IL89636A - Preparation of substituted 2,2-difluoro-1,3- benzodioxoles and certain such novel compounds - Google Patents
Preparation of substituted 2,2-difluoro-1,3- benzodioxoles and certain such novel compoundsInfo
- Publication number
- IL89636A IL89636A IL8963689A IL8963689A IL89636A IL 89636 A IL89636 A IL 89636A IL 8963689 A IL8963689 A IL 8963689A IL 8963689 A IL8963689 A IL 8963689A IL 89636 A IL89636 A IL 89636A
- Authority
- IL
- Israel
- Prior art keywords
- formula
- radical
- compound
- substituted
- unsubstituted
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims description 24
- DGCOGZQDAXUUBY-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole Chemical class C1=CC=C2OC(F)(F)OC2=C1 DGCOGZQDAXUUBY-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 33
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 125000006501 nitrophenyl group Chemical group 0.000 claims abstract description 22
- 125000006239 protecting group Chemical group 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 15
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 3
- 150000003254 radicals Chemical group 0.000 claims description 63
- -1 carboxylic acid lactam Chemical class 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 50
- 239000011541 reaction mixture Substances 0.000 claims description 19
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 229910001507 metal halide Inorganic materials 0.000 claims description 9
- 150000005309 metal halides Chemical class 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 5
- 102100027456 Cytochrome c oxidase subunit 2 Human genes 0.000 claims description 4
- 101000725401 Homo sapiens Cytochrome c oxidase subunit 2 Proteins 0.000 claims description 4
- 101000605127 Homo sapiens Prostaglandin G/H synthase 2 Proteins 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 4
- 239000003513 alkali Substances 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 150000004292 cyclic ethers Chemical class 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 150000003944 halohydrins Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 56
- 125000001207 fluorophenyl group Chemical group 0.000 abstract description 13
- 125000004802 cyanophenyl group Chemical group 0.000 abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 239000002917 insecticide Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 239000000417 fungicide Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000003641 microbiacidal effect Effects 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical compound C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101150041968 CDC13 gene Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- KTMGNAIGXYODKQ-UHFFFAOYSA-N ethyl 2-cyano-3-ethoxyprop-2-enoate Chemical compound CCOC=C(C#N)C(=O)OCC KTMGNAIGXYODKQ-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 3
- JSEIXLJMGSQUDY-UHFFFAOYSA-N 1-(2,2-difluoro-1,3-benzodioxol-4-yl)-2,2-dimethylpropan-1-ol Chemical compound CC(C)(C)C(O)C1=CC=CC2=C1OC(F)(F)O2 JSEIXLJMGSQUDY-UHFFFAOYSA-N 0.000 description 2
- 150000005246 3-cyanopyrroles Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229940124561 microbicide Drugs 0.000 description 2
- OYVXVLSZQHSNDK-UHFFFAOYSA-N n-methoxy-n-methylacetamide Chemical compound CON(C)C(C)=O OYVXVLSZQHSNDK-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- SQCHBHRTAXOVCH-UHFFFAOYSA-N (2,2-difluoro-1,3-benzodioxol-4-yl)-dimethoxyborane Chemical compound COB(OC)C1=CC=CC2=C1OC(F)(F)O2 SQCHBHRTAXOVCH-UHFFFAOYSA-N 0.000 description 1
- CZTFWGBAYFFJOK-UHFFFAOYSA-N (2,2-difluoro-1,3-benzodioxol-4-yl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=CC2=C1OC(F)(F)O2 CZTFWGBAYFFJOK-UHFFFAOYSA-N 0.000 description 1
- HUPVIAINOSTNBJ-HWKANZROSA-N (e)-3-ethoxyprop-2-enenitrile Chemical compound CCO\C=C\C#N HUPVIAINOSTNBJ-HWKANZROSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JZYKNIBCQRIYQP-UHFFFAOYSA-N 1-fluoroprop-1-yne Chemical compound CC#CF JZYKNIBCQRIYQP-UHFFFAOYSA-N 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- RXIKYXZKSIARLN-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxol-4-amine Chemical compound NC1=CC=CC2=C1OC(F)(F)O2 RXIKYXZKSIARLN-UHFFFAOYSA-N 0.000 description 1
- RZLKNZQTCHZQNT-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxol-4-ol Chemical compound OC1=CC=CC2=C1OC(F)(F)O2 RZLKNZQTCHZQNT-UHFFFAOYSA-N 0.000 description 1
- ZGAQVJDFFVTWJK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=C1OC(F)(F)O2 ZGAQVJDFFVTWJK-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- DBTWOTKWIVISQR-UHFFFAOYSA-N 2-bromopropan-1-ol Chemical compound CC(Br)CO DBTWOTKWIVISQR-UHFFFAOYSA-N 0.000 description 1
- XYFMKXAUKVXBTM-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl.OCCCl XYFMKXAUKVXBTM-UHFFFAOYSA-N 0.000 description 1
- WPYUCWSMVJJWFI-UHFFFAOYSA-N 2-ethoxyacetonitrile Chemical compound CCOCC#N WPYUCWSMVJJWFI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SIAUVSHCIQYVSI-UHFFFAOYSA-N 3-(2,2-difluoro-1,3-benzodioxol-4-yl)prop-2-enenitrile Chemical compound C1=CC(C=CC#N)=C2OC(F)(F)OC2=C1 SIAUVSHCIQYVSI-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- SZRHWHHXVXSGMT-UHFFFAOYSA-N 5-bromo-2,2-difluoro-1,3-benzodioxole Chemical compound C1=C(Br)C=C2OC(F)(F)OC2=C1 SZRHWHHXVXSGMT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000974482 Aricia saepiolus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZAMOIWKLADPRSK-UHFFFAOYSA-N FC1(F)Oc2cccc([K])c2O1 Chemical compound FC1(F)Oc2cccc([K])c2O1 ZAMOIWKLADPRSK-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-M bromoacetate Chemical compound [O-]C(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical group CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- MIMDWZINAQUQEF-RMKNXTFCSA-N ethyl (e)-2-cyano-3-(2,2-difluoro-1,3-benzodioxol-4-yl)prop-2-enoate Chemical compound CCOC(=O)C(\C#N)=C\C1=CC=CC2=C1OC(F)(F)O2 MIMDWZINAQUQEF-RMKNXTFCSA-N 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- UURRQOSQUBEJSP-UHFFFAOYSA-N ethyl 2-cyano-3-(4-methylphenyl)sulfonyloxyprop-2-enoate Chemical compound CCOC(=O)C(C#N)=COS(=O)(=O)C1=CC=C(C)C=C1 UURRQOSQUBEJSP-UHFFFAOYSA-N 0.000 description 1
- MVUMJYQUKKUOHO-UHFFFAOYSA-N ethyl 3-(dimethylamino)prop-2-enoate Chemical compound CCOC(=O)C=CN(C)C MVUMJYQUKKUOHO-UHFFFAOYSA-N 0.000 description 1
- PYENOQXWEQRZLD-UHFFFAOYSA-N ethyl 4-chlorobut-2-ynoate Chemical compound CCOC(=O)C#CCCl PYENOQXWEQRZLD-UHFFFAOYSA-N 0.000 description 1
- XCPXPFNKTCFWTA-UHFFFAOYSA-N ethyl carbonobromidate Chemical compound CCOC(Br)=O XCPXPFNKTCFWTA-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000006332 fluoro benzoyl group Chemical group 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000004009 herbicide Substances 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
- 125000004051 hexyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- FYXVHJJZGRTONS-UHFFFAOYSA-N methyl 2-cyano-3-ethoxyprop-2-enoate Chemical compound CCOC=C(C#N)C(=O)OC FYXVHJJZGRTONS-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
- FHVMATOIMUHQRC-UHFFFAOYSA-N n,n-dimethyl-2-phenylacetamide Chemical compound CN(C)C(=O)CC1=CC=CC=C1 FHVMATOIMUHQRC-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002347 octyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical class C(CCCC)* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- LNPDTQAFDNKSHK-UHFFFAOYSA-N valdecoxib Chemical group CC=1ON=C(C=2C=CC=CC=2)C=1C1=CC=C(S(N)(=O)=O)C=C1 LNPDTQAFDNKSHK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Indole Compounds (AREA)
Abstract
The reaction of 2,2-difluorobenzo-1,3-dioxol with (a) an alkali metal or an alkali metal compound and then with (b) a compound R<1>-Z<1> where Z<1> has the meaning of a leaving group, or an aldehyde, gives compounds of the formula I <IMAGE> in which R<1> represents -OH, -SH, -CHO, -CN, -COOH, -B(OH)2, -COX where X represents Cl or Br, furthermore -COOR<2>, -SiR@ or -B(OR<2>)2 where R<2> has the meaning of a C1-C12-alcohol radical minus the hydroxyl group, in which R1 furthermore represents -CnH2nCOOR<2> where n has the meaning of a number from 1 to 4, or linear or branched C1-C12-hydroxyalkyl which is unsubstituted or substituted by -F, -CN, C1-C6-alkoxy, phenyl, fluorophenyl, C1-C4-alkoxyphenyl, C1-C4-alkylthiophenyl, C1-C4-alkylphenyl, C1-C4-fluoroalkylphenyl, nitrophenyl or cyanophenyl, or in which R1 represents a benzyl alcohol which is unsubstituted or substituted by F, C1-4-alkoxy, -alkylthio, -alkyl, -fluoroalkyl, nitro or cyano, or is C1-C12-acyl, or in which R1 represents a radical of the formula II <IMAGE> in which R<5> represents -CN, -CF3, -COOR<2>, -CONH2, -CO-NHR<2> or -CONR@, R<3> and R<4> represent a direct bond or in each case represent H, or R<3> is H and R<4> independently has the meaning of R<5>, or R<3> and R<4> together represent -CH2-NR<6>-CH2-, -CH2-NR<6>-CO- or -CO-NR<6>-CO- where R<6> is the radical of a protective group which can be eliminated, or where, furthermore, R<1> represents a radical of the formula III <IMAGE> Insecticides or fungicides can be prepared from the compounds of the formula I.
