under c)
- j) CHO oder C1-C4-CHO sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C4-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- oderArylhydrazone und -Oximej) CHO or C 1 -C 4 -CHO and, if desired, their acetals or thioacetals with C 1 -C 4 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl or aryl hydrazones and oximes
steht,
dadurch gekennzeichnet, daß man ein Zimtsäurederivat der Formelstands,
characterized in that a cinnamic acid derivative of the formula
ACH=CHCOR1 (IIa)ACH = CHCOR 1 (IIa)
oder
ein Zimtsäurederivat der Formelor
a cinnamic acid derivative of the formula
BCH=CHCOR1 (IIb)BCH = CHCOR 1 (IIb)
unter Pd-(0)-Katalyse mit einem Halogenid der Formelwith Pd (0) catalysis with a halide of the formula
oderor
in der Hal für Chlor, Brom oder Jod, vorzugsweise für Brom oder Jod steht, umsetzt.in the Hal for chlorine, bromine or iodine, preferably for bromine or iodine stands, implements.
Die Reaktion - eine Palladium-katalysierte Vinylilierung von Halogenbenzolen ist als Heck-Reaktion bekannt geworden, (R. F. Heck, Organic Reactions, Vol 27, 345 H).The reaction - palladium-catalyzed vinylilation of Halogen benzenes have become known as the Heck reaction, (R. F. Heck, Organic Reactions, Vol 27, 345 H).
Als Halogenbenzole besonders geeignet sind entsprechend substituierte Brombenzole und Jodbenzole der Formel III.Correspondingly substituted ones are particularly suitable as halogenobenzenes Bromobenzenes and iodobenzenes of the formula III.
Die Reaktion kann mit und ohne Lösungsmittel durchgeführt werden. Geeignet sind polare und unpolare Lösungsmittel z. B. Nitrile, wie Acetonitril, Propionitril; Alkohole wie Methanol, Ethanol, Propanol, Isopropanol; Ketone wie Aceton, Methylethylketon; Ether wie Diethylether, Tetrahydrofuran, Di-isopropylether, Glyme, Diglyme etc.; Amide, wie Dimethylformamid oder N-Methylpyrrolidon oder Hexamethylphosphorsäuretriamid, Aromaten, wie Benzol, Toluol, Xylol, Chlorbenzol. The reaction can be carried out with or without a solvent. Polar and non-polar solvents are suitable, for. B. nitriles, such as Acetonitrile, propionitrile; Alcohols such as methanol, ethanol, propanol, Isopropanol; Ketones such as acetone, methyl ethyl ketone; Ethers such as diethyl ether, Tetrahydrofuran, di-isopropyl ether, glyme, diglyme, etc .; Amides like Dimethylformamide or N-methylpyrrolidone or Hexamethylphosphoric triamide, aromatics such as benzene, toluene, xylene, Chlorobenzene.
Die Anwesenheit geringer Mengen an Wasser ist im allgemeinen nicht störend.The presence of small amounts of water is generally not annoying.
Die Reaktion kann bei Temperaturen zwischen Raumtemperaturen und der Siedetemperatur des Lösungsmittels durchgeführt werden. In geschlossenen Apparaturen kann auch bei noch höheren Temperaturen unter Druck gearbeitet werden. Bevorzugt ist der Temperaturbereich von 30 bis 160°C zu nennen.The reaction can take place at temperatures between room temperature and Boiling temperature of the solvent can be carried out. In closed Apparatus can be pressurized even at higher temperatures be worked. The temperature range from 30 to 160 ° C. is preferred to call.
Bei einer Reaktionstemperatur von etwa 100°C ist eine Menge von 1 Mol-% des Palladium-Katalysators (bezogen auf die Menge an Halogenbenzol III) ausreichend. Höhere Katalysatormengen können die Reaktionsgeschwindigkeit verbessern oder erlauben eine Verminderung der Reaktionstemperatur.At a reaction temperature of about 100 ° C, an amount of 1 mol% is of the palladium catalyst (based on the amount of halogenobenzene III) sufficient. Higher amounts of catalyst can affect the reaction rate improve or allow a reduction in the reaction temperature.
Im Reaktionsverlauf wird Halogenwasserstoffsäure freigesetzt zu deren Neutralisation Basen zugesetzt werden. Sofern als Edukte Carbonsäuren eingesetzt werden ist es vorteilhaft eine der Carboxyfunktion äquivalente Menge an Base zusätzlich einzusetzen.Hydrohalic acid is released in the course of the reaction Neutralization bases are added. If carboxylic acids as starting materials it is advantageous to use one equivalent to the carboxy function Use additional amount of base.
Als Basen sind zu nennen:
anorganische Basen, wie Soda, Natriumacetat, Natriumbicarbonat etc.
Amine, wie Triethylamin DABCO u. a. Heterocyclen, wie Pyridin, Chinolin
etc.The bases are:
inorganic bases such as soda, sodium acetate, sodium bicarbonate etc.
Amines, such as triethylamine DABCO and others, heterocycles, such as pyridine, quinoline etc.
Als Palladium-Katalysator können sowohl der laborübliche Pd-C-Katalysatoren oder aber Palladium (II)-salze, wie Palladiumacetat oder Palladiumhalogenide verwendet werden. Die Salze werden unter den Reaktionsbedingungen zu Palladium-(0) reduziert. Oft ist es von Vorteil - insbesondere bei Verwendung von Palladium-II-salzen - komplexierende Mittel, - wie Triarylphosphine zuzusetzen. The standard laboratory laboratory can be used as the palladium catalyst Pd-C catalysts or palladium (II) salts, such as palladium acetate or palladium halides can be used. The salts are among the Reaction conditions reduced to palladium- (0). It is often an advantage - especially when using palladium-II salts - complexing Agents, such as triarylphosphines.
Zur Diskussion des Reaktionsmechanismus wird auf die Literaturstelle Heck verwiesen.To discuss the reaction mechanism, reference is made to Heck referred.
Die Verbindungen der Formel I, in der R1 für OH steht, sind wertvolle Ausgangsverbindungen zur Synthese von Verbindungen der der Formel I, in denen R1 von OH verschieden ist. Aus den Carbonsäuren I (mit R1 = OH) können nach an sich bekannten Verfahren durch Umsetzung mit Alkoholen der Formel (VII) bzw. Verbindungen Formel (VI)The compounds of the formula I in which R 1 represents OH are valuable starting compounds for the synthesis of compounds of the formula I in which R 1 is different from OH. The carboxylic acids I (with R 1 = OH) can be prepared by processes known per se by reaction with alcohols of the formula (VII) or compounds of the formula (VI)
R2OH (VII)
R3R4NH (VI)R 2 OH (VII)
R 3 R 4 NH (VI)
durch Veresterungs- bzw. Amidierungsreaktionen die genannten Verbindungen der Formel I hergestellt werden, wobei im allgemeinen in Gegenwart wasserbindender Mittel gearbeitet wird oder die Carbonsäure I (R1 = OH) zunächst nach allgemein bekannten Verfahren in eine reaktive Form, wie z. B. Halogenide, Anhydride, Imidazolide etc. überführt und dann durch Umsetzung mit VI bzw. VII zum Ester bzw. Amid reagieren.the stated compounds of the formula I are prepared by esterification or amidation reactions, the procedure generally being carried out in the presence of water-binding agents or the carboxylic acid I (R 1 = OH) first being converted into a reactive form, for example by conventional methods. B. halides, anhydrides, imidazolides etc. and then react by reaction with VI or VII to give the ester or amide.
Die Erfindung betrifft somit Verfahren zur Herstellung von Verbindungen der Formel I in der R1 von OH verschieden ist, dadurch gekennzeichnet, daß man Verbindungen der Formel Ia bzw. Ib, in der R1 für OH steht mittels üblicher Verfahren durch Umsetzung mit Alkoholen der Formel VII oder Verbindungen der Formel VI gewünschtenfalls in Gegenwart wasserbindender Mittel umsetzt oder in dem man Verbindungen der Formel I in der R1 für OH steht mittels üblicher Verfahren in eine reaktive Form, wie etwa Säurehalogenid, Imidazolid oder gemischtes Anhydrid, überführt und dann durch Umsetzung mit VI bzw. VII in Verbindungen der Formel I in der R1 von OH verschieden ist überführt. The invention thus relates to processes for the preparation of compounds of the formula I in which R 1 is different from OH, characterized in that compounds of the formulas Ia or Ib in which R 1 is OH are used by customary processes by reaction with alcohols of the formula VII or compounds of the formula VI, if desired, in the presence of water-binding agents or in which compounds of the formula I in which R 1 is OH are converted into a reactive form, such as, for example, acid halide, imidazolide or mixed anhydride, by conventional methods and then by reaction with VI and VII are converted into compounds of the formula I in which R 1 is different from OH.
