NO316446B1 - Dimethyl furanecarboxyanilide derivatives and wood preservative - Google Patents
Dimethyl furanecarboxyanilide derivatives and wood preservative Download PDFInfo
- Publication number
- NO316446B1 NO316446B1 NO19964369A NO964369A NO316446B1 NO 316446 B1 NO316446 B1 NO 316446B1 NO 19964369 A NO19964369 A NO 19964369A NO 964369 A NO964369 A NO 964369A NO 316446 B1 NO316446 B1 NO 316446B1
- Authority
- NO
- Norway
- Prior art keywords
- group
- carbon atoms
- wood
- dimethylfuran
- general formula
- Prior art date
Links
- 239000003171 wood protecting agent Substances 0.000 title description 24
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000002023 wood Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000005169 cycloalkylcarbonylamino group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005080 alkoxycarbonylalkenyl group Chemical group 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 229940099451 3-iodo-2-propynylbutylcarbamate Drugs 0.000 claims description 2
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 claims description 2
- BYFUOVKERSMJTC-UHFFFAOYSA-N (5-bromo-2,5-diiodopent-3-enyl)carbamic acid Chemical compound C(C(C=CC(Br)I)I)NC(=O)O BYFUOVKERSMJTC-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- -1 nitro-substituted phenyl Chemical group 0.000 description 17
- 238000000921 elemental analysis Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000002335 preservative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 241000233866 Fungi Species 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 101150041968 CDC13 gene Proteins 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- 230000028644 hyphal growth Effects 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- LZFCBBSYZJPPIV-UHFFFAOYSA-M magnesium;hexane;bromide Chemical compound [Mg+2].[Br-].CCCCC[CH2-] LZFCBBSYZJPPIV-UHFFFAOYSA-M 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RWORXZHVOUPMMM-UHFFFAOYSA-N 2,5-dimethylfuran-3-carbonyl chloride Chemical compound CC1=CC(C(Cl)=O)=C(C)O1 RWORXZHVOUPMMM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 241000218692 Cryptomeria Species 0.000 description 3
- 240000005109 Cryptomeria japonica Species 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000001888 Peptone Substances 0.000 description 3
- 108010080698 Peptones Proteins 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- DNYLSCDHFCSDRM-UHFFFAOYSA-N ethyl 2,5-dimethylfuran-3-carboxylate Chemical compound CCOC(=O)C=1C=C(C)OC=1C DNYLSCDHFCSDRM-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000019319 peptone Nutrition 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- CNTHHNPBADVTRY-UHFFFAOYSA-N 2,5-dimethylfuran-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=C(C)O1 CNTHHNPBADVTRY-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 150000003931 anilides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 230000002538 fungal effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 239000013585 weight reducing agent Substances 0.000 description 2
- YTMFJEGOQFCLMX-UHFFFAOYSA-N (5-bromo-2,5-diiodopent-3-enyl) carbamate Chemical compound NC(=O)OCC(I)C=CC(Br)I YTMFJEGOQFCLMX-UHFFFAOYSA-N 0.000 description 1
- GOSHEZZPLYXNIQ-UHFFFAOYSA-N (5-bromo-2,5-diiodopent-3-enyl) hydrogen carbonate Chemical compound C(C(C=CC(Br)I)I)OC(=O)O GOSHEZZPLYXNIQ-UHFFFAOYSA-N 0.000 description 1
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- LNJXZKBHJZAIKQ-UHFFFAOYSA-N 1,1,1,2-tetrachloro-3-(2,3,3,3-tetrachloropropoxy)propane Chemical compound ClC(Cl)(Cl)C(Cl)COCC(Cl)C(Cl)(Cl)Cl LNJXZKBHJZAIKQ-UHFFFAOYSA-N 0.000 description 1
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 1
- DRTQHJPVMGBUCF-UCVXFZOQSA-N 1-[(2s,3s,4s,5s)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]pyrimidine-2,4-dione Chemical compound O[C@H]1[C@H](O)[C@H](CO)O[C@@H]1N1C(=O)NC(=O)C=C1 DRTQHJPVMGBUCF-UCVXFZOQSA-N 0.000 description 1
- CPAWBGYESSPHRY-UHFFFAOYSA-N 2,5-dimethyl-n-(3-propan-2-ylphenyl)furan-3-carboxamide Chemical compound CC(C)C1=CC=CC(NC(=O)C2=C(OC(C)=C2)C)=C1 CPAWBGYESSPHRY-UHFFFAOYSA-N 0.000 description 1
- CNTHHNPBADVTRY-UHFFFAOYSA-M 2,5-dimethylfuran-3-carboxylate Chemical compound CC1=CC(C([O-])=O)=C(C)O1 CNTHHNPBADVTRY-UHFFFAOYSA-M 0.000 description 1
- FFCSRWGYGMRBGD-UHFFFAOYSA-N 3-iodoaniline Chemical compound NC1=CC=CC(I)=C1 FFCSRWGYGMRBGD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005896 Etofenprox Substances 0.000 description 1
- 241001105467 Fomitopsis palustris Species 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 241001674251 Serpula lacrymans Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
- 241000222355 Trametes versicolor Species 0.000 description 1
- 241001646063 Tyromyces Species 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- WURGXGVFSMYFCG-UHFFFAOYSA-N dichlofluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1 WURGXGVFSMYFCG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YREQHYQNNWYQCJ-UHFFFAOYSA-N etofenprox Chemical compound C1=CC(OCC)=CC=C1C(C)(C)COCC1=CC=CC(OC=2C=CC=CC=2)=C1 YREQHYQNNWYQCJ-UHFFFAOYSA-N 0.000 description 1
- 229950005085 etofenprox Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000004995 haloalkylthio group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- JNJVPLPNYYELRZ-UHFFFAOYSA-N n-(3-butylphenyl)-2,5-dimethylfuran-3-carboxamide Chemical compound CCCCC1=CC=CC(NC(=O)C2=C(OC(C)=C2)C)=C1 JNJVPLPNYYELRZ-UHFFFAOYSA-N 0.000 description 1
- UCKWSSKMOYXDNC-UHFFFAOYSA-N n-(3-ethylphenyl)-2,5-dimethylfuran-3-carboxamide Chemical compound CCC1=CC=CC(NC(=O)C2=C(OC(C)=C2)C)=C1 UCKWSSKMOYXDNC-UHFFFAOYSA-N 0.000 description 1
- FIDDYGVCXWMAOB-UHFFFAOYSA-N n-(3-hexylphenyl)-2,5-dimethylfuran-3-carboxamide Chemical compound CCCCCCC1=CC=CC(NC(=O)C2=C(OC(C)=C2)C)=C1 FIDDYGVCXWMAOB-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000005527 organic iodine compounds Chemical class 0.000 description 1
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- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 1
- 229950001664 phoxim Drugs 0.000 description 1
- 230000008654 plant damage Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
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- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- BZNDWPRGXNILMS-VQHVLOKHSA-N propetamphos Chemical compound CCNP(=S)(OC)O\C(C)=C\C(=O)OC(C)C BZNDWPRGXNILMS-VQHVLOKHSA-N 0.000 description 1
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- YWSCPYYRJXKUDB-KAKFPZCNSA-N tralomethrin Chemical compound CC1(C)[C@@H](C(Br)C(Br)(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 YWSCPYYRJXKUDB-KAKFPZCNSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Description
Teknisk område Technical area
Foreliggende oppfinnelse angår nye dimethylfurancarboxyanilidderivater som utviser en glimrende antimikro- The present invention relates to new dimethylfurancarboxyanilide derivatives which exhibit an excellent antimicro-
biell effekt, et trekonserveringsmiddel inneholdende dimethyl-furancarboxyanilidderivatet som aktiv bestanddel, og et trekonserveringspreparat hvori dimethylfurancarboxyanilid- bial effect, a wood preservative containing the dimethylfurancarboxyanilide derivative as active ingredient, and a wood preservative preparation in which dimethylfurancarboxyanilide
derivatet som én av de aktive bestanddeler er kombinert med ethvert kommersielt tilgjengelig trekonserveringsmiddel hvis effekt allerede er blitt bekreftet. the derivative as one of the active ingredients is combined with any commercially available wood preservative whose effect has already been confirmed.
Kjent teknikk Known technique
Forskjellige typer av uorganiske eller organiske forbindelser har tidligere vært anvendt for å konservere tømmer mot råte på grunn av forskjellige tre-råtnende fungi. Various types of inorganic or organic compounds have previously been used to preserve timber against rotting due to various wood-rotting fungi.
Disse har imidlertid ulemper slik som å påvirke det menneske- However, these have disadvantages such as affecting the human
lige legeme på grunn av deres høye toksisitet, de utviser miljøforurensning, krever en høy konsentrasjon når de anvendes og er kostbare. body due to their high toxicity, they exhibit environmental pollution, require a high concentration when used and are expensive.