Description
89636/2 "mamm cp inn in α-ί?ιορ κ-''τη ---3,ι- ι ιί>οΐ'τ-2,2 man ηί?ί niBTh tii ^ion Preparation of substituted 2,2-difluoro-l ,3-benzodioxoles and certain such novel compounds CIBA-GEIGY A.G.
C. 77064 The invention relates to a process for the preparation of 2 , 2-difluoro- benzo-1.3-dioxoles that are substituted in the 4-position, by reaction of 2 , 2-difluorobenzo-1 , 3-dioxole with an alkali metal or with an alkali metal or alkaline earth metal compound and subsequent reaction with an aldehyde or a compound having a leaving group, and to novel 2,2-di- fluorobenzo-1 , 3-dioxoles that are substituted in the 4-position.
EP-A-0 206 999 and Israel Patent 79167 describe unsubstituted or N-substituted 3-(2, 2-difluorobenzo-1 , 3-dioxol-4-y1) -4-cyanopyrroles which are valuable agents for controlling microorganisms. The compounds are prepared by a multi-stage synthesis. The 3-( 2 , 2-difluorobenzo-1 , 3-dioxol-4-yl)-2-propenoic acid nitrile which is required as starting material is obtained by diazotisa- tion of 4-amino-2, 2-difluorobenzo-1 , 3-dioxole, subsequent reaction with acrylonitrile in the presence of CuCl and dehalogenation of the resulting 4-( 2-chloro-2-cyano-eth-l-yl)-2 , 2-difluoroben2o-l , 3-dioxole . ( 2 , 2-Di- fluorobenzo-1, 3-dioxol-4-yl)-methyl esters of pyrethroid or pyrethroid- like carboxylic acids, for example, are described as insecticides in DE-OS 2 819 788 and Israel Patent 57192.
The benzodioxolylmethyl alcohols are in this case prepared by customary methods, for example with the reduction of aldehydes. 2 , 2-Difluorobenzo-1 , 3-dioxole-4-carbaldehyde , however, is not mentioned.
In J. Org. Chem. , Vol. 37, page 673 (1972), E.L. Stogryn describes the preparation of , 2-difluorobenzo-1 , 3-dioxole-5-carbaldehyde by formyla-tion of 2,2-difluorobenzo-l , 3-dioxol-5-yllithium with dimethy fornamide .
The lithium compound is obtained by reaction of 5-bromo-2 , 2-difluorobenzo-1 , 3-dioxole with butyllithium.
It has now been found that 2 , 2-difluorobenzo-1 , 3-dioxole that is free of halogen at the benzene nucleus can be reacted, with alkali metals or alkali metal or alkaline earth metal compounds directly and with high specificity with regard to position to give 2 , 2-difluorobenzo-1.3-dioxole metallated in the 4-position which can be reacted further with electro-philic compounds to give corresponding benzenes substituted in the A-position .
The present invention relates to a process for the preparation of compounds of formula I 89 wherein R1 is -OH, -SH, -CHO, -CN, -COOH, -B(OH)2, -COX, with X being CI or Br, or is -COOR2, -SiR^ or -B(0R2)2, with R2 being a Cj-C^alcohol 1 ? moiety without the hydroxy group, wherein is further -^l^COOR , with n being an integer from 1 to 4, or linear or branched C^-C^2hydroxy- alkyl or C^-C^2alkanoyl each being unsubstituted or substituted by -F, -CN, Cj-Cgalkoxy, phenyl, fluorophenyl, Cj-C^alkoxy-phenyl, Cj-C^- alk lthio-phenyl, C^-C^alkyl-phenyl, C^-C^fluoroalkyl-phenyl, nitrophenyl 9 ot kv cyanophenyl, or wherein R^ is a benzyl alcohol or a benzoyl radical each being unsubstituted or substituted by F, C^-C^alkoxy, C^-C^alkylthio, C^-C^alkyl, C^-C^fluoroalkyl, nitro or by cyano, or wherein R is a radical of formula II RJ R wherein R5 is -CN, -CF3, -COOR2, -C0NH2, -CO-NHR2 or -CONR^, R3 and R4 are a direct bond or each is H, or R is H and R independently has the meanings of R5, or R3 and R4 together are -CH2-NR6-CH2-, -CH2-NR6-CO- or -CO-NR^-CO- wherein R6 as the radical of a removable protecting group methyl, Cj-Cgtrialkylsilyl, -COOR , wherein IT is as defined above, or R7-CO- wherein R7 is C1-C11alk l, which is unsubstituted or is substituted by -F, -CN, C^-C^alkoxy, phenyl, fluorophenyl, Cj-C^- alkoxyphenyl, Cj-C^alkylphenyl, Cj-C^alkylthiophenyl, C^-C^fluoroalkyl- phenyl, nitrophenyl or by cyanophenyl, or R' is phenyl which is unsubstituted or is substituted by -F, cyano, nitro, Cj-C^alkyl, C^-C^alkoxy, C^-C^alkylthio or by Cj-C^fluoroalkyl, or wherein further is a radical of formula III which process comprises a) in an inert solvent, in the presence or absence of a complexing agent, reacting 2,2-difluorobenzo-l,3-dioxole with an alkali metal or with an alkali metal or alkaline earth metal compound with a strong anion base to give a compound of formula IV wherein Y is an alkali metal or an alkaline earth metal, and optionally then reacting with an anhydrous metal halide from the group MgZ2, ZnZz, CdZ2> CuZ, CuZi, PdZz, NiZ2 , A1Z3, SiZ , SnZi, SnZu , TiZu, BZ3 or ZrZ to give a compound of formula IV wherein Y is -Cu , -MgZ, -ZnZ, -CdZ, -CuZ, -PdZ, -NiZ, -AlZz, -SiZ3, -SnZ, -SnZ3 , -TiZj, -BZ2 or -ZrZj and Z is -Cl , -Br or -I and, in the case of boron, is also -OCi-Ci,alkyl or -O-aryl, b) reacting the group of formula IV with an electrophilic compound from the group X-CN, C02, S8, COX2, B(OR2)3, X-SiR^, R20-Si 3 or XCOOR2, with X being -Cl or -Br, or with a formylating reagent, C^O, an epoxide, a benzaldehyde which is unsubstituted or is substituted by F, Cj-C^alkoxy, C^C^alkylthio, - 3a - Cj-C^alkyl, C^-C^fluoroalkyl, nitro or by cyano, a Cj-Cj jalkyl-CHO which is unsubstituted or is substituted by -F, -CI, -rCN, C ■ C^alkox , phenyl, fluorophenyl, Cj-C^alkoxyphenyl, C^-C^alkylthiophenyl, Cj-C^alkylphenyl, C^-C^fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or with R^-CO-X^ wherein R^ is as defined above and wherein X^ is -CI, -Br, C^-C^alkoxy or the radical of a secondary amine, or with X2CnH2nCOOR2, X2-CR3=CR½5 or a compound of formula Ilia wherein X as a leaving group is halogen, C^-C^alkoxy, Cg-C ^aryloxy , C , -C^secondary amino, C^-Cgalk anoyloxy, benzoyloxy, or i<3 the radical of an aliphatic sulfonic acid or an aromatic sulfonic acid, and c) isolating the compound of formula I or first hydrolyzing ttie reaction mixture and then isolating the compound of formula I.