Des weiteren betrifft die Erfindung ein Verfahren zur Synthese von Verbindungen der Formel I, in der R1, für NR3R4 steht, dadurch gekennzeichnet, daß man Ester der allgemeinen Formel I, in der R1 für OR2 steht mit Verbindungen der Formel VI umsetzt.The invention further relates to a process for the synthesis of compounds of the formula I in which R 1 is NR 3 R 4 , characterized in that esters of the general formula I in which R 1 is OR 2 with compounds of the formula VI implements.
Zimtsäuren der Formel II sind wertvolle Ausgangsverbindungen zur Durchführung des erfindungsgemäßen Verfahrens. Sie können nach an sich bekannten Verfahren hergestellt werden, z. B. durchCinnamic acids of formula II are valuable starting compounds for Implementation of the method according to the invention. You can look at yourself known methods are prepared, e.g. B. by
-
a) Umsetzung von Aldehyden der Formel
ACHO,6(IVa)oderBCHO,6(IVb)in denen A, B und R1 wie zuvor definiert sind und R′ und R″ für
Alkyl vorzugsweise C1-C4 stehen mit Derivaten der
Phosphonoessigsäure nach Wittig-Horner
erhalten werden.
Dabei bilden sich überwiegend die E-Produkte. Bei diesem Verfahren ist R1 von OH verschieden.a) Reaction of aldehydes of the formula ACHO, 6 (IVa) or BCHO, 6 (IVb) in which A, B and R 1 are as previously defined and R ′ and R ″ are preferably alkyl C 1 -C 4 with derivatives of phosphonoacetic acid after Wittig-Horner be preserved.
Mostly the e-products are formed. In this process, R 1 is different from OH. - b) Durch Umsetzung der Aldehyde IVa bzw. IVb nach Perkin (Lit. Krauch Kunz, Reaktionen der organischen Chemie S-Auflage, Hüthing Heidelberg S. 748 f) zu Zimtsäuren der Formel (IIa) bzw. (IIb), in der R1 für OH steht.b) By conversion of the aldehydes IVa or IVb according to Perkin (Lit. Krauch Kunz, reactions of organic chemistry S-edition, Hüthing Heidelberg p. 748 f) to cinnamic acids of the formula (IIa) or (IIb), in which R 1 stands for OH.
- c) Zimtsäuren der Formel II, in denen R1 von OH verschieden sind können nach an sich bekannten Methoden ausgehend von Zimtsäuren der Formel II mit R1 = OH durch Veresterungs- bzw. Amidierungsreaktionen hergestellt werden, wobei im allgemeinen in Gegenwart wasserbindender Mittel gearbeitet wird.c) Cinnamic acids of the formula II, in which R 1 is different from OH, can be prepared by methods known per se, starting from cinnamic acids of the formula II with R 1 = OH, by esterification or amidation reactions, the procedure generally being in the presence of water-binding agents .
- d) Zimtsäuren der Formel II, in denen R1 für NR3R4 steht können durch Umsetzungen von Zimtsäureestern der Formel II, in der R1 für OR2 steht mit Verbindungen der Formel VI hergestellt werden.d) Cinnamic acids of the formula II in which R 1 is NR 3 R 4 can be prepared by reacting cinnamic acid esters of the formula II in which R 1 is OR 2 with compounds of the formula VI.
- e) Des weiteren können Zimtsäuren der Formel (II) unter Pd-(0)-Katalyse nach dem Verfahren von Heck durch Umsetzung von Acrylsäurederivaten der Formel VII mit Halogenbenzolen der Formel IIIa bzw. IIIb gemäß nachstehendem Reaktionsschema hergestellt werden: Dabei haben die Reste A, B und R1 die zuvor genannten Bedeutungen. Die Reaktionsbedingungen entsprechen den bei dem erfindungsgemäßen Verfahren zur Herstellung von Ia bzw. Ib diskutierten Parametern.e) Furthermore, cinnamic acids of the formula (II) can be prepared under Pd (0) catalysis by the Heck process by reacting acrylic acid derivatives of the formula VII with halobenzenes of the formula IIIa or IIIb in accordance with the following reaction scheme: The radicals A, B and R 1 have the meanings mentioned above. The reaction conditions correspond to the parameters discussed in the process according to the invention for producing Ia or Ib.
In den Zimtsäureverbindungen der Formel II haben die Substituenten A, B und R1 die zuvor genannten Bedeutungen. Sie können als cis- oder trans-Verbindungen oder auch als Gemisch beider Isomeren vorliegen.In the cinnamic acid compounds of the formula II, the substituents A, B and R 1 have the meanings mentioned above. They can exist as cis or trans compounds or as a mixture of both isomers.
Besonders bevorzugt sind Zimtsäuren der FormelCinnamic acids of the formula are particularly preferred
ACH=CHCOR1 (IIa)ACH = CHCOR 1 (IIa)
oderor
BCH=CHCOR1 (IIb)BCH = CHCOR 1 (IIb)
in der für
3,4-Dimethoxyphenyl, 3-Methyl-4-methoxyphenyl, 3-Chlor-4-methoxyphenyl,
4-Methyl-3-methoxyphenyl, 3-Ethyl-4-methoxyphenyl, 3-Ethoxy-4-
methoxyphenyl, 4-Ethoxy-3-methoxyphenyl, 4-Amino-3,5-dichlorphenyl,
4-Amino-3-methylphenyl, 3-Amino-4-methoxyphenyl, 3-Amino-4-methoxyphenyl,
3-Acetamido-4-methoxyphenyl, 3-n-Propyl-4-methoxyphenyl,
3,5-Dichlorphenyl, 3-Methylthiomethyl-4-methoxyphenyl, 3,4-Dimethylphenyl
und für B
4-Chlorphenyl, 4-Biphenyl, 4-Trifluormethylphenyl, 4-Hydroxyphenyl,
4-Aminophenyl, 4-Trifluormethoxyphenyl, 3-Biphenylyl, 4-Acetylphenyl,
4-Benzoylphenyl, 4-Difluormethoxyphenyl, 4-Ethylphenyl, 4-n-Propylphenyl,
4-n-Butylphenyl, 4-Bromphenyl
stehen.
in the for
3,4-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3-chloro-4-methoxyphenyl, 4-methyl-3-methoxyphenyl, 3-ethyl-4-methoxyphenyl, 3-ethoxy-4-methoxyphenyl, 4-ethoxy- 3-methoxyphenyl, 4-amino-3,5-dichlorophenyl, 4-amino-3-methylphenyl, 3-amino-4-methoxyphenyl, 3-amino-4-methoxyphenyl, 3-acetamido-4-methoxyphenyl, 3-n- Propyl-4-methoxyphenyl, 3,5-dichlorophenyl, 3-methylthiomethyl-4-methoxyphenyl, 3,4-dimethylphenyl
and for B
4-chlorophenyl, 4-biphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-aminophenyl, 4-trifluoromethoxyphenyl, 3-biphenylyl, 4-acetylphenyl, 4-benzoylphenyl, 4-difluoromethoxyphenyl, 4-ethylphenyl, 4-n-propyl 4-n-butylphenyl, 4-bromophenyl
stand.