Med hensyn til forbindelsene som tilhører dimethyl-furancarboxyanilidderivatene ifølge foreliggende oppfinnelse er forbindelser representert ved den nedenfor angitte formel blitt beskrevet i japansk patentsøknad (Kokai) Sho 50-10376 With regard to the compounds belonging to the dimethyl-furancarboxyanilide derivatives of the present invention, compounds represented by the formula below have been described in Japanese Patent Application (Kokai) Sho 50-10376
som et kjemikalium for forhindring av planteskade, hvori imidlertid R er begrenset til fenyl, nitro-substituert fenyl, carboxy-substituert fenyl, fenyl-substituert fenyl, methyl-substituert fenyl, halogen-substituert fenyl eller methoxy-substituert fenyl. I tillegg er dette patentskrift taust med hensyn til de andre derivater, og ingen aktivitet av disse forbindelser på tre-råtnende fungi er blitt beskrevet. as a plant damage prevention chemical, wherein, however, R is limited to phenyl, nitro-substituted phenyl, carboxy-substituted phenyl, phenyl-substituted phenyl, methyl-substituted phenyl, halogen-substituted phenyl, or methoxy-substituted phenyl. In addition, this patent document is silent with regard to the other derivatives, and no activity of these compounds on wood-rotting fungi has been described.
Sammendrag av oppfinnelsen Summary of the invention
Et mål med den foreliggende oppfinnelse er å til-veiebringe et nytt trekonserveringsmidel som er sikkert og som er mulig å anvende effektivt med en lav konsentrasjon og/ eller til en lav pris. An aim of the present invention is to provide a new wood preservative which is safe and which can be used effectively with a low concentration and/or at a low price.
Under hensyntagen til det ovenfor angitte mål har foreliggende oppfinnere foretatt et grundig studium av furan-carboxyanilidderivater. Denne studie resulterte i den observasjon at de nye dimethylfurancarboxyanilidderivater representert ved formel (I) nedenfor er meget anvendbare som et trekonserveringsmiddel, og hvis enn videre dimethylfuran-carboxyanilidderivatene som aktive bestanddeler kombineres med ethvert annet kommersielt tilgjengelig trekonserveringsmiddel, kan en forsterket effekt observeres og et trekonserveringspreparat kan fremstilles. Taking into account the above stated objective, the present inventors have made a thorough study of furan-carboxyanilide derivatives. This study resulted in the observation that the new dimethylfurancarboxyanilide derivatives represented by formula (I) below are very useful as a wood preservative, and if furthermore the dimethylfurancarboxyanilide derivatives as active ingredients are combined with any other commercially available wood preservative, an enhanced effect can be observed and a wood preservative preparation can be produced.
Forbindelsene ifølge foreliggende oppfinnelse er dimethylfurancarboxyanilidderivater kjennetegnet ved generell formel (I) The compounds according to the present invention are dimethylfurancarboxyanilide derivatives characterized by general formula (I)
hvori in which
R<1> betegner R<1> denotes
en 3-alkoxycarbonylgruppe med fra 1 til 3 carbonatomer i alkoxydelen, a 3-Alkoxycarbonyl group with from 1 to 3 carbon atoms in the alkoxy part,
en 3-alkoxymethylgruppe med fra 1 til 3 carbonatomer i alkoxydelen, a 3-Alkoxymethyl group with from 1 to 3 carbon atoms in the alkoxy part,
en cykloalkylcarbonylaminogruppe med fra 4 til 6 carbonatomer i cykloalkyldelen, a cycloalkylcarbonylamino group with from 4 to 6 carbon atoms in the cycloalkyl part,
en benzylgruppe som kan være substituert med en methoxygruppe, en benzoylgruppe, eller a benzyl group which may be substituted with a methoxy group, a benzoyl group, or
en alkoxycarbonylalkenylgruppe med fra 1 til 3 carbonatomer i alkoxydelen og som har fra 2 til 3 carbonatomer i alkenyldelen, og an alkoxycarbonylalkenyl group having from 1 to 3 carbon atoms in the alkoxy part and having from 2 to 3 carbon atoms in the alkenyl part, and
R2 betegner et hydrogenatom R 2 denotes a hydrogen atom
Foreliggende oppfinnelse angår enn videre et trekonserveringspreparat som er kjennetegnet ved at det omfatter en bærer i kombinasjon med en mengde som er effektiv til å konservere tre av et dimethylfurancarboxyanilidderivat av generell formel (I') som definert nedenfor som aktiv bestanddel The present invention further relates to a wood preservation preparation which is characterized in that it comprises a carrier in combination with an amount effective to preserve wood of a dimethylfurancarboxyanilide derivative of general formula (I') as defined below as active ingredient
hvori in which
R<1>' betegner R<1>' denotes
en 3-alkylgruppe med fra 2 til 6 carbonatomer, a 3-alkyl group of from 2 to 6 carbon atoms,
en 3-alkoxycarbonylgruppe med fra 1 til 3 carbonatomer i alkoxydelen, a 3-Alkoxycarbonyl group with from 1 to 3 carbon atoms in the alkoxy part,
en 3-alkoxymethylgruppe med fra 1 til 3 carbonatomer i alkoxydelen, a 3-Alkoxymethyl group with from 1 to 3 carbon atoms in the alkoxy part,
en cykloalkylcarbonylammogruppe med fra 4 til 6 carbonatomer i cykloalkyldelen, a cycloalkylcarbonylamino group with from 4 to 6 carbon atoms in the cycloalkyl part,
en benzylgruppe som kan være substituert med en methoxygruppe, en benzoylgruppe, eller a benzyl group which may be substituted with a methoxy group, a benzoyl group, or
en alkoxycarbonylalkenylgruppe med fra 1 til 3 carbonatomer i alkoxydelen og med fra 2 til 3 carbonatomer i alkenyldelen, og R<2>' betegner et hydrogenatom an alkoxycarbonylalkenyl group with from 1 to 3 carbon atoms in the alkoxy part and with from 2 to 3 carbon atoms in the alkenyl part, and R<2>' denotes a hydrogen atom
Oppfinnelsen angår også et trekonserveringspreparat som er kjennetegnet ved at minst ett dimethylfurancarboxyanilidderivat av generell formel (I<1>) som definert i krav 3, er kombinert med minst én forbindelse valgt fra 3-brom-2,3-dijod-2-propenyl-ethylcarbamat, 3-jod-2-propynylbutylcarbamat og 4-klorfenyl-3-j odpropargylformal The invention also relates to a wood preservative preparation which is characterized in that at least one dimethylfurancarboxyanilide derivative of general formula (I<1>) as defined in claim 3 is combined with at least one compound selected from 3-bromo-2,3-diiodo-2-propenyl- ethyl carbamate, 3-iodo-2-propynylbutyl carbamate and 4-chlorophenyl-3-iodopropargyl formal
Beste måte for utførelse av oppfinnelsen Best method for carrying out the invention
I den ovenfor angitte generelle formel (I) er en alkylgruppe med fra 2 til 6 carbonatomer, som er innbefattet i definisjonen for r\ en rettkjedet eller forgrenet alkylgruppe slik som ethyl, propyl, isopropyl, butyl, isobutyl, sek-butyl, tert-butyl, pentyl, isopentyl, neo-pentyl, hexyl, isohexyl eller sek-hexyl; fortrinnsvis en alkylgruppe med fra 2 til 6 carbonatomer. In the general formula (I) given above, an alkyl group of from 2 to 6 carbon atoms, which is included in the definition of r\, is a straight chain or branched alkyl group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert- butyl, pentyl, isopentyl, neo-pentyl, hexyl, isohexyl or sec-hexyl; preferably an alkyl group with from 2 to 6 carbon atoms.