A preferred process is that for the preparation of compounds of formula I wherein R1 is -CHO, -CN, -COOH, -B(OH)2, -COX, with X being CI or Br, or is COOR2 or -B(OR2)2> with R2 being a C^C^alcohol moiety without the hydroxy 1 2 group, wherein R is further ~cnH2nC00R ' witn n being an integer from 1 to 4, or linear or branched C^-Cj^hydroxyalkyl or C^-C^alkanoyl each unsubstituted or substituted by -F, -CN, C^-C^alkoxy, phenyl, fluorophenyl, C^-C^alkoxyphenyl, C^-C^alkylthiophenyl, C^-C^alkylphenyl, C^-C^fluoroalkylphenyl , nitrophenyl or by cyanophenyl, or wherein R^" is benzoyl which is unsubstituted or substituted by F, C C^alkoxy, C C^alkylthio , C^-C^alkyl, Cj-C^fluoroalkyl, nitro or by cyano, or wherein R^ is a radical of formula II wherein R5 is -C , -CF3, -COOR2 , -CONH2 , -CO-NHR2 or -CONR¾ , R3 and R1* are a direct bond or each is H, or R3 is H and R independently has the meanings of Rs , or R3 and R* together are -CH2-NR6 -CH2- , -CH2-NRs-CO- or -CO-NR8-CO- wherein R6 is the radical of a removable protecting group as defined herein, or whether further R1 is a radical of formula III which process comprises a) in an inert solvent, in the presence or absence of a complexing agent , reacting 2,2-difluorobenzo-l,3-dioxole with an alkali metal or with an alkali metal or alkaline earth metal compound with a strong anion base to give a compound of formula IV (IV) - 5 - wherein Y is an alkali metal or an alkaline earth metal, and optionally then reacting with an anhydrous nietal halide from the group MgZ2 , nZ2 , CdZj, CuZ, CuZ2, PdZ2, NiZ2 , A1Z3 , SiZu , SnZ2, SnZ¾, ΤϊΖι», BZ3 or ZrZ*. to give a compound of formula IV wherein Y is -Cu, -MgZ, -ZnZ, -CdZ, -CuZ, -PdZ, -NiZ, -A1Z2, -S1Z3 , -SnZ, -SnZ3, -TiZ3, -BZ2 or -ZrZ3 and Z is -CI, -Br or -I and, in the case of boron, is also -0-C,-Ci,alkyl , b) reacting the compound of formula IV with an electrophilic compound III.89 from the group X-CN, C02 , B(OR2 ) 3 , COX2 or XCOOR2 , with X being -Cl or -Br, or with a formylating reagent, CH20, an epoxide, a C1-C1 ialkyl-CHO which is unsubstituted or is substituted by -F, -Cl, -CN, Ci-C6alkoxy, phenyl, fluorophenyl, Cj-Cualkoxyphenyl, Ci-Cit-alkylthiophenyl , Ci~C - alkylphenyl, Ci -Cufluoroalkylphenyl , nitrophenyl or by cyanophenyl, or with C1-C1 jacyl-X1 wherein X1 is -Cl, -Br, Cj-Csalkoxy or the radical of a secondary amine, or with X2 C H„ COOR2 , X2 -CR3 ^CR1* R5 or a compound of n 2n formula Ilia wherein X2 is a leaving group, and c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
A preferred process in this connection is considered to be that for the preparation of compounds of formula I wherein Rl is -CHO, -CN, -COOH, -COX, with X being Cl or Br, -COOR2, with R2 being a C1-C12alcohol moiety without the hydroxy group, wherein R1 is further -^i^COOR2, with n being an integer from 1 to 4, linear or branched C^-Cj^hydroxyalkyl unsubstituted or substituted by -F, -CN, C Cgalkoxy, phenyl, fluorophenyl, C^-C^alkoxyphenyl, C^C^alkylthiophenyl , Cj^-C^alkylphenyl, Cj-C^fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or R is R -CO- where R is as defined above, " or is a radical of formula II wherein R5 is -CN, -CF3 , -COOR* or -CONRz , R3 and R1* are a direct bond or each is H, or R3 is H and R* independently has the meanings of R5 , or t3 and R" together are -CH2-NR6 -CH2- , -CH2-NR6 -CO- or -CO-NR6 -CO- wher Rs is the radical of a removable protecting group, as defined above or wherein R is a radical of formula III which process comprises a) in an inert solvent, in the presence or absence of a complexing agent, reacting 2, 2-difluorobenzo-1 ,3-dioxole with an alkali metal or with an alkali metal compound with a strong anion base to give a compound of formula IV wherein Y is an alkali metal, and optionally then reacting with an anhydrous metal halide from the group MgZ2 , ZnZ2 , CdZ2, CuZ, CuZ2, PdZ2 , NiZ2, A1Z3, SiZ , SnZ2, SnZ.., TiZu or ZrZ., to give a compound of. formula IV wherein Y is -Cu , -Mg2, -ZnZ, -CdZ, -CuZ, -PdZ, -NiZ, -A1Z2 , -SiZi, -SnZ, -SnZi, -TiZj or -ZrZ3 and Z is -CI, -Br or -I, b) reacting the compound of formula IV with an electrophilic compound from the group X-CN , C02 , COX2 or XCOOR2 , with X being -CI or -Br, or with- a formylating reagent, a C 2 -C 12haloalcohol which is unsubsti.uced or is substituted by -F, -CN, Ci-C6alkoxy, phenyl, fluorophenyl, Ci-C,-alkoxyphenyl, Ci -Calkylthiophenyl , Ci -d.alkylphenyl , Ci-Cfluoroalkyl-phenyl, nitrophenyl or by cyanophenyl , CH20, a C1-C1 ialkyl-CHO which is unsubstituted or is substituted by -F , -CN , Ci-Csalkoxy, phenyl, fluorophenyl, Ci-Calkoxyphenyl, C 1 -C, a lkylthiophenyl , Ci -Chalkylphenyl , nitrophenyl or by cyanophenyl, an epoxide, a benzaldehyde which is unsubstituted or is substituted by -F, Cj-C^alkox , C^-C^alkylthio, C^-C^alkyl, C^-C^fluoroalkyl, nitro or by cyano", or with R^-CO-X1, wherein is as defined above and X1 is -CI, -Br, C"^-Cgalkoxy or the radical of a seconary amine, or with 2CnH2nCOOR2, X2-CR3=CR^R5 or a compound of formula Ilia wherein X2 is a leaving group, and c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
Also preferred is a process for the preparation of compounds of formula I wherein R1 is -CHO, -CN, -COOH, -COX, with X being CI or Br, or a radical of formula II wherein R5 is -CN, -CF3, -COOR2 or -CONH2, R3 and R* are a direct bond or each is H, or R3 is H and R1* independently has the meanings of R5 , or R3 and R1* together are -CH2-NR6-CO- wherein R6 is the radical of a removable protecting group as defined above, or wherein R^ is a radical of formula III which process comprises a) in an inert solvent in the presence or absence of a complexing agent, reacting 2,2-difluorobenzo-l,3-dioxole with an alkali metal or with an alkali metal compound with a strong anion base to give a compound of formula IV ( iv) - 8 - wherein Y is an alkali metal, and optionally then reacting with an anhydrous metal halide from the group M Z2 , ZnZ2 , CdZ2, CuZ, CuZz, PdZz , Νΐ ϊ, AIZ3, SiZ , SnZ2, SnZ , TiZt, , BZs or ZrZi, to give a compound of formula IV wherein Y is -Cu , -MgZ, -ZnZ, -CdZ, -CuZ, -PdZ, -NiZ, -AIZ2 , -SiZ3, -SnZ, -SnZj, -TiZj, -BZ2 or -ΖΓΖ3 and Z is -CI, -Br or -I, b) reacting the compound of formula IV with an electrophilic compound from the group X-CN, CC-2 or COX , with X being -Cl or -Br, a formylating reagent, Xz -CR3 =0 Rs or a compound of formula Ilia wherein X2 is a leaving group as defined above, and c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
Prominence is to be given in this connection to that variant for the preparation of compounds of formula I wherein R1 is -CHO or a radical of formula II wherein Rs is -CN, -COOR2 or -CONHz, each of R3 and R" is H, or R3 is H and R1* independently has the meanings of R5.
A preferred embodiment of the process is that in which, in formula I, R is -CHO or -COOR2, in formula II R3 and R1* are a direct bond and R5 is -CN, or R3 is H, R1* is -CN and R5 is -COOR2, -CONR¾ or -CN, or R3 and R together are -CH2-NR6 -CH2- , -CO-NR6 -CO- or -CH2-NR6-C0- and R5 is -CN, and R5 in formula III is -CN.
When R2 is an alcohol moiety without a hydroxy group it can be, for example, linear or branched alkyl having pref-erably from 1 to 12, especially from 1 to 6, carbon atoms, or unsubstituted or Cj-Cualkyl-substituted C5- or Cg-cycloalkyl or Cs~ or C6-cycloalkyl-C - or phenyl-C H„ wherein m is 0 or an integer from 1 to 4, especially 0, 1 - 9 - or 2. Examples are methyl, ethyl, the isomers of propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, methylcyclopentyl or methylcyclohexyl , (methyl- or ethyl-cyclohexyl)methyl , benzyl, methyl-or ethyl-benzyl, phenylethyl or (methylphenyl) ethyl .
When R1 is C H„ COOR2 , n is an integer from 1 to 4, especially 1 or 2. n -in The -cnH2n~ SrouP may De linear or branched. Examples of this group are methylene, ethylene, ethylidene, propylidene, 1,2- or 1 , 3-propylene , butylidene, 1,2-, 1 , 3- or 1 , 4-butylene .
When R1 is unsubstituted or substituted hydroxyalkyl , it contains preferably from 1 to 6, especially from 1 to , carbon atoms. The hydroxy group may be bonded to a primary, secondary or tertiary carbon atom.
Examples of hydroxyalkyl are hydroxymethyl, 1- or 2-hydroxyethyl , 1-, 2-or 3-hydroxyprop-l- or -2-yl, 1-, 2-, 3- or 4-hydroxybut-l- or -2-yl, hydroxypentyl, hydroxyhexyl, phenyl(hydroxymethyl) , l-phenyl-2-hydroxy-ethyl, fluorophenyl(hydroxymethyl) , l-methoxy-2-hydroxyeth-2-yl, 1,1,1-trifluoro-2-hydroxyethyl and cyanophenyl(hydroxymethyl) .
When R1 is unsubstituted or substituted acyl, it contains preferably from 1 to 6 and especially from 1 to A carbon atoms. The acyl radical may, for example, be one of formula R7-CO- wherein R7 is Ci-Cnalkyl, especially Ci-C6alkyl, which is unsubstituted or is substituted by -F, -CN, Ci-C$-alkoxy, phenyl, fluorophenyl, Ci-Ci,alkoxyphenyl, Ci-Ctialkylphenyl , Ci-C¾alkylthiophenyl , Ci-Cvfluoroalkylphenyl , nitrophenyl or by cyano-phenyl, or may be phenyl which is unsubstituted or is substituted by -F, cyano, nitro, Ci-Ci*alkyl, Ci-C<,alkoxy , Ci-Ci,alkylthio or by Ci-C^fluoro-alkyl. Examples are formyl, acetyl, fluoroacetyl , trifluoroacetyl, chlorodifluoroacetyl, propionyl, butyryl, benzoyl, phenylacetyl , 3-phenylpropionyl or fluorobenzoyl .
As the radical of a secondary amine, X1 contains preferably from 2 to 12, especially from 2 to 8, carbon atoms. The radical may correspond to the formula Rs R9 N- wherein R8 is Ci-C6alkyl or Ci-C6alkoxy and R9 is Ci-C6-alkyl, or R8 is and R9 is Ci-C6alkyl or has the meaning of R8 , or R8 and R9 together are tetra- or penta- methylene or tetra- or penta-methylene interrupted by -0- or by a group.