Des weiteren betrifft die Erfindung ein zweistufiges Verfahren zur Synthese von E/Z-isomeren Verbindungen der Formel I ausgehend von Acrylsäuren der Formel (VII) gemäß nachstehendem SchemaFurthermore, the invention relates to a two-stage process for Synthesis of E / Z isomeric compounds of formula I starting from Acrylic acids of formula (VII) according to the scheme below
(IIIa) + (VII) → (IIa)
(IIa) + (IIIb) → (Ib)
(IIIb) + (VII) → (IIb)
(IIb) + (IIIa) → (Ia)(IIIa) + (VII) → (IIa)
(IIa) + (IIIb) → (Ib)
(IIIb) + (VII) → (IIb)
(IIb) + (IIIa) → (Ia)
Stufe 1 und Stufe 2 können dabei jeweils unter Pd-(0)-Katalyse nach dem Verfahren von Heck durchgeführt werden. Die vorstehend genannten Reaktionsbedingungen, welche zur Durchführung der Heck Reaktion geeignet sind, gelten hier entsprechend. Level 1 and level 2 can each under Pd (0) catalysis after Procedures to be carried out by Heck. The above Reaction conditions suitable for carrying out the Heck reaction are valid here accordingly.
Besonders ist darauf hinzuweisen, daß das zweistufige Reaktionsverfahren auch ohne Isolierung der Zimtsäurederivate IIa bzw. IIb im Sinne einer "Eintopfreaktion" durchgeführt werden kann. Dazu wird zunächst ein Halogenbenzol der Formel IIIa bzw. IIIb mit einer Acrylsäure der Formel VII unter den Bedingungen der Heck-Reaktion zu einem Zimtsäurederivat der Formel IIa bzw. IIb umgesetzt, wobei das Halogenbenzol IIIa bzw. IIIb vollständig, verbraucht wird. Danach wird das Halogenbenzol IIIb bzw. IIIa zugesetzt, welches in der zweiten Stufe an IIa bzw. IIb zum Produkt Ib bzw. Ia reagiert. Die bei dem "Eintopfverfahren" eingesetzten Äquivalente an Base sind so bemessen, daß sie die gesamte bei der Reaktion freiwerdende Halogenstoffsäure zu binden vermögen.It is particularly noteworthy that the two-stage reaction process even without isolation of the cinnamic acid derivatives IIa or IIb in the sense of a "One-pot reaction" can be carried out. To do this, first a Halogenbenzene of the formula IIIa or IIIb with an acrylic acid of the formula VII under the conditions of the Heck reaction to a cinnamic acid derivative Formula IIa and IIb implemented, the halogenobenzene IIIa and IIIb completely, is consumed. Then the halogenobenzene IIIb or IIIa added, which in the second stage to IIa or IIb to the product Ib or Ia reacts. Those used in the "one-pot process" Equivalents of base are dimensioned so that they are the whole at Can bind reaction released halogen acid.
1,96 g = 10 mMol 4-Chlorzimtsäuremethylester, 2,64 g = 10 mMol 4-Jodveratrol, 22,5 mg = 0,1 mMol Palladium-II-acetat, 5 ml Triethylamin und 5 ml Dimethylformamid werden gemischt und 8 Std. unter Rückfluß gekocht. Nach dem Abkühlen wird mit 25 ml Toluol und 50 ml 1 n Salzsäure geschüttelt, die org. Phase nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 20 g Kieselgel getrennt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 95 : 5, dann 90 : 10. Die Fraktionen mit der Substanz vom Rf = 0,5 (Toluol-Aceton 90 : 10) werden im Vakuum eingedampft.1.96 g = 10 mmol of 4-chlorocinnamic acid methyl ester, 2.64 g = 10 mmol of 4-iodoveratrol, 22.5 mg = 0.1 mmol of palladium-II-acetate, 5 ml of triethylamine and 5 ml of dimethylformamide are mixed and 8 hours. cooked under reflux. After cooling, shaken with 25 ml of toluene and 50 ml of 1N hydrochloric acid, the org. Phase washed again with water, dried and separated on a column with 20 g of silica gel. Elution is carried out with toluene, toluene-acetone mixture 95: 5, then 90:10. The fractions with the substance of Rf = 0.5 (toluene-acetone 90:10) are evaporated in vacuo.
Ausbeute: 1,85 g = 56% der Titelverbindung als Öl.Yield: 1.85 g = 56% of the title compound as an oil.
Analog zu Beispiel 1 erhält man die Titelverbindung aus 3,4-Dimethoxyzimtsäuremethylester und 4-Chlorjodbenzol. Analogously to Example 1, the title compound is obtained 3,4-Dimethoxycinnamic acid methyl ester and 4-chloroiodobenzene.
2,52 g = 10 mMol 4-Chlorzimtsäuremorpholid, 2,90 g = mMol 4-Jodveratrol, 22,5 mg = 0,1 mMol Palladium-II-acetat werden mit 5 ml Triethylamin und 5 ml Dimethylformamid 8 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wird mit Wasser/Toluol geschüttelt. Die org. Phase wird nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 30 g Kieselgel getrennt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 95 : 5, 90 : 10, 80 : 2. Die Fraktionen mit der Substanz vom Rf = 0,42 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft.2.52 g = 10 mmol of 4-chlorocinnamic acid morpholide, 2.90 g = mmol of 4-iodoveratrol, 22.5 mg = 0.1 mmol of palladium-II-acetate are boiled under reflux for 8 hours with 5 ml of triethylamine and 5 ml of dimethylformamide. After cooling, shake with water / toluene. The org. The phase is washed again with water, dried and separated on a column containing 30 g of silica gel. Elution is carried out with toluene, toluene-acetone mixture 95: 5, 90: 10, 80: 2. The fractions with the substance of Rf = 0.42 (toluene-acetone 70:30) are evaporated in vacuo.
Ausbeute: 3,1 g (80%) der Titelverbindung als langsam erstarrendes Öl. Das E/Z-Verhältnis wurde H-NMR-spektrokopisch mit 83/17 bestimmt.Yield: 3.1 g (80%) of the title compound as a slowly solidifying oil. The E / Z ratio was found to be 83/17 by H-NMR spectroscopy.
Die Umsetzung wird analog Beispiel 3a durchgeführt jedoch unter Verwendung von 210 mg (0,1 mMol) Palladium auf Aktivkohle (5%-ig) anstelle des Palladium-II-acetats. Man isoliert 3,0 g der Titelverbindung (77% d. Th.) mit einem E/Z-Verhältnis von 95 : 5.The reaction is carried out analogously to Example 3a, but under Use of 210 mg (0.1 mmol) palladium on activated carbon (5%) instead of the palladium-II-acetate. 3.0 g of the title compound (77% of theory) are isolated with a E / Z ratio of 95: 5.
2,52 g = 10 mMol 4-Chlorzimtsäuremorpholid, 2,60 g = 12 mMol 4-Bromveratrol, 22,5 mg = 0,1 mMol Palladium-II-acetat, 61 mg = 0,2 mMol Tri-o-tolylphosphin werden mit 5 ml Triethylamin und 5 ml Dimethylformamid 18 Stunden unter Rückfluß gekocht und wie unter 3a beschrieben aufgearbeitet.2.52 g = 10 mmol 4-chlorocinnamic acid morpholide, 2.60 g = 12 mmol 4-bromveratrol, 22.5 mg = 0.1 mmol palladium-II-acetate, 61 mg = 0.2 mmol tri-o-tolylphosphine with 5 ml triethylamine and 5 ml Dimethylformamide boiled under reflux for 18 hours and as in 3a described worked up.
Ausbeute: 2,9 (75%) der Titelverbindung. Yield: 2.9 (75%) of the title compound.
2,77 g = 10 mMol 3,4-Dimethoxyzimtsäuremorpholid, 1,91 g = 10 mMol 1-Brom-4-Chlorbenzol, 22,5 mg = 0,1 mMol Palladium-II-acetat, 61 mg = 0,2 mMol, Tri-o-tolylphosphine werden mit 5 ml Triethylamin und 5 ml Dimethylformamid werden 8 Stunden unter Rückfluß gekocht und wie unter 3 beschrieben aufgearbeitet.2.77 g = 10 mmol 3,4-dimethoxycinnamic acid morpholide, 1.91 g = 10 mmol 1-bromo-4-chlorobenzene, 22.5 mg = 0.1 mmol palladium-II-acetate, 61 mg = 0.2 mmol, tri-o-tolylphosphine with 5 ml of triethylamine and 5 ml of dimethylformamide are refluxed for 8 hours and as below 3 described worked up.