Som en alkoxygruppe med fra 1 til 3 carbonatomer inne-holdt i en alkoxyalkylgruppe med fra 1 til 3 carbonatomer i alkoxygruppen, og som er innbefattet i definisjonen for R<1> i generell formel (I) ovenfor, kan nevnes en rettkjedet eller forgrenet alkoxygruppe slik som methoxy, ethoxy, propoxy eller isopropoxy As an alkoxy group with from 1 to 3 carbon atoms contained in an alkoxyalkyl group with from 1 to 3 carbon atoms in the alkoxy group, and which is included in the definition for R<1> in general formula (I) above, a straight-chain or branched alkoxy group can be mentioned such as methoxy, ethoxy, propoxy or isopropoxy
Som en alkoxycarbonylgruppe med fra 1 til 3 carbonatomer i alkoxygruppen, som er innbefattet i definisjonen for R<1 >i generell formel (I) ovenfor, kan nevnes methoxycarbonyl, ethoxycarbonyl eller isopropoxycarbonyl As an alkoxycarbonyl group with from 1 to 3 carbon atoms in the alkoxy group, which is included in the definition for R<1> in general formula (I) above, methoxycarbonyl, ethoxycarbonyl or isopropoxycarbonyl can be mentioned
Som en cykloalkylcarbonylaminogruppe med fra 4 til As a cycloalkylcarbonylamino group with from 4 to
6 carbonatomer i cykloalkylgruppen, og som er innbefattet innen definisjonen for R<1> i generell formel (I) ovenfor, kan nevnes cyklobutylcarbonylammo, cyklopentylcarbonylamino eller cyklo-hexylcarbonylammo, fortrinnsvis cyklohexylcarbonylamino 6 carbon atoms in the cycloalkyl group, and which are included within the definition for R<1> in general formula (I) above, may be mentioned cyclobutylcarbonylamino, cyclopentylcarbonylamino or cyclohexylcarbonylamino, preferably cyclohexylcarbonylamino
Nye dimethylfurancarboxyanilidderivater som kan anvendes som en aktiv bestanddel av trekonservermgsmidlet ifølge foreliggende oppfinnelse, er eksemplifisert i den etterfølgende tabell New dimethylfurancarboxyanilide derivatives that can be used as an active component of the wood preservative according to the present invention are exemplified in the following table
I tabell 1 nedenunder er de angitte forkortelser som følger In table 1 below, the indicated abbreviations are as follows
Blant forbindelsene nevnt ovenfor, innbefatter de foretrukne forbindelser nr 3, 10, 20, 21, 23, 24, 25, 26, 69, 70, 71, 72, 75, 80, 81, 82, 83 og 85, og mer foretrukket innbefatter forbindelser nr 3, 10, 24, 26, 69, 70, 81, 83 og 85 Among the compounds mentioned above, the preferred compounds include No. 3, 10, 20, 21, 23, 24, 25, 26, 69, 70, 71, 72, 75, 80, 81, 82, 83 and 85, and more preferably include compounds no. 3, 10, 24, 26, 69, 70, 81, 83 and 85
Forbindelsene av generell formel (I) kan fremstilles i henhold til den prosedyre som er angitt i enten den etterfølgende Metode A eller Metode B The compounds of general formula (I) may be prepared according to the procedure set forth in either the following Method A or Method B
Metode A Method A
Metode B Method B
I de ovenfor angitte formler er R<1> som definert ovenfor R<1>" betegner en C2-C6-alkylgruppe eller benzylgruppe som eventuelt kan ha en methoxysubstituent Forbindelsen av formel (Ia) er den av generell formel (I<1>) hvori R<1>' er R<1>" og R2 angir et hydrogenatom Forbindelsen av formel (V) er 3od-substituert anilin X angir et halogenatom slik som klor, brom eller jod, fortrinnsvis klor X<1> angir et halogenatom slik som klor, brom eller jod, fortrinnsvis brom eller jod In the formulas given above, R<1> is as defined above R<1>" denotes a C2-C6 alkyl group or benzyl group which may optionally have a methoxy substituent. The compound of formula (Ia) is that of general formula (I<1>) wherein R<1>' is R<1>" and R2 denotes a hydrogen atom The compound of formula (V) is 3od-substituted aniline X denotes a halogen atom such as chlorine, bromine or iodine, preferably chlorine X<1> denotes a halogen atom such such as chlorine, bromine or iodine, preferably bromine or iodine
Forbindelsene ifølge oppfinnelsen kan fremstilles The compounds according to the invention can be prepared
ved velkjente prosedyrer. by well-known procedures.
Trinn Al består av fremstillingen av en forbindelse Step Al consists of the preparation of a compound
av generell formel (I) ved omsetning av en forbindelse av generell formel (III) med en forbindelse av generell formel (IV) 1 et mert løsningsmiddel 1 nærvær av et dehydrohaloge-neringsmiddel. of general formula (I) by reacting a compound of general formula (III) with a compound of general formula (IV) 1 a mercantile solvent 1 presence of a dehydrohalogenating agent.
En forbindelse av formel (III) anvendt som utgangs-materiale 1 dette trinn kan fremstilles ved hydrolyse av 2,5-dimethylfuran-3-carboxylat, som kan fremstilles ved konden-sering av kloraceton med acetoacetat, etterfulgt av haloge-ne r ing. A compound of formula (III) used as starting material in this step can be prepared by hydrolysis of 2,5-dimethylfuran-3-carboxylate, which can be prepared by condensation of chloroacetone with acetoacetate, followed by halogenation.
En forbindelse av formel (IV) anvendt som utgangs-materiale i dette trinn er et anilmderivat som er kommersielt tilgjengelig eller kan fremstilles ved velkjente metoder. A compound of formula (IV) used as starting material in this step is an anilm derivative which is commercially available or can be prepared by well-known methods.
Eksempler på de anvendte inerte løsningsmidler innbefatter for eksempel ethere slik som ether, isopropylether, tetrahydrofuran eller dioxan; aromatiske hydrocarboner slik som benzen, toluen eller xylen; halogenerte hydrocarboner slik som diklormethan, kloroform eller carbontetraklorid; og blandinger av to eller flere av disse løsningsmidler; fortrinnsvis aromatiske hydrocarboner (i særdeleshet toluen). Examples of the inert solvents used include, for example, ethers such as ether, isopropyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride; and mixtures of two or more of these solvents; preferably aromatic hydrocarbons (in particular toluene).
Eksempler på de anvendte dehydrohalogeneringsmidler innbefatter for eksempel tertiære aminer slik som triethylamin, N,N-dimethylammo<p>yridin eller lignende, og pyridiner. Denne reaksjon kan utføres i nærvær eller i fravær av et løsnings-middel. For å utføre reaksjonen glatt under anvendelse av et løsningsmiddel utføres reaksjonen ved en temperatur på 0° C til tilbakeløpstemperaturen for det anvendte løsningsmiddel, fortrinnsvis ved romtemperatur til 100° C. Den nødvendige tid for reaksjonen tar generelt fra 30 minutter til 5 timer, fortrinnsvis fra 30 minutter til 2 timer. Examples of the dehydrohalogenating agents used include, for example, tertiary amines such as triethylamine, N,N-dimethylamino<p>yridine or the like, and pyridines. This reaction can be carried out in the presence or in the absence of a solvent. In order to carry out the reaction smoothly using a solvent, the reaction is carried out at a temperature of 0° C to the reflux temperature of the solvent used, preferably at room temperature to 100° C. The time required for the reaction generally takes from 30 minutes to 5 hours, preferably from 30 minutes to 2 hours.
Trinn Bl består av fremstillingen av en forbindelse av generell formel (IV) ved omsetning av en forbindelse av generell formel (III) med en forbindelse av generell formel (V) i et inert løsningsmiddel i nærvær av et dehydrohalogene-ringsmiddel. Step B1 consists of the preparation of a compound of general formula (IV) by reacting a compound of general formula (III) with a compound of general formula (V) in an inert solvent in the presence of a dehydrohalogenating agent.
En forbindelse av formel (IV) anvendt som utgangs-materiale i dette trinn er et anilmderivat som er kommersielt tilgjengelig eller som kan fremstilles ved velkjente metoder. A compound of formula (IV) used as starting material in this step is an anilm derivative which is commercially available or which can be prepared by well-known methods.
Reaksjonsbetingelsene anvendt i dette trinn er lik de som anvendes i trmn Al. The reaction conditions used in this step are similar to those used in step Al.
Trinn B2 består i fremstillingen av en forbindelse av generell formel (Ia) ved omsetning av en forbindelse av generell formel (VI) med et Grignard-reagens av generell formel: R i »MgX' i et inert løsningsmiddel i nærvær av en katalysator. Step B2 consists in the preparation of a compound of general formula (Ia) by reacting a compound of general formula (VI) with a Grignard reagent of general formula: R i »MgX' in an inert solvent in the presence of a catalyst.
Eksempler på foretrukne xnerte løsningsmidler innbefatter for eksempel ethere slik som diethylether, isopropylether, tetrahydrofuran eller dioxan; i særdeleshet diethylether. Examples of preferred inert solvents include, for example, ethers such as diethyl ether, isopropyl ether, tetrahydrofuran or dioxane; in particular diethyl ether.
Som en særlig foretrukken katalysator kan anvendes [1,1'-bis(difenylfosfino)ferrocen]palladium(II)klorid. [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride can be used as a particularly preferred catalyst.
Grignard-reagensene anvendt i denne fremgangsmåte er kommersielt tilgjengelig eller kan fremstilles ved omsetning av magnesium med et alkylhalogenid representert ved formelen: R X (hvori R og X' er som ovenfor definert) i henhold til velkjente metoder. The Grignard reagents used in this method are commercially available or can be prepared by reacting magnesium with an alkyl halide represented by the formula: R X (wherein R and X' are as defined above) according to well known methods.
Reaksjonen utføres normalt ved en temperatur på 0° C til 50° C, fortrinnsvis ved romtemperatur. Selv om den nød-vendige tid for reaksjonen varierer avhengig av arten av løs-ningsmiddel og det reagens som anvendes, fullføres reaksjonen normalt innen en periode på 10 timer til 10 dager. The reaction is normally carried out at a temperature of 0° C to 50° C, preferably at room temperature. Although the time required for the reaction varies depending on the nature of the solvent and the reagent used, the reaction is normally completed within a period of 10 hours to 10 days.