In a preferred embodiment, X1 is Ci-C,alkyl-l!r-OCi-C,alkyl, Ci-C,alkyl-J¾-CH2CH20-Ci-C¾-alkyl, (Ci-C,alkylOCH2CH2) 2N- or the radical of a 5- or 6-membered heterocyclic amine which may contain a further hetero atom from the group -0- and =N-Ci -C,alkyl . Examples are dimethyl- amino, diethylamino , methoxymethylamino , ethoxymethylamino , methyl- (methoxyethyl)amino , di ( methoxymethyl) amino , pyrrolidino, piperidino, tnorpholino and N-methylpiperazino .
R5 is preferably -CN, -CF3 , -C00R2 or -C0NH2 - The removable protecting group R6 may, ' for example, be Ci -Ci,alkoxymethyl , or phenoxymethyl which is unsubstitu- ted or substituted by Ci-C,alkyl or Ci-Ci,alkoxy . Suitable groups are also benzyl, diphenylmethyl and triphenylmethyl . In a preferred embodiment the protecting groups are trialkylsilyl groups having a total of from 1 to 18, preferably from 1 to 10, carbon atoms, R7-C0- wherein R7 is Cj-C^alkyl especially Cj-C^alkyl, groups or -COOR^ groups in which R has the meanings mentioned hereinbefore. T he trialkylsilyl group may be, for example, trimeth l' silyl, triethylsilyl, tri-n- or -iso-propylsilyl, tert.-butyldimeth lsilyl or 2 2 (1,1, 2, 2-te tramethylethyl) dimethylsllyl. In the group -C00R , R is preferably C^-Cgalkyl. Examples of these groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl.
The leaving group X2 is a halide, especially -CI or -Br, C^-Cgalkoxy, for example methoxy, ethoxy or propoxy, Cg-Cj^arylox , for example phenoxy or naphthoxy, C^-C ^-secondary amino, especially C^-Cg-secondary amino, for example dimethylamino, diethylamino, piperidino, C j-Cgalkano loxy , especially C^-C^alkanoyloxy, for example acetyloxy, benzoyloxy or the radical of a sulfonic acid which may be an aliphatic sulfonic acid, for example methyl-, ethyl- or propyl-sulfonic acid, or an aromatic sulfonic acid, for example benzene- or p-toluene-sulfonic acid. 2 , 2-Difluorobenzo-1 , 3-dioxole is known and can be obtained, for example, by fluorination of 2 , 2-dichlorobenzo-l , 3-dioxole . - 1 1 - Reaction step a) is carried out in an inert solvent, for example in a non-polar or polar aprotic solvent. Suitable solvents are aliphatic or aromatic hydrocarbons, ethers, tertiary amines, N-alkylated acid amides, lactams or cyclic ureas, sulfoxides, sulfones, nitriles, or mixtures thereof. Examples are pentane, isopentane, hexane, heptane, cyclohexane, methylcyclohexane , benzene, toluene, xylene, diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, tri-ethylamine, Ν,Η,Ν' ,Ν'-tetramethylethylenediamine , hexamethylphosphoric acid triamide, dimethylformamide , dimethylacetamide, N-methylpyrrolidone , ethylenedimethylurea, propylenedimethylurea , dimethyl sulfoxide, tetra-methylenesulfone , acetonitrile. Solvents that may at the same time be reactants in process step b) , such as, for example, carboxylic acid amides, are not added until process step b) and are then added in the form of an excess of those reactants.
The reaction temperature may preferably be from -1 50 to 1 50°C , especially from -100 to 80°C , in both process steps.
If non-polar or weakly polar solvents are employed, it is advantageous for the reaction mixture to contain, in addition, a complexing agent, for example in an amount of from 0.01 ol. % up to a 10-fold excess, based on the compound of formula IV. Such complexing agents may be, for example, tertiary amines or N-substituted acid amides, lactams or cyclic ureas, ethers or sulfoxides, such as those mentioned hereinbefore under solvents. Further suitable complexing agents are crovn ethers, such as, for example, 1 5-crown- 5 , 18-crown-6 , dibenzo-1 8-crown-6 , dicyclohexyl- 18-crown-6 , dibenzo-24-crown-8 or dicyclohexyl-2A-crown-8. Alkali metal halides, especially lithium, sodium and potassium halides, magnesium halide and copper halide are also suitable. Halide is preferably chloride, bromide and iodide.
Suitable alkali metals and alkaline earth metals, also in the alkali metal and alkaline earth metal compounds, for use in reaction step a) are, for example, Li, Na, K, Rb, Cs, Ca, Sr or Ea, with Li, Na and being preferred. The strongly basic anions may be, for example, linear or branched Ci-Cealkyl®, especially Ci-Ci,alkyie, Ce-Ci Η0Θ, Η2ΪϊΘ, ΗΘ, 12 - Ci-C6alko y , especially Ci-Cualkoxy , Ci-C6alkyl-NH , especially Ci-d.alkyl-NH0, or diCCi-CsalkyDN®, especially di(Ci-Ci*alkyl)N0, or diiCs-CscycloalkyDN0. In a preferred embodiment, the alkali metal is Li, Na or K and the alkali metal or alkaline earth metal compound is a Li-, Na-, K- , Ca-, Sr- or Ba-alkyl, -arylhydride , -amide or -alcoholate.
The metallation of 2 , 2-difluorobenzo-1 , 3-dioxole is effected in a manner known per se by reaction thereof with an alkali metal or with an alkali metal or alkaline earth metal compound in an inert solvent at preferably from 20 to -80°C . In this reaction, the alkali metal, for example in the form of a suspension, or the alkali metal or alkaline earth metal compound can be introduced into the reaction vessel first and the benzodioxole can be slowly added thereto. The procedure may also be reversed.
Reaction b) can be carried out directly after reaction step a). It is also possible, however, for the alkali metal or alkaline earth metal compound of formula IV to be reacted prior to reaction step b) with an anhydrous metal halide, for example M Z2, ZnZj, CdZ2, CuZ , CuZ2, PdZ2 , NiZ2, A1Z3, SiZi,, SnZ2, SnZi, , TiZi», BZ3 or ZrZi» wherein Z is CI, Br or I , especially CI or Br, to give a compound of formula IV wherein Y is -MgZ, -ZnZ, -CdZ, -CuZ, -PdZ, -NiZ, -AIZ2 , -SiZ3 , -SnZ, -SnZ3, -TiZ3, -BZ2 or -ZrZ3. Z is especially CI or Br. In this reaction, the metal halide can be added in solid form or in the form of a suspension in an inert solvent. The reaction temperature is preferably from 0 to -80°C.
The electrophilic compounds used in reaction step b) are known or can be prepared by known processes. A few examples are cyanogen chloride or bromide, carbon dioxide, carboxylic acid dichloride or dibromide, methyl chlorocarbonate, ethyl bromocarbonate ; formylating reagents preferably from the group Ci-C6alkoxymethyleneanilines , formyl halide, especially formyl chloride and bromide, formates having preferably from 1 to 6, especially from 1 to 4, carbon atoms in the alcohol moiety, for example methyl or ethyl formate, orthoformic acid esters having preferably from 1 to 6 carbon atoms in the alcohol moiety, N-disubstituted formamides having from 2 to 12 , preferably from 2 to 6 , carbon atoms and, optionally, -0- or N-Ci-Ci,alkyl groups in the amide radical, for example di- - 13 - methyl-, diethyl-, methyl-me hoxyformamide , formic acid morpholide or formic acid N-methylpiperazide ; formaldehyde, acetaldehyde , benzaldehyde , acetyl chloride or bromide, propionyl chloride, methyl acetate, ethyl propionate, dimethylacetamide , N-methyl-N-me hoxypropionic acid amide, ethyl benzoate, N ,N-dimethylphenylacetic acid amide, ethyl chloroacetate or bromoacetate , 2-chloro- or 2-bromo-ethanol, 2-chloro- or 2-bromo-propan-l-ol, 4-chlorobutan-l-ol , 3-chloro- or 3-bromo-propynoic acid nitrile, 1-chloro— or l-bromo-3, , 3-tri'fluoropropyne, ethyl 3-chloro-propynecarboxylate , ethoxyacetonitrile, l-ethoxy-3, 3, 3-trifluoroprop-1-ene, ethylene oxide, propylene oxide, ethyl β-dimethylaminoacrylate , β-ρ-toluenesulfonyloxyacrylonitrile, N ,N-dimethyl-B-chloroacrylic acid amide, β-ethoxy-acrylonitrile, β-ρ-toluenesulfonyloxy-a-cyanoacrylo-nitrile, ethyl N, N-dimethylaminomethylenecyanoacetate , a-trifluoro-methyl-fl-chloroacrylonitrile , ethyl ethoxymethylenecyanoacetate , ethyl p-toluenesulfonyloxymethylenecyanoacetate , Δ 3-l-acetyl-3-cyano-4-chloro-pyrroline , Δ 3-l-trimethylsilyl-3-cyano-4-tosyloxy-pyrrolin-2-one , l-acetyl-3-cyano-4-chloro-pyrrole , trimethyl borate, triphenyl borate, trimethylchlorosilane , diphenylmethylchlorosilane , sulfur. Formylating reagents are described by Olah et al. in Chem. Rev. 1987, 87_, page 671.
It may be of advantage to carry out reaction b) in the presence of Pd, Rh or Ru compounds.
The reaction temperature in step b) may, for example, be from -80°C to 100°C, preferably from -80°C to 50°C. The electrophilic compound may be added in solid form or in the form of a solution, it being possible for the solvent to be the same as or different from that used in reaction step a) .
The isolation of the compounds of formula 1 is carried out by methods that are known per se by distilling, crystallising or chromatographing the filtrate obtained after filtration of the reaction mixture. It is generally advantageous to hydrolyse the reaction mixture, for example with dilute mineral acids, such as, for example, hydrochloric acid or sulfuric acid. If the electrophilic compound is C02 , an aldehyde, an epoxide or a carboxylic acid amide or ester, salts will initially be - Informed which make hydrolysis necessary in order to isolate the compounds of formula I. The hydrolysis conditions are so selected that the protecting group is not split off.