Ausbeute: 1,95 g (= 50%) der Titelverbindung. Das E/Z-Verhältnis wurde H-NMR-spektroskopisch mit 5/95 bestimmt.Yield: 1.95 g (= 50%) of the title compound. The E / Z ratio was H-NMR spectroscopically determined to be 5/95.
4,16 g = 15 mMol 3,4-Dimethoxyzimtsäuremorpholid, 3,93 = 16,5 mMol 1-Chlor-4-jodbenzol, 33,7 mg = 0,15 mMol Palladium-II-acetat werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 8 Stunden unter Rückfluß gekocht und wie unter 3a beschrieben aufgearbeitet.4.16 g = 15 mmoles of 3,4-dimethoxycinnamic acid morpholide, 3.93 = 16.5 mmoles 1-chloro-4-iodobenzene, 33.7 mg = 0.15 mmol of palladium-II-acetate are added 10 ml of triethylamine and 10 ml of dimethylformamide under reflux for 8 hours cooked and worked up as described under 3a.
Ausbeute: 3,5 g (= 60%) der Titelverbindung mit einem E/Z-Verhältnis von 25/75. Yield: 3.5 g (= 60%) of the title compound with an E / Z ratio of 25/75.
4,4 g = 15 mMol E-4-Phenylzimtsäuremorpholid, 4,35 g = 16,5 mMol 4-Jodveratrol, 315 mg = 0,15 mMol Palladium/Aktivkohle, 5%ig, werden mit 7,5 ml Triethylamin und 10 ml Dimethylformamid 8 Stunden unter Rückfluß gekocht. Die noch heiße Lösung wird mit 20 ml Toluol versetzt, filtriert und das Filtrat 2 × mit Wasser ausgeschüttelt. Nach dem Trocknen wird die Lösung über eine Säule mit 50 g Kieselgel getrennt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 95 : 5, 90 : 10, 80 : 20. Die Fraktionen mit der Substanz vom Rf = 0,37 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft und das erhaltene zähe Öl aus Methanol- Diisopropylether umkristallisiert.4.4 g = 15 mmol E-4-phenylcinnamic acid morpholide, 4.35 g = 16.5 mmol 4-iodoveratrol, 315 mg = 0.15 mmol palladium / activated carbon, 5%, are mixed with 7.5 ml triethylamine and 10 ml of dimethylformamide boiled under reflux for 8 hours. The still hot solution is mixed with 20 ml of toluene, filtered and the filtrate is shaken twice with water. After drying, the solution is separated on a column with 50 g of silica gel. Is eluted with toluene, toluene-acetone mixture 95: 5, 90: 10, 80: 20. The fractions with the substance of Rf = 0.37 (toluene-acetone 70:30) are evaporated in vacuo and the viscous oil obtained recrystallized from methanol-diisopropyl ether.
Ausbeute: 4,3 g (= 69%) der Titelverbindung als Kristalle vom Schmp. 127-128°C. ′H-NMR-spektroskopisch konnte keine Z-Verbindung nachgewiesen werden.Yield: 4.3 g (= 69%) of the title compound as crystals of mp. 127-128 ° C. 'H-NMR spectroscopy showed no Z compound will.
Analog zu Beispiel 5 kann die Titelverbindung ausgehend von 3,4-Dimethoxyzimtsäuremorpholid und 4-Brom-biphenyl hergestellt werden. Analogously to example 5, the title compound can be started from 3,4-Dimethoxycinnamic acid morpholide and 4-bromobiphenyl can be produced.
5,55 g = 20 mMol 3,4-Dimethoxyzimtsäuremorpholid, 4,98 = 25 mMol 4-Bromacetophenon, 45 mg= 0,2 mMol Palladium-II-acetat, 122 mg = 0,4 mMol Tri-o-tolylphosphin werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 18 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wird mit Toluol/Wasser geschüttelt, die org. Phase nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 50 g Kieselgel getrennt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 90 : 10, 80 : 20, 70 : 30. Die Fraktionen mit der Substanz vom Rf-0,31 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft.5.55 g = 20 mmol of 3,4-dimethoxycinnamic acid morpholide, 4.98 = 25 mmol of 4-bromoacetophenone, 45 mg = 0.2 mmol of palladium-II-acetate, 122 mg = 0.4 mmol of tri-o-tolylphosphine are added 10 ml of triethylamine and 10 ml of dimethylformamide are boiled under reflux for 18 hours. After cooling, the mixture is shaken with toluene / water, the org. Phase washed again with water, dried and separated on a column with 50 g of silica gel. It is eluted with toluene, toluene-acetone mixture 90:10, 80:20, 70:30. The fractions with the substance of Rf -0.31 (toluene-acetone 70:30) are evaporated in vacuo.
Ausbeute: 3,3 g der Titelverbindung als langsam kristallisierendes Öl mit einem E/Z-Verhältnis von 5/95.Yield: 3.3 g of the title compound as a slowly crystallizing oil with an E / Z ratio of 5/95.
Ausgehend von 4-Acetylzimtsäuremorpholid und 4-Bromveratrol kann die Titelverbindung hergestellt werden. Starting from 4-acetylcinnamic acid morpholide and 4-bromveratrol, the Title connection can be established.
5,55 g = 20 mMol 3,4-Dimethoxyzimtsäuremorpholid, 5,63 g = 25 mMol 4-Brombenzotrifluorid, 45 mg= 0,2 mMol Palladium-II-acetat, 122 mg = 0,4 mMol Tri-o-tolylphosphin werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 16 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wird mit Toluol/Wasser geschüttelt. Die org. Phase wird nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 60 g Kieselgel gereinigt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 95 : 5, 90 : 10, 80 : 20. Die Fraktionen mit der Substanz vom Rf = 0,36 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft.5.55 g = 20 mmol of 3,4-dimethoxycinnamic acid morpholide, 5.63 g = 25 mmol of 4-bromobenzotrifluoride, 45 mg = 0.2 mmol of palladium-II-acetate, 122 mg = 0.4 mmol of tri-o-tolylphosphine boiled under reflux with 10 ml of triethylamine and 10 ml of dimethylformamide for 16 hours. After cooling, it is shaken with toluene / water. The org. The phase is washed again with water, dried and purified on a column with 60 g of silica gel. Elution is carried out with toluene, toluene-acetone mixture 95: 5, 90: 10, 80: 20. The fractions with the substance of Rf = 0.36 (toluene-acetone 70:30) are evaporated in vacuo.
Ausbeute: 3,6 g (= 42%) der Titelverbindung als langsam erstarrendes Öl.Yield: 3.6 g (= 42%) of the title compound as a slowly solidifying oil.
Analog zu Beispiel 9 kann die Titelverbindung durch Umsetzung von 4-Trifluormethylzimtsäuremorpholid mit Bromveratrol hergestellt werden.Analogously to Example 9, the title compound can be converted by reacting 4-Trifluormethylzimtsäuremorpholid be prepared with bromveratrol.
5,83 g = 20 mMol 4-Ethoxy-3-methoxyzimtsäuremorpholid, 5,25 g = 22 mMol 1-Chlor-4-jodbenzol, 45 mg = 0,2 mMol Palladium-II-acetat werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 8 Stunden unter Rückfluß gekocht. Die noch warme Lösung wird mit Toluol/Wasser geschüttelt, die org. Phase nochmals mit Wasser gewaschen, wobei bereits Substanz auszukristallisieren beginnt. Durch Erwärmen wird nochmals die Lösung gebracht, getrocknet und im Vakuum eingeengt. Beim Abkühlen kristallisiert die Substanz aus.5.83 g = 20 mmol of 4-ethoxy-3-methoxycinnamic acid morpholide, 5.25 g = 22 mmol 1-chloro-4-iodobenzene, 45 mg = 0.2 mmol of palladium-II-acetate are added 10 ml of triethylamine and 10 ml of dimethylformamide under reflux for 8 hours cooked. The still warm solution is shaken with toluene / water org. Phase washed again with water, being already substance begins to crystallize. By heating again the solution becomes brought, dried and concentrated in vacuo. When cooling down the substance crystallizes out.
Ausbeute: 3,75 g (= 47%) der Titelverbindung als Kristalle vom Schmp. 163°C. Yield: 3.75 g (= 47%) of the title compound as crystals of mp. 163 ° C.