Forbindelsene av angitte generelle formel (I) ifølge oppfinnelsen har kraftig trekonserverende aktivitet ved lav konsentrasjon, sammenlignet med aktiviteten vist av eksiste-rende trekonservermgsmidler. Et preparat bestående av en kombinasjon av den foregående forbindelse (I) med et kjent trekonserveringsmiddel gir en synergistisk effekt, idet lavere konsentrasjoner av hver forbindelse er nødvendig enn hva som kunne forventes ut fra aktiviteten utvist av hver enkelt, slik at preparatet utviser en effektiv trekonserverende aktivitet ved en lav konsentrasjon. De nye dimethylfurancarboxyanilidderivater er derfor uhyre effektive som et trekonserveringsmiddel i lav konsentrasjon og løser derved ett av de problemer som er påpekt tidligere. The compounds of specified general formula (I) according to the invention have strong wood preservative activity at low concentration, compared to the activity shown by existing wood preservatives. A preparation consisting of a combination of the preceding compound (I) with a known wood preservative gives a synergistic effect, as lower concentrations of each compound are necessary than could be expected from the activity exhibited by each individual, so that the preparation exhibits an effective wood preservative activity at a low concentration. The new dimethylfurancarboxyanilide derivatives are therefore extremely effective as a wood preservative in low concentration and thereby solve one of the problems pointed out earlier.
De etterfølgende eksempler illustrerer fremstillingen og formuleringen av forbindelsen ifølge oppfinnelsen mere i detalj. Disse eksempler skal ikke betraktes som å begrense oppfinnelsens ramme. The following examples illustrate the preparation and formulation of the compound according to the invention in more detail. These examples should not be considered as limiting the scope of the invention.
Eksempel 1 Example 1
2, 5- dime thy1furan- 3- carboxy( 3- acetylaminoanilid) 2, 5- dime thy1furan- 3- carboxy( 3- acetylaminoanilide)
Til en løsning av 0,50 g 2,5-dimethylfuran-3-carbonylklorid i 10 ml diklormethan ble det tilsatt 0,44 ml tnethylamm og 0,47 g 3-acetylammoamlin under isavkjøling, og den resulterende blanding ble omrørt ved romtemperatur i 2,5 timer, etterfulgt av oppvarming til tilbakeløpskokning i 4,5 timer. Etter at reaksjonsblandingen var avkjølt ble den fortynnet ved tilsetning av 10 ml diklormethan. Den fortynnede blanding ble suksessivt vasket med IN natriumhydroxyd, To a solution of 0.50 g of 2,5-dimethylfuran-3-carbonyl chloride in 10 ml of dichloromethane was added 0.44 ml of triethylamine and 0.47 g of 3-acetylaminoamine under ice cooling, and the resulting mixture was stirred at room temperature for 2 .5 hours, followed by heating to reflux for 4.5 hours. After the reaction mixture had cooled, it was diluted by adding 10 ml of dichloromethane. The diluted mixture was washed successively with 1N sodium hydroxide,
IN saltsyre og en mettet vandig løsning av natriumklorid og ble tørket over natriumsulfat, etterfulgt av avdestillenng av løsningsmidlet. Residuet ble renset ved kolonnekromatografi gjennom silicagel, og de ønskede fraksjoner ble omkrystalli-sert fra ethylacetat under dannelse av 0,51 g av den ønskede forbindelse som hvite krystaller i et utbytte på 59,4 %. Sm.p.: 172,0 - 172,5° C 1N hydrochloric acid and a saturated aqueous solution of sodium chloride and was dried over sodium sulfate, followed by distillation of the solvent. The residue was purified by column chromatography through silica gel, and the desired fractions were recrystallized from ethyl acetate to give 0.51 g of the desired compound as white crystals in a yield of 59.4%. Melting point: 172.0 - 172.5° C
<1>H NMR (CDC13 + DMSO) 6 ppm: <1>H NMR (CDC13 + DMSO) 6 ppm:
8.4 (1H, b), 7,95 (1H, b), 7,88 (1H( m), 7,4 (1H, 8.4 (1H, b), 7.95 (1H, b), 7.88 (1H( m), 7.4 (1H,
m), 7,32 (1H, m), 7,25 (1H, t, J=8Hz), 6,25 (1H, m), 7.32 (1H, m), 7.25 (1H, t, J=8Hz), 6.25 (1H,
s), 2,55 (3H, s), 2,25 (3H, s), 2,15 (3H, s) s), 2.55 (3H, s), 2.25 (3H, s), 2.15 (3H, s)
IR (KBr) cm"<1>: 3306, 1672, 1651, 1086, 781 IR (KBr) cm"<1>: 3306, 1672, 1651, 1086, 781
Elementaeranalyse (%) : beregnet for C-^H^g^O-j: Elemental analysis (%) : calculated for C-^H^g^O-j:
C 66,16 H 5,92 N 10,29 C 66.16 H 5.92 N 10.29
Funnet: C 66,30 H 5,98 N 10,32 Found: C 66.30 H 5.98 N 10.32
Ved å følge en lignende prosedyre som angitt ovenfor, men ved anvendelse av et egnet anilmderivat istedenfor 3-acetylaminoamlin, ble følgende forbindelser erholdt. By following a similar procedure as stated above, but using a suitable anilm derivative instead of 3-acetylaminoamine, the following compounds were obtained.
Eksempel 2 Example 2
2, 5- dimethylfuran- 3- carboxy( 3- methoxycarbonylanilid) 2, 5- dimethylfuran- 3- carboxy (3- methoxycarbonylanilide)
Utbytte: 77,1 % Yield: 77.1%
Sm.p.: 104,0 - 106,0° C Melting point: 104.0 - 106.0° C
<1>H NMR (CDC13) 6 ppm: <1>H NMR (CDC13) 6 ppm:
8.05 (1H, ra), 7,98 (1H, m), 7,8 (1H, m), 7,42 8.05 (1H, ra), 7.98 (1H, m), 7.8 (1H, m), 7.42
(1H, t, J=8Hz), 7,38 (1H, b), 6,1 (1H, s), 3,92 (1H, t, J=8Hz), 7.38 (1H, b), 6.1 (1H, s), 3.92
(3H, s), 2,55 (3H, s), 2,25 (3H, s) (3H, s), 2.55 (3H, s), 2.25 (3H, s)
IR (KBr) cm"<1>: 3437, 1704, 1675, 1070, 759 IR (KBr) cm"<1>: 3437, 1704, 1675, 1070, 759
Elementaeranalyse (%) : Beregnet for C-^H^i-NO^: Elemental analysis (%) : Calculated for C-^H^i-NO^:
C 65,92 H 5,53 N 5,13 C 65.92 H 5.53 N 5.13
Funnet: C 66,02 H 5,60 N 5,08 Found: C 66.02 H 5.60 N 5.08
Eksempel 3 Example 3
2, 5- dimethylfuran- 3- carboxy( 3- benzoylanilid) Utbytte: 69,1 % 2, 5-dimethylfuran-3-carboxy(3-benzoylanilide) Yield: 69.1%
Sm.p.: 137,0 - 139,0° C Melting point: 137.0 - 139.0° C
<1>H NMR (CDC13) 6 ppm: <1>H NMR (CDC13) 6 ppm:
8,05 (1H, m), 7,85-7,7 (3H, m), 7,6 (1H, m), 7,55-7,35 (5H, m), 6,1 (1H, s), 2,55 <3H, s) , 8.05 (1H, m), 7.85-7.7 (3H, m), 7.6 (1H, m), 7.55-7.35 (5H, m), 6.1 (1H, s), 2.55 <3H, s) ,
2,25 (3H, s) 2.25 (3H, s)
IR (KBr) cm"1: 3386, 1672, 1647, 1069, 707 Elementæranalyse (%): Beregnet for C20H17NO3: C 75,22 H 5,37 N 4,39 IR (KBr) cm"1: 3386, 1672, 1647, 1069, 707 Elemental analysis (%): Calculated for C20H17NO3: C 75.22 H 5.37 N 4.39
Funnet: C 75,38 H 5,43 N 4,38 Found: C 75.38 H 5.43 N 4.38
Eksempel 4 Example 4
2, 5- dimethylfuran- 3- carboxy( 3- cyklohexylcarbonylaminoanilid) Utbytte: 45,1 % 2, 5-dimethylfuran-3-carboxy(3-cyclohexylcarbonylaminoanilide) Yield: 45.1%
Sm.p.: 212,5 - 213,0° C Melting point: 212.5 - 213.0° C
<1>H NMR (CDC13) 6 ppm<*.>;7,92 (1H, b), 7,88 (1H, b), 7,45-7,35 (2H, m), 7,25 (1H, t, J=8Hz), 6,22 (1H, s) , 2,55 (3H, s) , 2,25 (3H, s), 2,25-2,2 (1H, m), 2,0-1,2 (10H, m) IR (KBr) cm"<1>: 3238, 1651, 1639, 1076, 781 ;Elementæranalyse (%): Beregnet for C2<gH>24<N>2<0>3: ;C 70,57 H 7,11 N 8,23 Funnet: C 70,56 H 7,26 N 8,16 ;Eksempel 5 ;2, 5- dimethylfuran- 3- carboxy (- 3- methoxymethylanil3. d) Utbytte: 73,3 % ;Sm.p.: 102,5 - 103,5° C ;<X>H NMR (CDC13) <S ppm: ;7,55 (1H, m) , 7,52 (1H, d, J=8Hz), 7,32 (1H, t, J=8Hz), 7,32 (1H, b), 6,9 (1H, d, J=8Hz), 6,1 ;<1H, s), 4,45 (2H, s), 3,4 (3H, s), 2,55 (3H, s), ;2,25 (3H, s) ;IR (KBr) cm"<1>: 3278, 1645, 1237, 1107, 784 Elementæranalyse (%); Beregnet for ci5Hi7N03: C 69,48 H 6,61 N 5,40 ;Funnet: C 69,22 H 7,02 N 5,37 ;Eksempel 6 ;2, 5- dimethylfuran- 3- carboxy( 3- ethoxymethylanilid) Utbytte: 64,4 % ;Sm.p.: 85,0 - 85,5° C ;<X>H NMR (CDC13) <S ppm: ;7,65-7,55 (2H, m) , 7,38 (1H, t#iJ=8Hz), 7,35 (1H, b), 7,15 (1H, d, J=8Hz), 6,15 (1H, s), 4,55 (2H, s), 3,58 (2H, q, J=8Hz), 2,55 (3H, s), 2,25 (3H, ;s), 1,3 (3H, t, J=8Hz) ;IR (KBr) cm"<1>: 3279, 1646, 1115, 785 ;Elementæranalyse (%) : Beregnet for C^gH^^NO^: ;C 70,31 H 7,01 N 5,12 ;Funnet: C 70,14 H 7,27 N 5,06 ;Eksempel 7 2, 5- dimethylfuran- 3- carboxy( 3- isopropyloxymethylan llid) Utbytte: 92,7 % ;Sm.p.: 68,0 - 69,5° C ;<1>H NMR (CDC13) <5 ppm: ;7,55 (1H, d, J=8Hz), 7,5 (1H, m), 7,3 (1H, t, J=8Hz), 7,3 (1H, b), 7,12 (1H, d, J=8Hz), 6,1 (1H, s), 4,5 (2H, s), 3,7 (1H, m), 2,55 (3H, s) , ;2,25 (3H, s), 1,25 (6H, d, J=7Hz) ;IR (væskefilm) cm"<1>: 3321, 1651, 1072, 785 Elementæranalyse (%) : Beregnet for C^<H>2j<N>03: C 71,06 H 7,37 N 4,87 ;Funnet: C 70,35 H 7,14 N 4,91 ;Eksempel 8 ;2, 5- dimethylfuran- 3- carboxy[ 3-( 4- methoxvbenzyl) anilid] Utbytte: 86,8 % ;Sm.p.: 100,0 - 102,5° C ;^■H NMR (CDC13) 6 ppm: ;7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, t, J=8Hz), ;7,25 (1H, b), 7,1 (2H, d, J=8Hz), 6,92 (1H, d, ;J=8Hz), 6,88-6,75 (1H, m), 6,82 (2H, d, J=8Hz), ;6,05 (1H, s), 3,9 (2H, s), 3,75 (3H, s), 2,55 ;(3H, s), 2,25 (3H, s) ;IR (KBr) cm"*1: 3345, 1656, 1246, 1074, 694 <1>H NMR (CDCl3) 6 ppm<*.>; 7.92 (1H, b), 7.88 (1H, b), 7.45-7.35 (2H, m), 7.25 ( 1H, t, J=8Hz), 6.22 (1H, s) , 2.55 (3H, s) , 2.25 (3H, s), 2.25-2.2 (1H, m), 2 ,0-1.2 (10H, m) IR (KBr) cm"<1>: 3238, 1651, 1639, 1076, 781 ;Elementary analysis (%): Calculated for C2<gH>24<N>2<0> 3: ;C 70.57 H 7.11 N 8.23 Found: C 70.56 H 7.26 N 8.16 ;Example 5 ;2, 5- dimethylfuran- 3-carboxy (- 3- methoxymethylanil3. d) Yield: 73.3% ;M.p.: 102.5 - 103.5° C ;<X>H NMR (CDCl 3 ) <S ppm: ;7.55 (1H, m) , 7.52 (1H, d, J=8Hz), 7.32 (1H, t, J=8Hz), 7.32 (1H, b), 6.9 (1H, d, J=8Hz), 6.1 ;<1H, s ), 4.45 (2H, s), 3.4 (3H, s), 2.55 (3H, s), ;2.25 (3H, s) ;IR (KBr) cm"<1>: 3278 , 1645, 1237, 1107, 784 Elementary analysis (%); Calculated for ci5Hi7N03: C 69.48 H 6.61 N 5.40 ; Found: C 69.22 H 7.02 N 5.37 ; Example 6 ; 2, 5- dimethylfuran- 3-carboxy( 3- ethoxymethylanilide) Yield : 64.4% ;M.p.: 85.0 - 85.5° C ;<X>H NMR (CDCl 3 ) <S ppm: ;7.65-7.55 (2H, m) , 7.38 (1H, t#iJ=8Hz), 7.35 (1H, b), 7.15 (1H, d, J=8Hz), 6.15 (1H, s), 4.55 (2H, s), 3.58 (2H, q, J=8Hz), 2.55 (3H, s), 2.25 (3H, ;s), 1.3 (3H, t, J=8Hz) ;IR (KBr) cm "<1>: 3279, 1646, 1115, 785 ;Elementary analysis (%) : Calculated for C^gH^^NO^: ;C 70.31 H 7.01 N 5.12 ;Found: C 70.14 H 7 .27 N 5.06 ; Example 7 2, 5- dimethylfuran- 3- carboxy( 3- isopropyloxymethylan lide) Yield: 92.7% ; M.p.: 68.0 - 69.5° C ; <1>H NMR (CDCl 3 ) <5 ppm: ;7.55 (1H, d, J=8Hz), 7.5 (1H, m), 7.3 (1H, t, J=8Hz), 7.3 (1H, b), 7.12 (1H, d, J=8Hz), 6.1 (1H, s), 4.5 (2H, s), 3.7 (1H, m), 2.55 (3H, s ) , ;2.25 (3H, s), 1.25 (6H, d, J=7Hz) ;IR (liquid film) cm"<1>: 3321, 1651, 1072, 785 Elemental analysis (%) : Calculated for C ^<H>2j<N>03: C 71.06 H 7.37 N 4.87 ;Found: C 70.35 H 7.14 N 4.91 ;Eczema pel 8 ; 2, 5- dimethylfuran- 3- carboxy[ 3-( 4- methoxybenzyl) anilide] Yield: 86.8% ; M.p.: 100.0 - 102.5° C ; ^■H NMR (CDC13 ) 6 ppm: ;7.45 (1H, m), 7.35 (1H, m), 7.25 (1H, t, J=8Hz), ;7.25 (1H, b), 7.1 ( 2H, d, J=8Hz), 6.92 (1H, d, ;J=8Hz), 6.88-6.75 (1H, m), 6.82 (2H, d, J=8Hz), ; 6.05 (1H, s), 3.9 (2H, s), 3.75 (3H, s), 2.55 ;(3H, s), 2.25 (3H, s) ;IR (KBr) cm"*1: 3345, 1656, 1246, 1074, 694
Elementæranalyse (%): Beregnet for C2iH21N03: Elemental analysis (%): Calculated for C2iH21N03:
C 75,20 H 6,31 N 4,18 C 75.20 H 6.31 N 4.18
Funnet: C 75,28 H 6,32 N 4,21 Found: C 75.28 H 6.32 N 4.21
Eksempel 9 Example 9
2, 5- dimethylfuran- 3- carboxy[ 3-( 2- methoxycarbonylvinyl) anilid] Utbytte: 63,3 % 2, 5- dimethylfuran- 3- carboxy[ 3-( 2- methoxycarbonylvinyl) anilide] Yield: 63.3%
Sm.p.: 159,5 - 161,5° C Melting point: 159.5 - 161.5° C
1H NMR (CDC13) 6 ppm: 1 H NMR (CDCl 3 ) 6 ppm:
7,82 (1H, m), 7,7 (1H, d, J=15Hz), 7,58 (1H, m), 7.82 (1H, m), 7.7 (1H, d, J=15Hz), 7.58 (1H, m),
7,38 (1H, b), 7,35 (1H, t, J=8Hz), 7,28 (1H, m), 7.38 (1H, b), 7.35 (1H, t, J=8Hz), 7.28 (1H, m),
6,48 (1H, d, J=15Hz), 6,12 (1H, s), 3,82 (3H, s), 6.48 (1H, d, J=15Hz), 6.12 (1H, s), 3.82 (3H, s),