The invention further relates to compounds of formula la 9 wherein R1 is -OH, -SH, -CHO, -COOH, -B(0H)2, -COBr, or is -COOR2, 2 2 2 -S1R3 or -B(ORi)2, with R^ being a Cj-C^alcohol moiety without the hydroxy group, wherein R1 is further -CnH2nC00R2, with n being an integer from 1 to 4, or linear or branched C^-C^hydroxyalkyl or C1-C12alk no l each being unsubstituted or substituted by -F, -CN, Cj-C^alkoxy, phenyl, fluorophenyl, Cj-C^alkoxyphenyl, Cj-C^alkylthio- phenyl, C C^alkylphenyl, C^C^fluoroalkyl-phenyl, nitrophenyl or by cyanophenyl, or wherein R is a benzyl alcohol or a benzoyl radical each being unsubstituted or , substituted by F, C^-C^alkoxy, Cj-C^alkylthio, C^-C^alkyl, Cj-C^fluoroalkyl , nitro or by cyano, or wherein R1 is a radical of formula II wherein R5 is -CN, -CF3, -COOR2 , -C0NH2 , -CO-NHR2 or -CONRz , R3 and R" are a direct bond or each is H, or R3 is H and R* independently has the meanings of R5 , or R3 and R1* together are -CH2-NR5 -CH2-, -CH2-NR6-CO- or -CO-NR6-CO- wherein R^ as the radical of a removable protecting group is C^-C^alkoxymeth l, phenoxyme hyl which is unsubstituted or substituted by Cj-C^alkyl or Cj-C^alkoxy, or is benzyl, diphenylmethyl, triphenylmeth l, Cj-Cgtrialkylsilyl, R7-CO-, wherein R7 is defined as above, or is -COOR2, wherein R2 is defined as above, or wherein further R is a radical of formula III with the proviso that in formula III is not -CN, and with the further proviso, that R in formula II is not -CN, if R and R are both H. 1 6 1 2 The preferred meanings indicted hereinbefore for R to R , X and X also apply here.
Among these compounds, there are preferred those in which R1 is -CHO, -COOH, -B(OH)2, -COBr, or is -COOR2 or -3(0R2)2, with R2 being a C^-Cj^alcohol moiety without the hydroxy group, wherein ^ is 2 further -CnI-2nC0O , with n being an integer from 1 to 4, or linear or branched C^-C^hydroxyalkyl or Cj-C^alkanoyl each being unsubstituted or substituted by -F, -CN, C^Cgalkoxy, phenyl, fluorophenyl, Cj^-C^- alkoxyphenyl, Cj-C^alkylthiophenyl, C^-C^alkylphenyl , C^-C^fluoroalkyl- phenyl, nitrophenyl or by cyanophenyl, -or wherein R^ is benzoyl radical unsubstituted or substituted by F, Cj-C^alkoxy, C -Chalkylthio , C^-C^alkyl, C^-C^fluorqalkyl, nitro or by cyano, or wherein R^ is a radical of formula II -rr <">· wherein R5 is -CN, -CFj , -COOR2 , -CONHz, -CO-NHR2 or -CONR¾ , R3 and R" are a direct bond or each is H, or R3 is H and R"1 independently has the meanings of R5 , or RJ and R1* together are -CH2-NR6 -CH2- , -CH2~NR6-CO- or -CO-NR5 -CO- wherein R6 , is the radical of a removable protecting group, as defined above, or wherein further R^" is a radical of formula III with the proviso that R^ in formula III is not -CN, and with the further proviso, that R5 in formula II is not -CN, if R3 and ^ are both H. - a - Preferred compounds of formula la are those in which R1 is -C , -CHO, -COOH, -COOR2 , and R2 is an alcohol moiety without a hydroxy group, or R1 is -C H„ COOR2 , with n being an integer from 1 to 4, or is a radical of n 2n formula II wherein each of R3 and R* is H and Rs is -C , -CF3, -CONR¾ or -COOR2 , or wherein R5 is -CN, -CF3, -COOR2 or -CONR¾ , R3 and R1* are a direct bond, or R3 is H and R" independently has the meanings of R5 , or R3 and R" together are -CH2-NR6 -CH2- , -CH2-NR6-CO- or -CO-NR6 -CO- wherein is the radical of a removable protecting group as defined above, or wherein R-'' is a radical of formula III, with the proviso that in formula III is not -CN, and with the further proviso, that in formula II is not -CN, if R^ and are both H.
The preferred meanings indicated hereinbefore for R^ to R^, and X2 also apply here.
Another preferred embodiment is that in which, in formula la, R1 is -CHO or -COOR2 or is a radical of formula II wherein R3 and R1* are a bond and R5 is -CN, or R3 is H, R* independently has the meanings of R5 and R5 is -CN, -COOR2 or -CONR¾ , or R3 and R" together are -CH2-NR6 -CH2- , -CO-NR6-CO- or -CH2-NR6-CO- wherein R6 s as def ned above and R5 is -CN.
R2 is preferably a C^Cgalkyl radical. The protecting group R6 is preferably a trialkylsilyl protecting group having a total of from 1 to 18 carbon 7 7 2 atoms, a R -CO- group wherein R is as defined above or a -COOR group.
Using the process of the invention, the compounds of formula I are obtained in high yield and purity whilst, in particular, position isomers are not formed or are formed only to an insignificant extent.
The compounds of formulae I and la are suitable for the preparation of insecticides and mic robicides . The carboxylic acids and carboxylic acid derivatives, aldehydes and ketones can be reduced by customary methods of reduction to the corresponding alcohols. From the alcohols it is possible to prepare with pyrethroid or pyrethroid-like carboxylic acids insectici- dal esters, such as those described in DE-OS 2 819 788 (Example 1) and Israel Patent 57192.
Compounds of formula I are furthermore used as intermediates for valuable herbicides of the sulfonylurea class, such as, for example, those described in European Application Publication No. 99 339 and Israel Patents 69225 and 81912.
Compounds in which R1 is -CN , -COOH , COX and COOR2 can be converted by customary methods into the aldehyde group. From the aldehydes of formula I it is possible to prepare by the process described in EP-A-0 206 999 (Example 1) the microbicidal 3-cyanopyr roles described therein.
In compounds having radicals of formulae II and III, the -CF3- group can be converted by the process described in US-A-4 705 801 into the nitrile group. The conversion of ester and amide groups into nitrile groups is known, as is the hydrogenation of acetylenes to ethylenes. By using the known methods, it is possible to obtain compounds of formula I in which the group R1 is -CH=CRlt , wherein R1* is H, -CN or -C00R! and R5 is -CN or -COOR2. These compounds are intermediates for the microbicides whose preparation using these intermediates is described in EP-A-0 206 999 and Israel Patents 79167 and 92109.
The mentioned msthods for conversion into the nitrile group and the dehydro-genation of compounds of formula I wherein R3 and R1* together are -CHj-NR6 -CH2- or -CH2-NR&-C0- also result in the microbicidal 3-cyano-pyrroles mentioned. Compounds having the radical of formula III are themselves these 3-c anopyr roles (Rs is -CN) or can be converted into - 17 - them, as mentioned, by known methods (R5 is -CF3, -CO0R2 or -CONRI). Methods of removing the protecting group. R6 are widely described in the literature .
The following Examples illustrate the invention in detail.
Example 1 : Preparation of 4-( tri luoroacetyl)-2 , 2-difluoro-1 , 3-benzodi- oxole In a 250 ml 3-necked flask under argon, 7.9 g (50 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole are dissolved in a mixture of 30 ml of tetrahydrofuran and 30 ml of diethyl ether and, at -70°C, AO ml (55 mmol) of tert.-butyllithium (1.39M in pentane) are added dropwise thereto over a period of 20 minutes. When the dropwise addition is complete, the yellow suspension is maintained at -70°C for 40 minutes. There is then added dropwise at that temperature, over a period of 10 minutes, a solution of 9.8 g (50 mmol) of α,α,α-trifluoroacetyl-N-methylpiperazide in 20 ml of diethyl ether. The turbid solution is then allowed to warm up to 0°C and is hydrolysed with 30 ml of 2N hydrochloric acid. The aqueous phase is separated off and extracted twice with 60 ml of diethyl ether each time. The organic solutions are washed once with 50 ml of 2N HC1 and once with 50 ml of H^O, dried over MgSOu and concentrated in a vacuum rotary evaporator. Upon distillation of the residue, 9.1 g (72 ) of the product distil over in the form of a colourless liquid at boiling point (b.p.) 108-110°C/40 mbar. 1 H-NMR (CDCI3 ; 300 MHz): 7.62 (d x d; J 7.9; 1.5; 1H); 7.29 (d x d; J 7.9; 1.5; 1H) ; 7.16 (t; J 7.9; 1H).