Analog zu Beispiel 11 kann die Titelverbindung durch Umsetzung von 4-Chlorzimtsäuremorpholid und 4-Ethoxy-3-methoxybrombenzol hergestellt werden.Analogously to Example 11, the title compound can be converted by reacting 4-chlorocinnamic acid morpholide and 4-ethoxy-3-methoxybromobenzene will.
5,83 g = 20 mMol 3-Ethoxy-4-methoxyzimtsäuremorpholid, 5,25 g = 22 mMol 1-Chlor-4-jodbenzol, 45 mg = 0,2 mMol Palladium-II-acetat werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 8 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wird mit Toluol/Wasser geschüttelt, die org. Phase nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 50 g Kieselgel gereinigt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 95 : 5, 90 : 10, 80 : 20. Die Fraktionen mit der Substanz vom Rf = 0,45 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft.5.83 g = 20 mmol of 3-ethoxy-4-methoxycinnamic acid morpholide, 5.25 g = 22 mmol of 1-chloro-4-iodobenzene, 45 mg = 0.2 mmol of palladium-II-acetate are mixed with 10 ml of triethylamine and 10 ml Dimethylformamide boiled under reflux for 8 hours. After cooling, the mixture is shaken with toluene / water, the org. Phase washed again with water, dried and purified on a column with 50 g of silica gel. Is eluted with toluene, toluene-acetone mixture 95: 5, 90: 10, 80: 20. The fractions with the substance of Rf = 0.45 (toluene-acetone 70:30) are evaporated in vacuo.
Ausbeute: 3,6 g (= 45%) der Titelverbindung mit einem E/Z-Verhältnis von 12/88 als Kristalle vom Schmp. 142-143°C.Yield: 3.6 g (= 45%) of the title compound with an E / Z ratio of 12/88 as crystals of mp. 142-143 ° C.
Analog zu Beispiel 13 kann die Titelverbindung durch Umsetzung von 4-chlorzimtsäuremorpholid und 3-Ethoxy-4-methoxybrombenzol hergestellt werden. Analogously to Example 13, the title compound can be converted by reacting 4-chlorocinnamic acid morpholide and 3-ethoxy-4-methoxybromobenzene will.
5,55 g = 20 mMol 3,4-Dimethoxyzimtsäuremorpholid, 5,7 g = 22 mMol 4-Brombenzophenon, 45 mg= 0,2 mMol Palladium-II-acetat, 122 mg = 0,4 mMol Tri-o-tolylphosphin werden mit 10 ml Triethylamin und 10 ml Dimethylformamid 15 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wird mit Toluol/Wasser geschüttelt, die org. Phase nochmals mit Wasser gewaschen, getrocknet und über eine Säule mit 60 g Kieselgel gereinigt. Eluiert wird mit Toluol, Toluol-Aceton-Gemisch 90 : 10. Die Fraktionen mit der Substanz vom Rf = 0,34 (Toluol-Aceton 70 : 30) werden im Vakuum eingedampft.5.55 g = 20 mmol 3,4-dimethoxycinnamic acid morpholide, 5.7 g = 22 mmol 4-bromobenzophenone, 45 mg = 0.2 mmol palladium-II-acetate, 122 mg = 0.4 mmol tri-o-tolylphosphine boiled under reflux with 10 ml of triethylamine and 10 ml of dimethylformamide for 15 hours. After cooling, the mixture is shaken with toluene / water, the org. Phase washed again with water, dried and cleaned on a column with 60 g of silica gel. Is eluted with toluene, toluene-acetone mixture 90:10. The fractions with the substance of Rf = 0.34 (toluene-acetone 70:30) are evaporated in vacuo.
Ausbeute: 4,0 g (= 44%) der Titelverbindung mit einem E/Z-Verhältnis von 10/90.Yield: 4.0 g (= 44%) of the title compound with an E / Z ratio of 10/90.
Analog zu Beispiel 15 kann die Titelverbindung durch Umsetzung von 4-Benzoylzimtsäuremorpholid und 4-Bromveratrol erhalten werden.Analogously to Example 15, the title compound can be converted by reacting 4-Benzoylzimtsäuremorpholid and 4-bromveratrol can be obtained.
Analog zu vorstehenden Beispielen kann die Titelverbindung durch Umsetzung von 3,4-Dimethoxyzimtsäuremorpholid und 4-Jodphenol hergestellt werden. Analogously to the examples above, the title compound can be obtained by Implementation of 3,4-dimethoxycinnamic acid morpholide and 4-iodophenol will.
Analog zu vorstehenden Beispielen kann die Titelverbindung durch Umsetzung von 4-Hydroxyzimtsäuremorpholid und 4-Bromvertrol hergestellt werden.Analogously to the examples above, the title compound can be obtained by Implementation of 4-hydroxycinnamic acid morpholide and 4-bromocompole will.
Analog zu den Beispielen kann die Titelverbindung (Rf = 0,32, Kieselgel, Toluol/Aceton = 7/3) aus 3,4-Dimethoxyzimtsäuremorpholid und 4-Bromphenylacetonitril hergestellt werden.Analogously to the examples, the title compound ( Rf = 0.32, silica gel, toluene / acetone = 7/3) can be prepared from 3,4-dimethoxycinnamic acid morpholide and 4-bromophenylacetonitrile.
Analog zu den Beispielen kann die Titelverbindung 4-Cyanomethoylzimtsäure- morpholid und 4-Bromveratrol hergestellt werden.Analogously to the examples, the title compound 4-cyanomethoyl cinnamic acid morpholide and 4-bromveratrol can be produced.
Analog zu den Beispielen erhält man die Titelverbindung als Kristalle vom Schmp. 192-194°C aus 3,4-Dimethoxyzimtsäuremorpholid und (4-Bromphenyl)- essigsäure. Analogously to the examples, the title compound is obtained as crystals of Mp 192-194 ° C from 3,4-dimethoxycinnamic acid morpholide and (4-bromophenyl) - acetic acid.
Analog zu den Beispielen erhält man die Titelverbindung aus 4-Carboxymethylzimtsäuremorpholid und 4-Bromveratrol.Analogously to the examples, the title compound is obtained 4-carboxymethylcinnamic acid morpholide and 4-bromveratrol.
Analog zu den Beispielen erhält man die Titelverbindung aus 3,4-Di- methoxyzimtsäuremorpholid und 4-Brombenzaldehyd.Analogously to the examples, the title compound is obtained from 3,4-di methoxycinnamic acid morpholide and 4-bromobenzaldehyde.
Analog zu den Beispielen erhält man die Titelverbindung aus4-Formylzimtsäuremorpholid und 4-Bromveratrol.Analogously to the examples, the title compound is obtained from 4-formylcinnamic acid morpholide and 4-bromveratrol.
Analog zu den Beispielen erhält man die Titelverbindung aus 3,4-Dimethoxyzimtsäuremorpholid und 2-(4-Bromphenyl)-1,3-dioxolan. Analogously to the examples, the title compound is obtained from 3,4-dimethoxycinnamic acid morpholide and 2- (4-bromophenyl) -1,3-dioxolane.
Analog zu den Beispielen erhält man die Titelverbindung aus 4-(1,3-Dioxolan-2-yl)-zimtsäuremorpholid und 4-BromveratrolAnalogously to the examples, the title compound is obtained 4- (1,3-dioxolan-2-yl) cinnamic acid morpholide and 4-bromoveratrol
Analog zu den Beispielen erhält man die Titelverbindung aus 4-(4-n-Propyl- 1,3-dioxolan-2-yl)-zimtsäuremorpholid und 4-BromveratrolAnalogously to the examples, the title compound is obtained from 4- (4-n-propyl- 1,3-dioxolan-2-yl) cinnamic acid morpholide and 4-bromoveratrol
Analog zu den Beispielen erhält man die Titelverbindung aus 2-(4-Bromphenyl)-4-n-propyl-1,3-dioxolan und 3,4-DimethoxyzimtsäuremorpholidAnalogously to the examples, the title compound is obtained 2- (4-bromophenyl) -4-n-propyl-1,3-dioxolane and 3,4-dimethoxycinnamic acid morpholide
Analog zu den Beispielen erhält man die Titelverbindung aus 4-(1,3-dithioxan-2-yl)-zimtsäuremorpholid und 4-Bromveratrol Analogously to the examples, the title compound is obtained 4- (1,3-dithioxan-2-yl) cinnamic acid morpholide and 4-bromoveratrol
Analog zu den Beispielen erhält man die Titelverbindung 3,4-Dimethoxyzimtsäuremorpholid und 2-(4-Bromphenyl)-1,3-dithian.The title compound is obtained analogously to the examples 3,4-dimethoxycinnamic acid morpholide and 2- (4-bromophenyl) -1,3-dithiane.