2,55 (3H, s), 2,25 (3H, s) 2.55 (3H, s), 2.25 (3H, s)
IR (KBr) cm"<1>: 3387, 1685, 1670, 1068, 800 IR (KBr) cm"<1>: 3387, 1685, 1670, 1068, 800
Elementæranalyse (%): Beregnet for C1?H^7N04: Elemental analysis (%): Calculated for C1?H^7N04:
C 68,22 H 5,72 N 4,68 C 68.22 H 5.72 N 4.68
Funnet: C 67,55 H 5,64 N 4,62 Found: C 67.55 H 5.64 N 4.62
Eksempel 10 Example 10
2, 5- dimethylfuran- 3- carboxy( 3- ethylanilid) 2, 5-dimethylfuran-3-carboxy(3-ethylanilide)
Utbytte: 91,0 % Yield: 91.0%
Sm.p.: 113 - 115° C Melting point: 113 - 115° C
Masse (m/z): 243 (M<+>), 123,94 Mass (m/z): 243 (M<+>), 123.94
<1>H NMR (CDC13) «5 ppm: <1>H NMR (CDC13) «5 ppm:
7,47-6,95 (4H, m), 6,1 (1H, s), 2,66 (3H, q), 7.47-6.95 (4H, m), 6.1 (1H, s), 2.66 (3H, q),
2,60 (3H, s), 2,29 <3H, s), 1,25 (3H, t) 2.60 (3H, s), 2.29 <3H, s), 1.25 (3H, t)
Eksempel 11 Example 11
2, 5- dimethylfuran- 3- carboxy( 3- isopropylanilid) 2, 5-dimethylfuran-3-carboxy(3- isopropylanilide)
Utbytte: 84,0 % Yield: 84.0%
Sm.p.: 79 - 80° C Melting point: 79 - 80° C
Masse (m/z): 257 (M<+>), 149,135 Mass (m/z): 257 (M<+>), 149.135
<1>H NMR (CDC13) 6 ppm: <1>H NMR (CDC13) 6 ppm:
7,47-6,98 (4H, m), 6,11 (1H, s), 2,91 (1H, q,q), 7.47-6.98 (4H, m), 6.11 (1H, s), 2.91 (1H, q,q),
2,60 (3H, s), 2,29 (3H, s), 1,26 (d, 6H) 2.60 (3H, s), 2.29 (3H, s), 1.26 (d, 6H)
Eksempel 12 Example 12
2,_, 5- dimethy lfuran- 3- carboxy ( 3- hexy lam lid) 2,_, 5- dimethyl furan- 3- carboxy (3- hexy lam lid)
(Trinn 1) Til en løsning av 3,95 g 2,5-dimethylfuran-3-carbonylklorid i 60 ml diklormethan ble det tilsatt 3,45 ml triethylamm og 2,99 ml m-jodanilm under"isavkjøling og den resulterende blanding ble omrørt ved romtemperatur i (Step 1) To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of dichloromethane was added 3.45 ml of triethylamine and 2.99 ml of m-iodanyl under ice cooling and the resulting mixture was stirred at room temperature i
6,5 timer. Etter at reaksjonsblandingen var avkjølt ble den fortynnet ved tilsetning av 50 ml diklormethan. Den fortynnede blanding ble suksessivt vasket med IN natriumhydroxyd, IN saltsyre og en mettet vandig løsning av natriumklorid, og 6.5 hours. After the reaction mixture had cooled, it was diluted by adding 50 ml of dichloromethane. The diluted mixture was washed successively with 1N sodium hydroxide, 1N hydrochloric acid and a saturated aqueous solution of sodium chloride, and
ble tørket over natriumsulfat etterfulgt av avdestillering av løsningsmidlet. Residuet ble underkastet kolonnekromatografi gjennom silicagel under dannelse av 7,64 g 2,5-dimethylfuran-3-carboxy(3-jodanilid) som blek-gule krystaller i et utbytte på 89,9 %. was dried over sodium sulfate followed by distillation of the solvent. The residue was subjected to column chromatography through silica gel to give 7.64 g of 2,5-dimethylfuran-3-carboxy(3-iodanilide) as pale yellow crystals in a yield of 89.9%.
(Trinn 2) Til en løsning av 0,68 g av krystallene erholdt i Trinn 1 i 8 ml diethylether ble det tilsatt 29,3 mg [1,1'-bis(difenylfosfino)ferrocen]palladium(Il)klorid og 11 ml IM hexylmagnesiumbromid, fremstilt fra hexylbromid og magnesium, oppdelt i seks like deler, og den resulterende blanding ble omrørt ved romtemperatur i 47 timer. Etter tilsetning av 2N saltsyre til reaksjonsblandmgen ble katalysatoren filtrert fra og filtratet ble ekstrahert med diethylether. Ekstraktet ble suksessivt vasket med en vandig løsning av natnumbicar-bonat og en mettet vandig løsning av natriumklorid og ble tørket over natriumsulfat. Etter avdestillering av løsnings-midlet ble residuet renset ved kromatografi gjennom silicagel og deretter en D-ODS-5, YMC-pakket kolonne under dannelse av 316 mg av den ønskede forbindelse som hvite krystaller i et utbytte på 52,8 %. (Step 2) To a solution of 0.68 g of the crystals obtained in Step 1 in 8 ml of diethyl ether was added 29.3 mg of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride and 11 ml of IM hexyl magnesium bromide, prepared from hexyl bromide and magnesium, divided into six equal parts, and the resulting mixture was stirred at room temperature for 47 hours. After adding 2N hydrochloric acid to the reaction mixture, the catalyst was filtered off and the filtrate was extracted with diethyl ether. The extract was successively washed with an aqueous solution of natnumbicarbonate and a saturated aqueous solution of sodium chloride and was dried over sodium sulfate. After distilling off the solvent, the residue was purified by chromatography through silica gel and then a D-ODS-5, YMC packed column to give 316 mg of the desired compound as white crystals in a yield of 52.8%.
Sm.p.: 71,5 - 72,0° C Melting point: 71.5 - 72.0° C
1H NMR (CDC13) 6 ppm: 1 H NMR (CDCl 3 ) 6 ppm:
7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, b), 7,22 7.45 (1H, m), 7.35 (1H, m), 7.25 (1H, b), 7.22
(1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (2H, m), 2,55 (3H, s), 2,25 (3H, s), (1H, t, J=8Hz), 6.95 (1H, d, J=8Hz), 6.1 (1H, s), 2.65-2.5 (2H, m), 2.55 (3H , s), 2.25 (3H, s),
1,7-1,5 (2H, m) , 1,4-1,2 (6H, m), 0,85 (3H, t, 1.7-1.5 (2H, m), 1.4-1.2 (6H, m), 0.85 (3H, t,
J=7Hz) J=7Hz)
IR (KBr) cm"<1>: 3310, 1643, 1077, 788 IR (KBr) cm"<1>: 3310, 1643, 1077, 788
Elementæranalyse (%): Beregnet for C^gH^NC^: Elemental analysis (%): Calculated for C^gH^NC^:
C 76,22 H 8,42 N 4,68 C 76.22 H 8.42 N 4.68
Funnet: C 76,15 H 8,54 N 4,55 Found: C 76.15 H 8.54 N 4.55
Ved å følge en lignende prosedyre som angitt ovenfor, men ved anvendelse av et egnet Grignard-reagens istedenfor hexylmagnesiumbromid ble følgende forbindelser erholdt. Following a similar procedure as above, but using a suitable Grignard reagent instead of hexylmagnesium bromide, the following compounds were obtained.