Example 2 : Preparation of 2 , 2-difluoro-1 , 3-benzodioxole-4-carbaldehyde a) Under nitrogen, 69 ml (110 mmol) of n-butyllithium (1.60M in hexane) are introduced into a 500 ml 3-necked flask and, while cooling with ice/sodium chloride, a solution of 13 g (110 mmol) of N, N, N ' , ' -tetra-methylethylenediamine (TMEDA) in 30 ml of hexane is added thereto over a period of 15 minutes. To the clear, pale yellow solution, 15.8 g (100 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole dissolved in 120 ml of hexane are added dropwise, at -10°C, over a period of 30 minutes, during which 2 , 2-difluoro-1 , 3-benzodioxol-4-yllithium gradually separates in the form of a voluminous precipitate. After stirring vigorously at -10°C for minutes, 20 ml (260 mmol) of dimethylformamide (DMF) are added to the white suspension. The oily reaction mixture is stirred at -10°C for 15 minutes and is then hydrolysed with 50 ml of 10 % hydrochloric acid. The aqueous phase is separated off and extracted twice with 100 ml of diethyl ether each time. The organic solutions are washed three times with 40 ml of IN HC1 each time, dried over MgSO and concentrated in a vacuum rotary evaporator at 50°C/200 mbar. Distillation yields 16.8 g (90 %) of colourless product of boiling point (b.p.) lOS-l mbar. b) The procedure of Example 3 is followed except that dimethylformamide is used instead of N-methyl-N-methoxy-acetamide . 2 , 2-Difluoro-1 , 3-benzodioxole-4-carbaldehyde is obtained in a yield of 73 %. c) 94.0 g (272 mmol) of n-butyllithium (18.5 % in toluene) are added dropwise under a nitrogen atmosphere, at from -15° to -10°C, over a period of 1.5 hours, to 29.5 g (254 mmol) of Ν,Ν,Ν' ,Ν'-tetramethyl-ethylenediamine and 40.0 g (253 mmol) of 2 ,2-difluoro-1 , 3-benzodioxole in 35 ml of toluene, an orange suspension being formed. 19.7 g (270 mmol) of DMF are then metered in at from -15° to -10°C over a period of hour. The pale yellow suspension is poured at +10°C onto 346 g (1.105 mol) of 11.6 % aqueous hydrochloric acid and the whole is stirred for hour to complete the reaction. The aqueous phase is separated off and the organic phase is concentrated by evaporation in a vacuum rotary evaporator at 50°C/200 mbar under nitrogen to yield the desired product. d) 39.3 g (339 mmol) of Ν,Ν,Ν' ,Ν'-tetramethylethylenediamine are added dropwise at from -15° to -10°C under a nitrogen atmosphere to 137.8 g (409 mmol) of n-butyllithium solution (19.0 % in toluene). The resulting reaction mixture is metered into a solution of 53.3 g (337 mmol) of 2 ,2-difluoro-1 , 3-benzodioxole in 46 ml of toluene over a period of 3 hours at from -15° to -10°C under a nitrogen atmosphere. 30 g (410 mmol) of Ν,Ν-dimethylformamide are then added over a period of hour at from -15° to -10°C. The resulting solution is poured onto 461.1 g (1.472 mol) of 11.6 % aqueous hydrochloric acid and the whole is stirred for -J hour to complete the reaction. The aqueous phase is - 19 - separated off and the organic phase is concentrated by evaporation in a vacuum rotary evaporator at 50°C/200 mbar under nitrogen to yield the desired aldehyde. 1H-NMR ( CDCI3 ; 300 MHz): 10.20 (s; 1H) ; 7.58 (d x d; J 7.9; 1.5; 1H); 7.34 (d x d; J 7.9; 1.5; 1H); 7.23 (t; J 7.9; 1H).
Example 3: Preparation of 4-acetyl-2 , 2-difluoro-1 , 3-ben2odioxole 6.2 g (55 mol) of potassium tert . -butoxide dissolved in 40 ml of tetrahydrofuran (THF) are added drop ise at -30°C under argon, over a period of 20 minutes, to a solution of 8.0 g (50 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole in 10 ml of THF in a 250 ml 3-necked flask. The mixture is then cooled to -90°C (methanol/liquid nitrogen), and 35 ml (55 mmol) of n-butyllithium (1.58M in hexane) are added thereto over a period of 30 minutes. The deep red solution of 2 , 2-difluoro-1 , 3-benzodioxol-4-yl-potassium is maintained at -78°C for 20 minutes. Then, 5.2 g (50 mmol) of N-methyl-N-methoxy-acetamide in 20 ml of THF are added thereto over a period of 15 minutes at -78°C. When the dropwise addition is complete, the beige reaction mixture is allowed to warm up to -10°C and is then hydrolysed with 40 ml of 10 % hydrochloric acid. The hydrolysed mixture is extracted three times with 70 ml of diethyl ether each time. The organic solutions are washed three times with 30 ml of IN HCl each time, dried over Na2S0it and concentrated in a vacuum rotary evaporator. Upon distillation of the residue, 7.1 g (79 %) of the product distil over in the form of a colourless oil at boiling point (b.p.) 114-116°C/30 mbar. 1 H-NMR (CDCI ; 300 MHz): 7.65 (d x d; J 7.9; 1.5; 1H); 7.27 (d x d; J 7.9; 1.5; 1H) ; 7.18 (t; J 7.9; 1H) ; 2.68 (s; 3H).
Example 4: Preparation of 2 , 2-dimethyl-l-(2 , 2-difluoro-1 , 3-benzodioxol- 4-yl)-propan-l-ol a) 23.7 ml (33 mmol) of tert . -butyllithium (1.4M in pentane) are added dropwise at -60°C under argon, over a period of 20 minutes, to a solution of 4.75 g (30 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole in 20 ml of tetrahydrofuran (THF) and 15 ml of diethyl ether in a 250 ml 3-necked flask. The yellow, turbid solution is subsequently maintained at -65°C for minutes and then a fine suspension of 6.45 g (35 mmol) of anhydrous magnesium bromide in 35 ml of THF (prepared from 1 , 2-dibromoe hane and magnesium in THF) is added thereto over a period of 10 minutes. The greenish-blue solution is allowed to warm up to 0°C and then 2.6 g (30 mmol) of pivalaldehyde dissolved in 10 ml of THF are added dropwise thereto. After stirring for 30 minutes at 25°C, the colourless reaction mixture is hydrolysed with 30 ml of 10 % hydrochloric acid. The aqueous phase is separated off and extracted twice with 50 ml of diethyl ether each time. The organic solutions are washed once with 30 ml of 2N HCl and once with 30 ml of ΗΪΟ, dried over MgSOu and concentrated in a vacuum rotary evaporator. The crystalline yellow residue is recrystallised from hexane to yield 5.1 g (70 %) of colourless platelets of melting point (m.p,) 68-69°C. b) The procedure of Example 1 is followed except that pivalaldehyde is used instead of trifluoroacetyl-N-methylpiperazide . 2 , 2-Dimethyl-l-(2 , 2-difluoro-1 , 3-benzodioxol-4-yl)-propan-l-ol is obtained in a yield of 81 . 1 H-NMR (CDC13; 300 MHz): 7.13 (d x d x d; J 8.0; 1.5; 0.5; 1H) ; 7.07 (t; J 8.0; 1H); 6.97 (d x d; J 8.0; 1.5; 1H); 4.63 (s; 1H); 2.05 (bs; OH); 0.95 (s; 9H) .
Example 5: Preparation of (E)-2-cyano-3-(2 , 2-difluoro-1 , 3-benzodioxol- 4-yl)-2-propenoic acid ethyl ester a) 7.9 g (50 mmol) of 2, 2-difluoro-1 , 3-benzodioxole are metallated according to Example 2 at -15°C with 35 ml (55 mmol) of n-butyllithium (1.60M in hexane) and 6.5 g (55 mmol) of TMEDA in 60 ml of hexane. To the 2 ,"2-difluoro-1 , 3-benzodioxol-4-yllithium which precipitates there is added at -20°C, over a period of 30 minutes, a solution of 9.3 g (55 mmol) of ethoxymethylenecyanoacetic acid ethyl ester in 30 ml of tetrahydrofuran , an orange-red turbid solution being formed during the reaction, which is exothermic. After stirring for 20 minutes at -15°C, the solution is hydrolysed with 50 ml of 2N hydrochloric acid. The aqueous phase is extracted twice with 80 ml of diethyl ether each time. The organic solutions are washed twice with 50 ml of water each time, - 21 - dried over MgSOi» and concentrated to dryness by evaporation in a vacuum rotary evaporator. The residue is crystallised from ethanol/water 4:1, affording 10.1 g ( 72 %) of colourless platelets of m.p. 87-88°C. b) 40.0 g (253 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole in 29.5 g (254 mmol) of TMEDA and 35 ml of toluene are metallated analogously to Example 2c) at from -15 to -10°C with 106.2 g (307 mmol) of n-butyl-lithium solution (18.5 % in toluene). 52.1 g (308 mmol) of ethoxy-methylenecyanoacetic acid ethyl ester in 115 ml of toluene are added to the reaction mixture at from -15 to -10°C over a period of 2 hours. The resulting suspension is poured, after 20 minutes at +10°C, into 350 ml of water, the aqueous phase is separated off and the organic phase is concentrated by evaporation in a vacuum rotary evaporator to yield the desired product. c) 53.3 g (337 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole in 46 ml of toluene are metallated according to Example 2d), at from -15 to -10°C, with 137.8 g (409 mmol) of n-butyllithium solution (19.0 % in toluene) in the presence of 39.3 g (339 mmol) of TMEDA. 69.1 g (409 mmol) of ethoxy-methylenecyanoacetic acid methyl ester in 150 ml of toluene are metered in at from -15 to -10°C over a period of 2^ hours. The reaction mixture is added at +10°C to 450 ml of water, the phases are separated and the organic phase is concentrated by evaporation in a vacuum rotary evaporator to yield the title compound. 1 H-NMR (CDC13; 300 MHz) : 8.35 (s; 1H) , 8.10 (m; X of ABX; 1H); 7.25 (m; AB of ABX; 2H); 4.42 (a; J 7.0; 2H) ; 1.42 (t; J; 7.0; 3H).
Example 6: The procedure of Example 4 is followed except that β-ρ-toluenesulfonyloxyacrylonitrile is used instead of pivalaldehyde . β-(2 ,2-Difluoro-1 , 3-benzodioxol-4-yl)acrylonitrile is obtained in a yield of 52 %.
Example 7 : The procedure of Example 1 is followed except that CO? is passed in instead of adding trifluoroacetyl-N-methylpiperazide . 2,2-Di-fluoro-1 , 3-benzodioxole-4-carboxylic acid is obtained in a yield of 61 %.