3,3 g = 110 mMol Natriumhydrid (mit 20% Paraffinöl) werden mit 40 mol abs. Tetrahydrofuran gerührt und eine Lösung von 29,2 g = 110 mMol Diethylphosphonacetmorpholid in 30 ml abs. Tetrahydrofuran zugetropft. Die Temperatur wird durch Kühlen bei 25° gehalten. Nach klarer Lösung werden 14,06 g = 100 mMol 4-Chlorbenzaldehyd, gelöst in 30 ml abs. Tetrahydrofuran, zugetropft, wobei die Temperatur durch Kühlen bei 30 bis 35° gehalten wird. Nach beendeter Zugabe wird 15 Min. bei Raumtemperatur nachgerührt, 30 Min. unter Rückfluß gekocht, dann unter Vakuum eingedampft. Der Rückstand wird mit Methylenchlorid/Wasser geschüttelt, die organische Phase nochmals mit Wasser gewaschen, getrocknet und eingedampft. Der Rückstand wird aus Toluol umkristallisiert. Ausbeute: 20,6 g (= 82%) der Titelverbindung als Kristalle vom Schmp. 140-141°C. 3.3 g = 110 mmol sodium hydride (with 20% paraffin oil) are mixed with 40 mol Section. Tetrahydrofuran stirred and a solution of 29.2 g = 110 mmol Diethylphosphonacetmorpholid in 30 ml abs. Tetrahydrofuran added dropwise. The temperature is kept at 25 ° by cooling. After a clear solution 14.06 g = 100 mmol of 4-chlorobenzaldehyde, dissolved in 30 ml of abs. Tetrahydrofuran, added dropwise, the temperature by cooling at 30 to Is held at 35 °. After the addition has ended, the mixture is left at room temperature for 15 minutes stirred, refluxed for 30 minutes, then under vacuum evaporated. The residue is shaken with methylene chloride / water, the organic phase washed again with water, dried and evaporated. The residue is recrystallized from toluene. Yield: 20.6 g (= 82%) of the title compound as crystals of mp. 140-141 ° C.
200 g eines E/Z-Isomerengemisches von 3-(3,4-Dimethoxy)-3-(4-Chlorphenyl)- acrylsäuremorpholid (E/Z-Isomerenverhältnis 76/24) erhältlich durch Wittig-Horner Reaktion ausgehend von 3,4-Dimethoxy-4′-chlorbenzophenon und Diethylphosphonoessigsäuremorpholid (analog zu den in der EP-A-1 20 321 beschriebenen Verfahren) werden in 650 ml Acetonitril bei Siedetemperatur 5 Stunden mit einer UV-Quarzlampe belichtet.200 g of an E / Z isomer mixture of 3- (3,4-dimethoxy) -3- (4-chlorophenyl) - acrylic acid morpholide (E / Z isomer ratio 76/24) available from Wittig-Horner reaction starting from 3,4-dimethoxy-4'-chlorobenzophenone and diethylphosphonoacetic acid morpholide (analogous to those in EP-A-1 20 321 described methods) are in 650 ml of acetonitrile at boiling temperature Exposed for 5 hours with a UV quartz lamp.
Nach dem Erkalten kristallisieren 59 g der Titelverbindung aus.After cooling, 59 g of the title compound crystallize out.
25 g eines E/Z-Isomerengemisches (E/Z = 76/24) der Titelverbindung (erhältlich wie in Beispiel 24 beschrieben) werden 5 Stunden in 200 ml Toluol unter p-Toluolsulfonsäurekatalyse (2,5 g) zum Sieden erhitzt. In der Lösung bestimmt man ein E/Z-Verhältnis von 50/50. Nach Ausschütteln der p-Toluolsulfonsäure und Abkühlen kristallisieren 9,5 g (38%) der Titelverbindung.25 g of an E / Z isomer mixture (E / Z = 76/24) of the title compound (obtainable as described in Example 24) are 5 hours in 200 ml Toluene heated to boiling under p-toluenesulfonic acid catalysis (2.5 g). In the solution has an E / Z ratio of 50/50. After shaking of p-toluenesulfonic acid and cooling crystallize 9.5 g (38%) of Title link.
Danach wird die Mutterlauge mit weiteren 10 g des Acrylsäuremorpholids (E/Z = 76/24) und 2,5 g p-Toluolsulfonsäure versetzt und erneut für 5 Stunden zum Sieden erhitzt.Then the mother liquor with a further 10 g of acrylic morpholide (E / Z = 76/24) and 2.5 g of p-toluenesulfonic acid were added and again for 5 Heated to boiling for hours.
Nach Abtrennen der p-Toluolsulfonsäure und Erkalten kristallisieren weitere 9,6 g der Titelverbindung in reiner Form.After separating the p-toluenesulfonic acid and cooling, crystallize another 9.6 g of the title compound in pure form.
Claims (22)
R1 für OH, OR2 oder NR3R4
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
R3 und R4 unabhängig voneinander für
- a) Wasserstoff
- b) C1-C6-Alkyl gewünschtenfalls ein- oder mehrfach substituiert durch Halogen, C1-C4 Alkoxy, Hydroxy
R 1 for OH, OR 2 or NR 3 R 4
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
R 3 and R 4 are independently for
- a) hydrogen
- b) C 1 -C 6 alkyl optionally substituted one or more times by halogen, C 1 -C 4 alkoxy, hydroxy
R3 und R4 gemeinsam mit dem Stickstoffatom ein ganz oder teilweise gesättigtes oder ungesättigtes heterocyclisches 4 bis 7 gliedriges Ringsystem bilden, welches bis zu 3 Heteroatome enthalten kann und welches gewünschtenfalls ein oder mehrfach durch
- a) C1-C4-Alkyl
- b) C1-C4-Alkoxy
- d) Hydroxy und/oder
- e) Oxo substituiert ist
R 3 and R 4 together with the nitrogen atom form a fully or partially saturated or unsaturated heterocyclic 4 to 7-membered ring system which can contain up to 3 heteroatoms and which, if desired, can be repeated one or more times
- a) C 1 -C 4 alkyl
- b) C 1 -C 4 alkoxy
- d) hydroxy and / or
- e) oxo is substituted
- a) Wasserstoff, Halogen, Amino, Mono- oder Di-C1-C4-Alkylamino C1-C4-Alkyl-CO-NH, Cyano oder Nitro
- b) C1-C4-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlor
- c) C1-C6-Alkyl, gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Hydroxy, Amino, Cyano, Carboxy, C1-C4-Alkoxy, C1-C4-Alkylthio C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoyl
- d) C1-C4-Alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor, C1-C4-Alkyl, Hydroxy, Cyano, Carboxy, Amino, C1-C4-Alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiert.
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiert
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituiert
- i) C1-C4-Alkylcarbonylamino, gewünschtenfalls wie vorstehend unter c) substituiert
- j) CHO oder C1-C4-Alkyl-O sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C6-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- und Arylhydrazone und -Oxime
- a) hydrogen, halogen, amino, mono- or di-C 1 -C 4 alkylamino C 1 -C 4 alkyl-CO-NH, cyano or nitro
- b) C 1 -C 4 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C 1 -C 6 alkyl, optionally substituted one or more times by fluorine, chlorine, hydroxy, amino, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio C 1 -C 4 - Alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, benzoyl
- d) C 1 -C 4 alkylthio
- e) phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl, hydroxy, cyano, carboxy, amino, C 1 -C 4 alkoxy
- f) phenoxy, if desired substituted as above under e).