Eksempel 13 Example 13
2, 5- dimethylfuran- 3- carboxy( 3- butylanilid) 2, 5-dimethylfuran-3-carboxy(3-butylanilide)
Utbytte: 36,4 % Yield: 36.4%
Sm.p.: 77,0 - 80,0° C Melting point: 77.0 - 80.0° C
<1>H NMR (CDC13) 6 ppm: <1>H NMR (CDC13) 6 ppm:
7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, b), 7,22 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,55 (2H, m), 2,55 (3H, s), 2,25 (3H, s), 1,6 (2H, m), 1,35 (2H, m), 0,92 (1H, t, J=7Hz) IR (KBr) cm"<1>: 3285, 1646, 1075, 702 Elementæranalyse (%) : Beregnet for Cj^H^N<C>^: C 75,25 H 7,80 N 5,16 7.45 (1H, m), 7.35 (1H, m), 7.25 (1H, b), 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.55 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.6 (2H, m ), 1.35 (2H, m), 0.92 (1H, t, J=7Hz) IR (KBr) cm"<1>: 3285, 1646, 1075, 702 Elemental analysis (%) : Calculated for Cj^H ^N<C>^: C 75.25 H 7.80 N 5.16
Funnet: C 75,13 H 7,87 N 5,13 Found: C 75.13 H 7.87 N 5.13
Eksempel 14 Example 14
2, 5- dimethylfuran- 3- carboxy( 3- sek- butylanilid) Utbytte: 38,1 % 2, 5-dimethylfuran-3-carboxy(3-sec-butylanilide) Yield: 38.1%
Sm.p.: 80,0 - 81,0° C Melting point: 80.0 - 81.0° C
1H NMR (CDC13) <5 ppm: 1 H NMR (CDCl 3 ) <5 ppm:
7,4 (1H, m) , 7,38 (1H, m), 7,25 (1H, b), 7,22 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (1H, m), 2,55 (3H, s), 2,25 (3H, s), 1,68-1,5 (2H, m), 1,25 (3H, d, J=7Hz), 0,85 (3H, 7.4 (1H, m), 7.38 (1H, m), 7.25 (1H, b), 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.5 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 1.68-1.5 (2H, m), 1.25 (3H, d, J=7Hz), 0.85 (3H,
t, J=7Hz) t, J=7Hz)
IR (KBr) cm"<1>: 3255, 1647, 1078, 791 Elementæranalyse (%): Beregnet for C^<I>^^<N>C^: C 75,25 H 7,80 N 5,16 IR (KBr) cm"<1>: 3255, 1647, 1078, 791 Elemental analysis (%): Calculated for C^<I>^^<N>C^: C 75.25 H 7.80 N 5.16
Funnet: C 75,19 H 7,68 N 5,14 Found: C 75.19 H 7.68 N 5.14
Eksempel 15 Example 15
2, 5- dimethylfuran- 3- carboxy( 3- pentylanilid) Utbytte: 18,3 % 2, 5-dimethylfuran-3-carboxy(3-pentylanilide) Yield: 18.3%
Sm.p.: 97,0 - 97,5° C Melting point: 97.0 - 97.5° C
1H NMR (CDC13) 6 ppm: 1 H NMR (CDCl 3 ) 6 ppm:
7,45 (1H, m), 7,35 (1H, m), 7,28 (1H, b), 7,25 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (2H, m), 2,55 (3H, s), 2,25 (3H, s), 1,7-1,5 (2H, m), 1,4-1,2 (4H,m), 0,88 (3H, t, J=7Hz) 7.45 (1H, m), 7.35 (1H, m), 7.28 (1H, b), 7.25 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.5 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.7-1.5 (2H, m), 1.4-1.2 (4H,m), 0.88 (3H, t, J=7Hz)
IR (KBr) cm"<1>: 3304, 1644, 1077, 710 IR (KBr) cm"<1>: 3304, 1644, 1077, 710
Elementæranalyse (%) : Beregnet for C-^H^NC^:Elemental analysis (%) : Calculated for C-^H^NC^:
C 75,76 H 8,12 N 4,91 C 75.76 H 8.12 N 4.91
Funnet: C 75,77 H 8,18 N 5,06 Found: C 75.77 H 8.18 N 5.06
Eksempel 16 Example 16
2, 5- dimethylfuran- 3- carboxy-( 3- cyklohexylanilid) 2, 5- dimethylfuran- 3- carboxy-( 3- cyclohexylanilide)
Utbytte: 52,7 % Yield: 52.7%
Sm.p.: 113,0 - 114,5° C Melting point: 113.0 - 114.5° C
"hi NMR (CDC13) 6 ppm: "hi NMR (CDCl 3 ) 6 ppm:
7,48 (1H, m), 7,35 (1H, m), 7,28 (1H, b), 7,25 7.48 (1H, m), 7.35 (1H, m), 7.28 (1H, b), 7.25
(1H, t, J=8Hz), 6,98 (1H, d, J=8Hz), 6,1 (1H, s), (1H, t, J=8Hz), 6.98 (1H, d, J=8Hz), 6.1 (1H, s),
2,58 (3H, s), 2,55-2,45 (1H, m), 2,25 (3H, s), 2.58 (3H, s), 2.55-2.45 (1H, m), 2.25 (3H, s),
1,95-1,68 (5H, m) , 1,55-1,15 (5H, m) 1.95-1.68 (5H, m) , 1.55-1.15 (5H, m)
IR (KBr) cm"<1>: 3324, 1646, 1230, 1074, 791 IR (KBr) cm"<1>: 3324, 1646, 1230, 1074, 791
Elementæranalyse (%) : Beregnet for ci<jH23N02: Elemental analysis (%) : Calculated for ci<jH23N02:
C 76,74 H 7,80 N 4,71 C 76.74 H 7.80 N 4.71
Funnet: C 76,62 H 7,78 N 4,67 Found: C 76.62 H 7.78 N 4.67
Eksempel 17 Example 17
2 , 5- dimethylfuran- 3- carboxy ( 3- benzylanilid) 2, 5-dimethylfuran-3-carboxy (3-benzylanilide)
Utbytte: 59.,8 % Yield: 59.8%
Sm.p.: 123,0 - 125,0° C Melting point: 123.0 - 125.0° C
XH NMR (CDC13) 6 ppm: 1 H NMR (CDCl 3 ) 6 ppm:
7,45 (1H, m), 7,38 (1H, m), 7,35-7,15 (7H, m), 7.45 (1H, m), 7.38 (1H, m), 7.35-7.15 (7H, m),
6,95 (1H, d, J=8Hz), 3,98 (2H, s), 2,55 (3H, s), 6.95 (1H, d, J=8Hz), 3.98 (2H, s), 2.55 (3H, s),
2,25 (3H, s) 2.25 (3H, s)
IR (KBr) cm"<1>: 3314, 1640, 1078, 777, 701 IR (KBr) cm"<1>: 3314, 1640, 1078, 777, 701
Elementæranalyse (%): Beregnet for C21H19N02: Elemental analysis (%): Calculated for C21H19N02:
C 78,66 H 6,27 N 4,59 C 78.66 H 6.27 N 4.59
Funnet: C 77,76 H 6,28 N 4,55 Found: C 77.76 H 6.28 N 4.55
Referanseeksempel 1 Reference example 1
Ethyl- 2, 5- dimethylfuran- 3- carboxylat Ethyl-2,5-dimethylfuran-3-carboxylate
Til en suspensjon av 2,4 g natriumhydrid (60 % dis-persjon i mineralolje) i 10 ml N,N-dimethylformamid (heretter forkortet som DMF) ble det dråpevis tilsatt en løsning av 6,5 ml ethylacetat i 5 ml DMF under omrøring og under isavkjøling, og 5,97 ml kloraceton ble dråpevis tilsatt under omrøring og under isavkjøling. Etter omrøring ved romtemperatur i 3 timer ble reaksjonsblandingen helt over i vann og den vandige blanding ble ekstrahert med ethylacetat. Ekstraktet ble vasket med en mettet vandig løsning av natriumklorid og ble tørket over vannfritt natriumsulfat. Etter avdestillering av løs-ningsmidlet under redusert trykk ble residuet destillert i vakuum under dannelse av 8,01 g ethylacetonitril-acetoacetat med kokepunkt 105°C/2 mmHg i et utbytte på 86 %. To a suspension of 2.4 g of sodium hydride (60% dispersion in mineral oil) in 10 ml of N,N-dimethylformamide (hereafter abbreviated as DMF) a solution of 6.5 ml of ethyl acetate in 5 ml of DMF was added dropwise with stirring and under ice-cooling, and 5.97 ml of chloroacetone was added dropwise with stirring and under ice-cooling. After stirring at room temperature for 3 hours, the reaction mixture was poured into water and the aqueous mixture was extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride and was dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was distilled in vacuum to form 8.01 g of ethylacetonitrile-acetoacetate with a boiling point of 105°C/2 mmHg in a yield of 86%.
Til en løsning av den således erholdte ester i 20 ml ethanol ble det tilsatt 2 g p-toluensulfonsyre og den resulterende blanding ble oppvarmet under tilbakeløpskjølmg i 2 timer. Reaksjonsblandingen fikk avkjøle til romtemperatur og løsningsmidlet ble destillert fra under redusert trykk. Residuet ble oppløst i ethylacetat og løsningen ble vasket med en mettet vandig løsning av natriumklorid, etterfulgt av tørking over vannfritt magnesiumsulfat. Etter avdestillering av løsningsmidlet under redusert trykk ble residuet renset ved kolonnekromatografi gjennom silicagel under anvendelse av en 10:1 blanding av n-hexan og ethylacetat som elueringsmiddel, under dannelse" av 5,14 g ethyl-2,5-dimethylfuran-3-carboxylat i et utbytte på 71 %. To a solution of the thus obtained ester in 20 ml of ethanol was added 2 g of p-toluenesulfonic acid and the resulting mixture was heated under reflux for 2 hours. The reaction mixture was allowed to cool to room temperature and the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate and the solution was washed with a saturated aqueous solution of sodium chloride, followed by drying over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by column chromatography through silica gel using a 10:1 mixture of n-hexane and ethyl acetate as eluent, yielding 5.14 g of ethyl 2,5-dimethylfuran-3-carboxylate in a yield of 71%.