Example 8 : Preparation of 4-hydroxy-2 , 2-difluoro-1 , 3-benzodioxole .8 g (100 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole are metallated according to Example 2, at -20°C, with 70 ml (110 mmol) of n-butyllithium (1.58M in hexane) and 12.8 g (110 mmol) of TMEDA in 120 ml of hexane. To the white suspension there is added dropwise at -100°C, over a period of 5 minutes, a solution of 10.4 g (100 mmol) of trimethyl borate in 50 ml of diethyl ether. When the reaction mixture has warmed up and has been stirred for 30 minutes at room temperature, there are added to the precipitated dimethoxy-( 2 , 2-difluoro-1 , 3-benzodioxol-4-yl)borane, while cooling with ice, 35 ml of 3N sodium hydroxide solution, immediately followed by the addition, over a period of 10 minutes, of 32 ml (~ 310 mmol) of 30 % hydrogen peroxide solution. The yellow-orange emulsion is adjusted to pH 3 with 10 % HC1. The aqueous phase is extracted three times with 150 ml of diethyl ether each time. The organic solutions are washed three times with 100 ml of 2N EeSOi, solution each time, then twice with 100 ml of 20 % sodium bisulfite solution each time and finally with 50 ml of brine, dried over MgSOi* and concentrated in a vacuum rotary evaporator. Upon distillation of the residue, 8.4 g (48 %) of the product distil over in the form of a pale yellow oil at boiling point (b.p.) 135-139°C/25 bar.
!H- MR (CDC13; 300 MHz): 6.93 (t; J 8.1; 1H) ; 6.67 (d x d; J 8.1; 1.0; 1H); 6.64 (d x d; J 8.1; 1.0; 1H); 6.15 Example 9 ; Preparation of 2 , 2-djfluoro-1 , 3-benzodioxole-4-boric acid 7.9 g (50 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole are metallated according to Example 1, at -70°C, with 40 ml of tert .-butyllithium (1.38M in pentane) in a mixture of 55 ml of diethyl ether and 30 ml of ΤΗΓ. 5.1 g (50 mmol) of trimethyl borate in 25 ml of diethyl ether are then added to the aryllithium compound at -100°C over a period of 2 minutes. The clear, yellow reaction solution is then allowed to warm up to room temperature and, after being stirred for 30 minutes while cooling with ice, is - 23 - hydrolysed with 100 ml of 2N HC1. The aqueous phase is extracted three times with 75 ml of diethyl ether each time. The organic solutions are washed neutral with water and brine and, without being dried, are concentrated in a vacuum rotary evaporator. The yellow crystalline residue is recrystallised from petroleum ether. 7.4 g (73 %) of pale yellow prisms of melting point (m.p.) 103-104°C are obtained. 1 H-NMR (CDCI3 ; 300 MHz): 7.51 (m; X of ABX; 1H) ; 7.18 ( ; AB of ABX; 2H) ; .33 (bs; 2 x OH).
Example 10: Preparation of 2 , 2-difluoro-1 , 3-benzodioxole-4-thio1 4.8 g (30 mmol) of 2 , 2-difluoro-1 , 3-benzodioxole are metallated as described in Example 1 with 24 ml (33 mmol) of ter .-butyllithium (1.38M in pentane) in a mixture of 35 ml of THF and 15 ml of diethyl ether. 1.1 g (34 mmol) of sulfur (SB) are then added in portions, at -30°C, over a period of 10 minutes. The orange reaction solution is subsequently maintained at -30°C for a further 20 minutes and is then hydrolysed with 30 ml of 2N HCl. The aqueous phase is extracted twice with 50 ml of diethyl ether each time. The organic phases are washed neutral with water and brine, dried over M SOit and concentrated in a vacuum rotary evaporator. Fractional distillation of the residue yields 3.4 g (60 %) of colourless product of boiling point (b.p.) 72-74°C/20 mbar. 1 H-NMR (CDCI3; 60 MHz): 6.85 (m; 3H) ; 3.49 (s, SH) .
Example 11; The procedure of Example 1 is followed except that trimethyl- chlorosilane is used instead of trifluoroacetyl-N-methylpiperazide . 4-Trimethylsilyl-2, 2-difluoro-1 , 3-benzodioxole (b.p. 80-81°C/160 mbar) is oDtained in a yield of 73 %. 1 H-NMR (CDClj ; 300 MHz): 7.09 (m; X of ABX); 7.05 (m; AB of ABX; 2H) ; 0.33 (s; 9H).
Claims (1)
1. 24 CLAIMS A process for the preparation of compounds of formula I wherein is with X being CI or or is or with R2 being a moiety without the hydroxy wherein R with n being an integer from 1 to or linear or branched alkyl or C each being unsubstituted or substituted by nitrophenyl or by or wherein is a benzyl alcohol or a benzoyl radical each being unsubstituted or substituted by nitro or by or wherein R is a radical of formula II wherein R5 is or R3 and are a direct bond or each is or R is H and R independently has the meanings of or R3 and together are or wherein as the radical of a removable protecting group is phenoxymethyl which is unsubstituted or substituted by or or is C wherein R2 is as defined or wherein is which is unsubstituted or is substituted by 25 nitrophenyl or by or is phenyl which is unsubstituted or is substituted by or by or wherein further is a radical of formula which process comprises in an inert in the presence or absence of a complexing reacting with an alkali metal or with an alkali metal or alkaline earth metal compound with a strong anion base to give a compound of formula IV wherein Y is an alkali metal or an alkaline earth and optionally then reacting with an anhydrous metal halide from the group or ZrZ to give a compound of formula IV wherein Y is or and Z is or in the case of is also or reacting the group of formula IV with an electrophilic compound from the group or with X being or or with a formylating an a benzaldehyde which is unsubstituted or is substituted by nitro or by a which is unsubstituted or is substituted by nitrophenyl or by or with wherein is as defined above and wherein is or a secondary amine 26 or with X or a compound of formula wherein X as a leaving group is or is the radical of an aliphatic sulfonic acid or an aromatic sulfonic and isolating the compound of formula I or first hydrolyzing the reaction mixture and then isolating the compound of formula A process for the preparation of compounds of formula I according to claim wherein is with X being or or is or with R2 being a moiety 1 without the hydroxy wherein R is further n being an integer from 1 to or linear or branched or C nitrophenyl or by or wherein is benzoyl which is unsubstituted or substituted by nitro or by or wherein is a radical of formula II R wherein R5 is or R3 and R are a direct bond or each is or R3 is H and independently has the meanings of or R3 and together are or wherein as the radical of a removable protecting group 27 as defined in Claim or wherein further is a radical of III which process comprises in an inert in the presence or absence of a complexing agent reacting with an alkali metal or with an alkali metal or alkaline earth metal compound with a strong anion base to give a compound of formula IV wherein Y is an alka i metal or an alkaline earth and optionally then reacting with an anhydrous metal halide from the group SnZ or to give a compound of IV wherein Y is or and Z i or case of is also reacting the compound formula IV with an ctrophili compound the group or XCOOR2 X being or or a an a C which is unsubst or is substituted by C 1 Ci luoroalkylphenyl niCrophenyl or by or 28 with wherein X1 is or the radical of a secondary or with COO X2 R5 or a compound of n 2n formula wherein is a leaving and isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula A process for the preparation of compounds of formula I according to claim wherein is with X being Cl or with R2 being a 2alcohol moiety without the hydroxy wherein is further with n being an integer from 1 to linear or branched unsubstituted or substituted by nitrophenyl or by or is where is as defined in or is a radical of II wherein is or R3 and are a direct bond or each is or is and independently has the meanings of or 29 R3 and together are or wherein R is the radical of a removable protecting as defined in claim or wherein is a radical of formula III which process comprises in an inert solvent in the presence or absence of a complexing reacting with an alkali metal or with an alkali metal compound with a strong anion base to give a compound of formula IV wherein Y is an alkali and optionally then reacting with an anhydrous metal halide from the group Ni or to give a compound formula IV wherein Y is or and Z is or reacting the compound of formula IV with an elec t rophilic compound the group C02 COX2 or XCOOR2 with X being or or with a a haloalcohol which is unsubstituted or is substituted by alkoxyphenyl C 1 f nitrophenyl or by a which is unsubstituted or is substituted by nitrophenyl or by an a which is unsubstituted or is substituted by C nitro or by or with wherein R7 is as defined in Claim 1 and X is or the radical of a secondary or with R5 or a compound of formula 30 wherein is a leaving and isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula A process the preparation of compounds of formula I according to wherein is with X heing or or a radical of II wherein is or R3 and are a direct bond or each is or R3 is H and independently has the meanings of or R3 and together are wherein R6 is the radical of a removable protecting group as defined in Claim or wherein is a radical of formula III which process comprises in an inert in the presence or absence of a complexing reacting with an alkali metal or with an alkali metal compound with a strong anion base to give a compound of formula IV wherein Y is an alkali and optionally then reacting with an anhydrous metal halide from the group ZnZ2 SnZ TiZ BZ3 or to give a compound of formula IV wherein Y is or and Z is or 1 reacting the compound of formula IV with an elect compound from the group CO2 or with X being or a formylating or a compound of formula wherein X2 is a leaving group as defined in Claim and 31 isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula A process for the preparation of compounds bf formula I according to claim wherein is or a radical of formula II wherein is or each of R3 and is or R3 is H and independently has the meanings of A process according to claim in formula is or in