- g) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, if desired substituted as above under e)
- i) C 1 -C 4 alkylcarbonylamino, if desired substituted as above under c)
- j) CHO or C 1 -C 4 alkyl-O and, if desired, their acetals or thioacetals with C 1 -C 6 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl and arylhydrazones and -Oxime
in der
R1 für OH, OR2 oder Morpholin
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
A für B für R5, R6 und R7 unabhängig voneinander für Wasserstoff, C1-C4- Alkyl, Amino, Chlor, Brom oder C1-C4-Alkoxy, Acetamido, C1-C4-Alkylthio C1-C4-Alkylthio-C1-C4-alkyl
die Substituenten R8 und R9 unabhängig voneinander für
- a) Wasserstoff, Fluor, Chlor, Brom, Cyano, Amino, Acetamido, Nitro
- b) C1-C6-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlor
- c) C1-C6-Alkyl, gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Hydroxy, Amino, C1-C4-Alkoxy, Phenyl, Carboxy, Cyano, Phenoxy, C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoyl
- d) C1-C4-Alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor, C1-C4-Alkyl, Hydroxy, Cyano, Carboxy, Amino, C1-C4-Alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiert
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiert
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituiert
- i) CHO oder C1-C4-Alkyl-CHO sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C6-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- undArylhydrazone
in the
R 1 for OH, OR 2 or morpholine
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
A for B for R 5 , R 6 and R 7 independently of one another are hydrogen, C 1 -C 4 -alkyl, amino, chlorine, bromine or C 1 -C 4 -alkoxy, acetamido, C 1 -C 4 -alkylthio C 1 -C 4 - Alkylthio-C 1 -C 4 alkyl
the substituents R 8 and R 9 independently of one another for
- a) Hydrogen, fluorine, chlorine, bromine, cyano, amino, acetamido, nitro
- b) C 1 -C 6 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C 1 -C 6 alkyl, optionally substituted one or more times by fluorine, chlorine, hydroxy, amino, C 1 -C 4 alkoxy, phenyl, carboxy, cyano, phenoxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, benzoyl
- d) C 1 -C 4 alkylthio
- e) phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 alkyl, hydroxy, cyano, carboxy, amino, C 1 -C 4 alkoxy
- f) phenoxy, if desired substituted as above under e)
- g) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, if desired substituted as above under e)
- i) CHO or C 1 -C 4 alkyl CHO and, if desired, their acetals or thioacetals with C 1 -C 6 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl and aryl hydrazones
3,4-Dimethoxyphenyl, 3-Methyl-4-methoxyphenyl, 3-Chlor-4-methoxyphenyl, 4-Methyl-3-methoxyphenyl, 3-Ethyl-4-methoxyphenyl, 3-Ethoxy-4- methoxyphenyl, 4-Ethoxy-3-methoxyphenyl, 4-Amino-3,5-dichlorphenyl, 4-Amino-3-methylphenyl, 3-Amino-4-methoxyphenyl, 3-Acetamido-4-methoxyphenyl, 3-n-Propyl-4-methoxyphenyl, 3,5-Dichlorphenyl, 3-Methylthiomethyl-4-methoxyphenyl, 3,4-Dimethylphenyl.
Und für den Ring B in Formel I:
4-Chlorphenyl, 4-Biphenyl, 4-Trifluormethylphenyl, 4-Hydroxyphenyl, 4-Aminophenyl, 4-Trifluormethoxyphenyl, 3-Biphenylyl, 4-Acetylphenyl, 4-Benzoylphenyl, 4-Difluormethoxyphenyl, 4-Ethylphenyl, 4-n-Propylphenyl, 4-n-Butylphenyl, 4-Formylphenyl, 4-(1,3-Dioxolan-2- yl)-phenyl, 4-(4-n-Propyl-1,3-dioxan-2-yl)-phenyl, 4-(1,3-Dithian-2- yl)-phenyl, 4-Bromphenyl
steht.3) Compounds according to claim 2 in which for ring A of formula I:
3,4-dimethoxyphenyl, 3-methyl-4-methoxyphenyl, 3-chloro-4-methoxyphenyl, 4-methyl-3-methoxyphenyl, 3-ethyl-4-methoxyphenyl, 3-ethoxy-4-methoxyphenyl, 4-ethoxy- 3-methoxyphenyl, 4-amino-3,5-dichlorophenyl, 4-amino-3-methylphenyl, 3-amino-4-methoxyphenyl, 3-acetamido-4-methoxyphenyl, 3-n-propyl-4-methoxyphenyl, 3, 5-dichlorophenyl, 3-methylthiomethyl-4-methoxyphenyl, 3,4-dimethylphenyl.
And for ring B in Formula I:
4-chlorophenyl, 4-biphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-aminophenyl, 4-trifluoromethoxyphenyl, 3-biphenylyl, 4-acetylphenyl, 4-benzoylphenyl, 4-difluoromethoxyphenyl, 4-ethylphenyl, 4-n-propyl 4-n-butylphenyl, 4-formylphenyl, 4- (1,3-dioxolan-2-yl) phenyl, 4- (4-n-propyl-1,3-dioxan-2-yl) phenyl, 4- (1,3-dithian-2-yl) phenyl, 4-bromophenyl
stands.
in der
R1 für OH, OR2 oder NR3R4
R2 für C1-C6-Alkyl, Phenyl oder Benzyl
R3 und R4 unabhängig voneinander für
- a) Wasserstoff
- b) C1-C6-Alkyl gewünschtenfalls ein- oder mehrfach substituiert durch Halogen, C1-C4 Alkoxy, Hydroxy
in the
R 1 for OH, OR 2 or NR 3 R 4
R 2 is C 1 -C 6 alkyl, phenyl or benzyl
R 3 and R 4 are independently for
- a) hydrogen
- b) C 1 -C 6 alkyl optionally substituted one or more times by halogen, C 1 -C 4 alkoxy, hydroxy
R3 und R4 gemeinsam mit dem Stickstoffatom ein ganz oder teilweise
gesättigtes oder ungesättigtes heterocyclisches 4 bis 7gliedriges Ringsystem bilden, welches bis zu 3 Heteroatome enthalten kann und welches gewünschtenfalls ein oder mehrfach durch
- a) C1-C4-Alkyl
- b) C1-C4-Alkoxy
- d) Hydroxy und/oder
- e) Oxo substituiert ist
R 3 and R 4 together with the nitrogen atom are all or part
Form saturated or unsaturated heterocyclic 4 to 7-membered ring system which can contain up to 3 heteroatoms and which, if desired, can be carried out one or more times
- a) C 1 -C 4 alkyl
- b) C 1 -C 4 alkoxy
- d) hydroxy and / or
- e) oxo is substituted
- a) Wasserstoff, Halogen, Amino, Mono- oder Di-C1-C4- Alkylamino, C1-C4-Alkyl-CO-NH, Cyano oder Nitro
- b) C1-C6-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor oder Chlor
- c) C1-C6-Alkoxy gewünschtenfalls ein- oder mehrfach substituiert durch Fluor, Chlor, Brom, Hydroxy, Amino, Cyano, Carboxy, C1-C4-Alkoxy, C1-C4-Alkylthio C1-C4-Alkoxy, Phenyl, Carboxy, Cyano, Phenoxy, C1-C4-Alkoxycarbonyl, C1-C4-Alkylcarbonyl, Benzoyl
- d) C1-C4-Alkylthio
- e) Phenyl, gewünschtenfalls substituiert durch Fluor, Chlor C1-C4-Alkyl Hydroxy, Cyano, Carboxy, Amino C1-C4-Alkoxy
- f) Phenoxy, gewünschtenfalls wie vorstehend unter e) substituiert
- g) C1-C4-Alkylcarbonyl, gewünschtenfalls wie vorstehend unter e) substituiert
- h) Benzoyl, gewünschtenfalls wie vorstehend unter e) substituiert
- i) C1-C4-Alkylcarbonylamino, gewünschtenfalls wie vorstehend unter c) substituiert
- j) CHO oder C1-C4-Alkyl-CHO sowie gewünschtenfalls deren Acetale bzw. Thioacetale mit C1-C6-Alkoholen, -Thiolen, -Diolen oder -Dithiolen sowie außerdem deren C1-C6-Alkyl- und Arylhydrazone und -Oxime
- a) hydrogen, halogen, amino, mono- or di-C 1 -C 4 - alkylamino, C 1 -C 4 alkyl-CO-NH, cyano or nitro
- b) C 1 -C 6 alkoxy, optionally substituted one or more times by fluorine or chlorine
- c) C 1 -C 6 alkoxy, if desired mono- or polysubstituted by fluorine, chlorine, bromine, hydroxy, amino, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio C 1 -C 4 Alkoxy, phenyl, carboxy, cyano, phenoxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyl, benzoyl
- d) C 1 -C 4 alkylthio
- e) phenyl, optionally substituted by fluorine, chlorine C 1 -C 4 -alkyl hydroxy, cyano, carboxy, amino C 1 -C 4 -alkoxy
- f) phenoxy, if desired substituted as above under e)
- g) C 1 -C 4 alkylcarbonyl, optionally substituted as above under e)
- h) Benzoyl, if desired substituted as above under e)
- i) C 1 -C 4 alkylcarbonylamino, if desired substituted as above under c)
- j) CHO or C 1 -C 4 alkyl CHO and, if desired, their acetals or thioacetals with C 1 -C 6 alcohols, thiols, diols or dithiols and also their C 1 -C 6 alkyl and arylhydrazones and -Oxime
dadurch gekennzeichnet, daß man ein Zimtsäurederivat der Formel ACH=CHCOR1,6(IIa)oder
ein Zimtsäurederivat der FormelBCH=CHCOR1,6(IIb)unter Pd-(0)-Katalyse mit einem Halogenid der Formel oder in der Hal für Chlor, Brom oder Jod vorzugsweise für Brom oder Jod steht, umsetzt.stands,
characterized in that a cinnamic acid derivative of the formula ACH = CHCOR 1 , 6 (IIa) or
a cinnamic acid derivative of the formula BCH = CHCOR 1 , 6 (IIb) under Pd (0) catalysis with a halide of the formula or Hal represents chlorine, bromine or iodine, preferably bromine or iodine.
- a) eine Verbindung der Formel Ia oder Ib in der R1 für OH steht mit
einer Verbindung der Formel
R3R4NH (VI)umsetzt, wobei man gewünschtenfalls in Gegenwart wasserbindender
Mittel arbeitet oder aber die als Edukt verwendete Säure mittels
an sich bekannter Verfahren in eine reaktive Form überführt und
danach mit VI umsetzt
oder - b) eine Verbindung der Formel Ia oder Ib, in der R1 für OR2 steht mit einer Verbindung der Formel VI nach an sich bekannten Verfahren umsetzt.
- a) a compound of the formula Ia or Ib in which R 1 is OH is reacted with a compound of the formula R 3 R 4 NH (VI), if desired working in the presence of water-binding agents or the acid used as starting material by means of known per se Process converted into a reactive form and then implemented with VI
or - b) a compound of the formula Ia or Ib in which R 1 is OR 2 is reacted with a compound of the formula VI by processes known per se.
- a) in der ersten Stufe ein Halogenbenzol der Formel IIIa mit einem Acrylsäurederivat der Formel VII zu einem Zimtsäurederivat der Formel IIa und
- b) in der zweiten Stufe das so erhaltene Zimtsäurederivat IIa mit
einem Halogenbenzol der Formel IIIb zu Ib umsetzt.
(IIIa) + (VII) → (IIa)
(IIa) + (IIIb) → (Ib)
- a) in the first stage a halobenzene of the formula IIIa with an acrylic acid derivative of the formula VII to a cinnamic acid derivative of the formula IIa and
- b) in the second stage, the cinnamic acid derivative IIa thus obtained is reacted with a halogenobenzene of the formula IIIb to give Ib. (IIIa) + (VII) → (IIa)
(IIa) + (IIIb) → (Ib)
- a) in der ersten Stufe ein Halogenbenzol der Formel IIIb mit einem Acrylsäurederivat der Formel VII zu einem Zimtsäurederivat der Formel IIb umsetzt und
- b) in der zweiten Stufe das so erhaltene Zimtsäurederivat IIb mit
einem Halogenbenzol der Formel IIIa zu Ia umsetzt.
(IIIb) + (VII) → (IIb)
(IIb) + (IIIa) → (Ia)
- a) in the first stage, a halogenobenzene of the formula IIIb is reacted with an acrylic acid derivative of the formula VII to give a cinnamic acid derivative of the formula IIb and
- b) in the second stage, the cinnamic acid derivative IIb thus obtained is reacted with a halogenobenzene of the formula IIIa to give Ia. (IIIb) + (VII) → (IIb)
(IIb) + (IIIa) → (Ia)
Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863615447 DE3615447A1 (en) | 1986-05-07 | 1986-05-07 | Novel E/Z isomeric, fungicidally active acrylic acid compounds, process for their preparation and intermediates for carrying out the process |
ES86113835T ES2061432T3 (en) | 1985-10-09 | 1986-10-06 | NEW ACRYLIC ACID AMIDES. |
EP86113835A EP0219756B1 (en) | 1985-10-09 | 1986-10-06 | Acrylic amides |
AT86113835T ATE99682T1 (en) | 1985-10-09 | 1986-10-06 | NEW ACRYLIC ACID EAMIDES. |
DE86113835T DE3689506D1 (en) | 1985-10-09 | 1986-10-06 | New acrylic acid amides. |
YU01725/86A YU172586A (en) | 1985-10-09 | 1986-10-07 | Process for preparing new amides of acrylic acid |
CS867259A CZ281649B6 (en) | 1985-10-09 | 1986-10-07 | Fungicidal agent and process for preparing active compounds |
PL1986261749A PL150836B1 (en) | 1985-10-09 | 1986-10-07 | Method of obtaining novel agrylamides |
BR8604917A BR8604917A (en) | 1985-10-09 | 1986-10-08 | COMPOUNDS, FUNGICIDED AGENTS, USE OF SUCH COMPOUNDS AND PROCESS FOR OBTAINING SUCH COMPOUNDS |
PT83504A PT83504B (en) | 1985-10-09 | 1986-10-08 | PROCESS FOR THE PREPARATION OF REPLACED ACRYLAMIDES |
AU63608/86A AU6360886A (en) | 1985-10-09 | 1986-10-08 | Acrylic acid amides |
NZ217845A NZ217845A (en) | 1985-10-09 | 1986-10-08 | Substituted acrylic acid amides and plant fungicidal composition |
FI864062A FI864062A (en) | 1985-10-09 | 1986-10-08 | NYA ACRYLSYRAAMIDER. |
IE265386A IE63475B1 (en) | 1985-10-09 | 1986-10-08 | Acrylic acid amides |
HU864222A HU206666B (en) | 1985-10-09 | 1986-10-08 | Process for producing acrylic amide sand fungicide compositions containing them as active components |
DK480286A DK480286A (en) | 1985-10-09 | 1986-10-08 | acrylic acid amides |
IL80257A IL80257A (en) | 1985-10-09 | 1986-10-08 | 3-phenyl-3-(3,4-dimethoxyphenyl)acrylic acid methyl ethylamides and morpholides,their preparation and fungicidal compositions containing them |
KR1019860008436A KR940009529B1 (en) | 1985-10-09 | 1986-10-08 | Process for preparing acrylic acid amide |
CA000520056A CA1290326C (en) | 1985-10-09 | 1986-10-08 | Acrylic acid amides |
JP61241130A JPH0772164B2 (en) | 1985-10-09 | 1986-10-09 | New acrylic acid amides |
US06/917,022 US4910200A (en) | 1985-10-09 | 1986-10-09 | Acrylic acid morpholides, fungicidal compositions and use |
AU65999/90A AU654470B2 (en) | 1985-10-09 | 1990-11-09 | Acrylic acid amides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863615447 DE3615447A1 (en) | 1986-05-07 | 1986-05-07 | Novel E/Z isomeric, fungicidally active acrylic acid compounds, process for their preparation and intermediates for carrying out the process |
Publications (1)
Publication Number | Publication Date |
---|---|
DE3615447A1 true DE3615447A1 (en) | 1987-11-12 |
Family
ID=6300343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19863615447 Withdrawn DE3615447A1 (en) | 1985-10-09 | 1986-05-07 | Novel E/Z isomeric, fungicidally active acrylic acid compounds, process for their preparation and intermediates for carrying out the process |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE3615447A1 (en) |
-
1986
- 1986-05-07 DE DE19863615447 patent/DE3615447A1/en not_active Withdrawn
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