formula II R3 and are a direct bond and R5 is or R3 is is and R5 is or or R3 and together are or and R5 is and R5 in formula III is A process according to claim wherein the reaction is carried out at from to A process according to claim wherein the solvent is a or polar aprotic A process according to claim wherein the solvent is an aliphatic or aromatic an a tertiary an acid a lactam a cyclic a a a a ketone or mixtures A process according to claim wherein the reaction mixture in a complexing A process according to claim wherein the complexing agent is a tertiary an carboxylic acid lactam or cyclic ether or a a crown an alkali metal magnesium halide or copper A process according to claim wherein the alkali metal is Na or and the alkali metal or alkaline earth metal compound is a or or A process according to claim wherein the formylating reagent is a formyl a formic acid an orthoformic acid an alkoxyraethyleneaniline or an A process according to claim as the radical of a secondary X1 is or the radical of a or heterocyclic amine which may contain a further hetero atom from the group and A process according to claim wherein as a leaving group is a or the radical of a sulfonic A process according to claim wherein the protecting group R5 is a trialkylsilyl group having a total of from 1 to 18 carbon or Compounds of formula la wherein is or is or with R2 being a C moiety without the 1 2 hydroxy wherein R is further with n being an integer from 1 to or linear or branched l or being substituted by nitrophenyl or by or wherein is a benzyl alcohol or a benzoyl radical each being unsubstituted or substituted by C nitro or by or wherein is a radical of II wherein R5 is and are a direct bond or each is or R3 is H and independently has the meanings of R5 or R3 and together are or wherein as the radical of a removable protecting group is which is unsubstituted or substituted by or is wherein R2 is as defined 7 7 or R wherein is which is unsubstituted or is substituted by nitrophenyl or by or is phenyl which is unsubstituted or is substituted by or by or wherein further is a radical of formula III 33a with the proviso that R in formula is not and with the further that in formula II is not if R and are both Compounds of formula according to Claim wherein is or is or with R2 being a moiety without the hydroxy wherein is further with n being an integer from 1 to or linear or branched or each being unsubstituted or substituted by 34 nitrophenyl or by or wherein is benzoyl radical unsubstituted or substituted by nitro or by or wherein is a radical of formula II wherein R5 is or R3 and are a direct bond or each is or R3 is and independently has the meanings of R5 or R3 and together are or wherein R6 is the radical of a removable protecting as defined in Claim or wherein further is a radical of formula III with the proviso that in formula III is not and with the further that R5 in formula II is not if R3 and are both Compounds of formula la according to claim wherein is and is an alcohol moiety without a hydroxy or is with n being an integer from 1 to or is a n 2n radical of formula II wherein each of R3 and is and R5 is or or is or R3 and a direct or R3 is and independently has the meanings of or R3 and together are or wherein R6 is the radical of a removable protecting group as defined in Claim wherein R is a radical of formula III in 35 with the proviso that R in formula III is not and with the further that R5 in formula II is not if R3 and are both Compounds according to claim in formula is or or is a radical of formula II wherein R3 and are a bond and R is or R is independently has the meanings of R5 and R5 is or or R3 and together are or wherein R6 is as defined in Claim 17 and R5 is Compounds according to claim wherein R is Compounds according to claim wherein the protecting group is a trialkylsilyl group having a total of from 1 to 18 carbon or For the Applicants insufficientOCRQuality
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH01044/88A CH687877A5 (en) | 1988-03-18 | 1988-03-18 | 2,2-difluorobenzo-1,3-dioxole-4-carbaldehyde. |
Publications (2)
Publication Number | Publication Date |
---|---|
IL89636A0 IL89636A0 (en) | 1989-09-28 |
IL89636A true IL89636A (en) | 1995-08-31 |
Family
ID=4201152
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IL8963689A IL89636A (en) | 1988-03-18 | 1989-03-16 | Preparation of substituted 2,2-difluoro-1,3- benzodioxoles and certain such novel compounds |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0333658B1 (en) |
JP (1) | JP2855337B2 (en) |
KR (1) | KR970002231B1 (en) |
AT (1) | ATE125536T1 (en) |
AU (1) | AU624123B2 (en) |
CA (1) | CA1338936C (en) |
CH (1) | CH687877A5 (en) |
DE (1) | DE58909357D1 (en) |
IL (1) | IL89636A (en) |
ZA (1) | ZA892047B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4705800A (en) * | 1985-06-21 | 1987-11-10 | Ciba-Geigy Corporation | Difluorbenzodioxyl cyanopyrrole microbicidal compositions |
DE58907537D1 (en) * | 1988-03-18 | 1994-06-01 | Ciba Geigy | Process for the preparation of a pyrrole derivative. |
DE4040021A1 (en) * | 1990-12-14 | 1992-06-17 | Bayer Ag | SUBSTITUTED 2,2-DIFLUOR-1,3-BENZODIOXYL-4-KETONE |
DE4213849A1 (en) | 1992-04-27 | 1993-10-28 | Bayer Ag | Process for chlorination of aryl ethers |
DE19530637A1 (en) * | 1995-08-21 | 1997-02-27 | Bayer Ag | Process for the preparation of 2,2-difluorobenzo [1.3] dioxolcarbaldehydes |
CN101851225B (en) * | 2010-06-09 | 2012-08-08 | 山东铂源化学有限公司 | Method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR8207267A (en) * | 1981-12-17 | 1983-10-18 | Du Pont | COMPOUNDS SUITABLE COMPOSITION AND PROCESS TO CONTROL GROWTH OF UNWANTED VEGETATION |
US4722935A (en) * | 1985-04-03 | 1988-02-02 | Ciba-Geigy Corporation | Pesticidal compositions |
US4705800A (en) * | 1985-06-21 | 1987-11-10 | Ciba-Geigy Corporation | Difluorbenzodioxyl cyanopyrrole microbicidal compositions |
DE3716652A1 (en) * | 1987-05-19 | 1988-12-08 | Bayer Ag | DIOXYALKYLENARYL DIHYDROPYRIDINE, INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION, METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
1988
- 1988-03-18 CH CH01044/88A patent/CH687877A5/en not_active IP Right Cessation
-
1989
- 1989-03-09 AT AT89810184T patent/ATE125536T1/en not_active IP Right Cessation
- 1989-03-09 DE DE58909357T patent/DE58909357D1/en not_active Expired - Lifetime
- 1989-03-09 EP EP89810184A patent/EP0333658B1/en not_active Expired - Lifetime
- 1989-03-16 IL IL8963689A patent/IL89636A/en unknown
- 1989-03-16 CA CA000593962A patent/CA1338936C/en not_active Expired - Lifetime
- 1989-03-17 JP JP1065801A patent/JP2855337B2/en not_active Expired - Lifetime
- 1989-03-17 ZA ZA892047A patent/ZA892047B/en unknown
- 1989-03-17 AU AU31452/89A patent/AU624123B2/en not_active Expired
- 1989-03-18 KR KR1019890003441A patent/KR970002231B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ZA892047B (en) | 1989-11-29 |
KR890014512A (en) | 1989-10-24 |
ATE125536T1 (en) | 1995-08-15 |
KR970002231B1 (en) | 1997-02-26 |
AU624123B2 (en) | 1992-06-04 |
IL89636A0 (en) | 1989-09-28 |
JPH01301674A (en) | 1989-12-05 |
AU3145289A (en) | 1989-09-21 |
EP0333658B1 (en) | 1995-07-26 |
CH687877A5 (en) | 1997-03-14 |
JP2855337B2 (en) | 1999-02-10 |
EP0333658A3 (en) | 1990-07-25 |
EP0333658A2 (en) | 1989-09-20 |
CA1338936C (en) | 1997-02-25 |
DE58909357D1 (en) | 1995-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Tatone et al. | Optically active heteroaromatic compounds. VII. Synthesis of the three optically active sec-butylpyridines | |
US5514816A (en) | Process for the preparation of substituted difluorobenzo-1,3-dioxoles | |
IL89636A (en) | Preparation of substituted 2,2-difluoro-1,3- benzodioxoles and certain such novel compounds | |
US5281718A (en) | Process for the preparation of substituted difluorobenzo-1,3-dioxoles | |
Piers et al. | Intermolecular homocoupling of alkenyltrimethylstannane functions mediated by CuCl: Preparation of functionalized conjugated diene and tetraene systems | |
US5087775A (en) | Process for the preparation of partially fluorinated alcohols | |
JP2011148818A (en) | Method for producing alkyl 3-(4-tetrahydropyranyl)-3-oxopropanoate compound and 4-acyltetrahydropyran | |
JP4176201B2 (en) | Method for producing 5-halogeno-2-substituted pyridine | |
JP2006509007A (en) | Process for the synthesis of cycloorganylphosphane and di (alkali metal / alkaline earth metal) oligophosphanedides | |
JPH06100487A (en) | Production of ether compound | |
JP3867213B2 (en) | Method for producing ketoaldehyde | |
JP4051967B2 (en) | Method for producing phosphonodihydropyran derivatives | |
JP2004526752A (en) | Method for producing Δ1-pyrrolines | |
WO2002053552A1 (en) | Process for preparation of esculetin compounds, esculetin compounds and intermediates thereof, and use of both | |
JPH0681734B2 (en) | Method for producing bicyclohymurenone | |
JP2006124347A (en) | New method for producing phenyl 2-pyrimidinyl ketones and new intermediate therefor | |
JP2004515473A (en) | Method for producing delta 1-pyrrolines | |
JP4800933B2 (en) | Process for producing cyclopropane monoacetal derivative and its intermediate | |
JPS6231696B2 (en) | ||
JPS62175456A (en) | 5-arenesulfonylalkanamide derivative | |
JP2000109438A (en) | New production of norbornene derivative having substituent group containing triple bond | |
JPH09278688A (en) | Stilbene compound, its production, liquid crystal composition containing the same as effective component and liquid crystal element using the composition | |
JP2006052144A (en) | METHOD FOR PRODUCING beta-SUBSTITUTED TYPE beta-METHOXYACRYLATE | |
JPH0246017B2 (en) | JIMECHIRUOKUTENJIOORUJUDOTAIOYOBISONOSEIZOHOHO | |
JP2003095997A (en) | Method for producing alkene derivative |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
KB | Patent renewed | ||
HC | Change of name of proprietor(s) | ||
KB | Patent renewed | ||
KB | Patent renewed |