Referanseeksempel 2 Reference example 2
2, 5- dimethylfuran- 3- carboxylsyre 2, 5- dimethylfuran- 3- carboxylic acid
En blanding av 3,2 g ethyl-2,5-dimethylfuran-3-carboxylat, 35 ml ethanol og 20 ml 2N natriumhydroxyd ble omrørt ved romtemperatur i 1,5 timer, etterfulgt av oppvarming under tilbakeløpskjøling i 1 time. Etter at reaksjonsblandingen var avkjølt til romtemperatur, ble den konsentrert under redusert trykk. Residuet ble oppløst i vann og ble surgjort med fortynnet svovelsyre. De utfelte krystaller ble oppsamlet ved filtrering, ble vasket med vann og tørket under dannelse av 2,27 g 2,5-dimethylfuran-3-carboxylsyre i et utbytte på 85 %. A mixture of 3.2 g of ethyl 2,5-dimethylfuran-3-carboxylate, 35 ml of ethanol and 20 ml of 2N sodium hydroxide was stirred at room temperature for 1.5 hours, followed by heating under reflux for 1 hour. After the reaction mixture was cooled to room temperature, it was concentrated under reduced pressure. The residue was dissolved in water and acidified with dilute sulfuric acid. The precipitated crystals were collected by filtration, washed with water and dried to give 2.27 g of 2,5-dimethylfuran-3-carboxylic acid in a yield of 85%.
Forbindelsen med generell formel (I) nevnt ovenfor og preparatet inneholdende forbindelsen (I) som aktiv bestanddel og som foreliggende oppfinnelse angår, kan anvendes ved blanding med bærere, eller om nødvendig, med ethvert annet additiv, etterfulgt av fremstilling av formuleringer som vanligvis anvendes, slik som oljeløsmng, emulgerbart konsentrat, oppløseliggjører, pasta, fuktbart pulver, strømbart materiale, tørt strømbart materiale, spray og maling, og formuleringen kan deretter anvendes i henhold til enhver kjent metode for trekonserveringsbehandlmg. Som additiver som hensiktsmessig anvendes for å bedre egenskapene av formuleringen og for å styrke den trekonserverende effekt, kan nevnes kationiske, anioniske og ikke-ioniske overflateaktive midler, forskjellige høypolymere forbindelser slik som methyl-cellulose og vmylacetatharpiks, og vann-avs tø tende midler slik som silikonolje og parafin. Det er unødvendig å si at kombinert anvendelse kan være mulig med andre trekonservenngs-midler, fungicider og baktericider, innbefattende organiske jodforbindelser slik som "Sanplas", "lF-1000" og "Troysan", azolforbmdelser slik som "Propiconazole" og "Tebuconazole", "Thiabendazole", "Dichlofluanid" og kvaternære ammoniumsalt-forbmdelser; med insekticider innbefattende pyrethroider slik som "Permethrin", "Etofenprox", "Cypermethrin", "Silaneophen", "Tralomethrin", organiske fosforforbindelser slik som "Chloropyrifos", "Phoxim" og "Propetamphos" og "Imidacroprid"; og med potensiermgsmidler slik som bis-(2,3,3,3-tetraklorpropyl)ether. En forøket effekt kan forventes ved kombinert bruk på denne måte. Selv om innholdet av forbindelsen ifølge oppfinnelsen kan variere innen et vidt område, avhengig av formuleringen eller av objektet, kan det ved påføring vanligvis være hensiktsmessig å anvende fra 0,1 til 95 vekt%, fortrinnsvis fra 0,2 til 60 vekt%. Disse formuleringer er anvendbare ved vanlige metoder for tre-behandling: for eksempel belegning, dispergering, dypp-behandlmg, blanding, impregnering eller blandmgsbehandlmg med et adhesiv. The compound with general formula (I) mentioned above and the preparation containing the compound (I) as active ingredient and to which the present invention relates, can be used by mixing with carriers, or if necessary, with any other additive, followed by the preparation of formulations that are usually used, such as oil solution, emulsifiable concentrate, solubilizer, paste, wettable powder, flowable material, dry flowable material, spray and paint, and the formulation can then be used according to any known method of wood preservation treatment. As additives which are suitably used to improve the properties of the formulation and to strengthen the wood preservative effect, mention can be made of cationic, anionic and non-ionic surface-active agents, various high-polymeric compounds such as methyl cellulose and vmylacetate resin, and water-repellent agents such as such as silicone oil and paraffin. Needless to say, combined application may be possible with other wood preservatives, fungicides and bactericides, including organic iodine compounds such as "Sanplas", "lF-1000" and "Troysan", azole compounds such as "Propiconazole" and "Tebuconazole". , "Thiabendazole", "Dichlofluanid" and quaternary ammonium salt compounds; with insecticides including pyrethroids such as "Permethrin", "Etofenprox", "Cypermethrin", "Silaneophen", "Tralomethrin", organophosphorus compounds such as "Chloropyrifos", "Phoxim" and "Propetamphos" and "Imidacroprid"; and with potentiating agents such as bis-(2,3,3,3-tetrachloropropyl)ether. An increased effect can be expected with combined use in this way. Although the content of the compound according to the invention can vary within a wide range, depending on the formulation or on the object, when applied it can usually be appropriate to use from 0.1 to 95% by weight, preferably from 0.2 to 60% by weight. These formulations are usable by common methods of wood treatment: for example coating, dispersing, dipping, mixing, impregnating or mixing treatment with an adhesive.
De etterfølgende forbindelser ifølge referanseeksempel 3 og 4 ble fremstilt på samme måte som i eksempel 1 The subsequent compounds according to reference examples 3 and 4 were prepared in the same way as in example 1
Referanseeksempel 3 Reference example 3
3'- ethyl- 2, 5- dimethylfuran- 3- carboxanilid 3'-ethyl-2,5-dimethylfuran-3-carboxanilide
Utbytte 91,0% Yield 91.0%
Smp 113-115 °C Mp 113-115 °C
Masse (m/z) 243 (M+) , 123,94 Mass (m/z) 243 (M+), 123.94
<X>H NMR (CDC13) 5 ppm <X>H NMR (CDCl 3 ) 5 ppm
7,47-6,95 (4H, m), 6,1 (1H, s), 2,66 (3H, q), 2,60 (3H, s), 2,29 (3H, s), 1,25 (3H, t) 7.47-6.95 (4H, m), 6.1 (1H, s), 2.66 (3H, q), 2.60 (3H, s), 2.29 (3H, s), 1 .25 (3H, h)
Referanseeksempel 4 Reference example 4
3'- isopropyl- 2, 5- dimethylfuran- 3- carboxanilid 3'-isopropyl-2,5-dimethylfuran-3-carboxanilide
Utbytte 84,0% Yield 84.0%
Smp 79-80 °C Mp 79-80 °C
Masse (m/z) 257 (M+) , 149,135 Mass (m/z) 257 (M+), 149.135
<X>H NMR (CDCI3) 5 ppm <X>H NMR (CDCl 3 ) 5 ppm
7,47-6,98 (4H, m), 6,11 (1H, s), 2,91 (1H, q, q), 2,60 <3H, s), 2,29 (3H, s), 1,26 (d, 6H) 7.47-6.98 (4H, m), 6.11 (1H, s), 2.91 (1H, q, q), 2.60 <3H, s), 2.29 (3H, s) , 1.26 (d, 6H)
Referanseeksempel 5 Reference example 5
3'- hexyl- 2, 5- dimethylfuran- 3- carboxanilid 3'-hexyl-2,5-dimethylfuran-3-carboxanilide
(Trinn 1) Til en løsning av 3,95 g 2,5-dimethylfuran-3-carbonylklorid 1 60 ml diklormethan ble det tilsatt 3,45 ml triethylamin og 2,99 ml m-jodanilin under isavkjøling, og den resulterende blanding ble omrørt ved romtemperatur 1 6,5 timer Etter at reaksjonsblandingen var avkjølt, ble den fortynnet ved tilsetning av 50 ml diklormethan Den fortynnede blanding ble suksessivt vasket med 1 N natriumhydroxyd, 1 N saltsyre og en mettet, vandig løsning av natriumklorid og ble tørket over natriumsulfat etterfulgt av avdestillering av løsningsmidlet Residuet ble underkastet kolonnekromatograf1 gjennom silikagel under dannelse av 7,64 g 2,5-dimethylfuran-3-carboxy(3-jodanilid) som blekgule krystaller 1 et utbytte på 89,9% (Step 1) To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of dichloromethane, 3.45 ml of triethylamine and 2.99 ml of m-iodaniline were added under ice-cooling, and the resulting mixture was stirred at room temperature 1 6.5 hours After the reaction mixture was cooled, it was diluted by adding 50 ml of dichloromethane. The diluted mixture was washed successively with 1 N sodium hydroxide, 1 N hydrochloric acid and a saturated aqueous solution of sodium chloride and was dried over sodium sulfate followed by of distilling off the solvent The residue was subjected to column chromatography 1 through silica gel forming 7.64 g of 2,5-dimethylfuran-3-carboxy(3-iodanilide) as pale yellow crystals 1 a yield of 89.9%
(Trinn 2) Til en løsning av 0,68 g av krystallene erholdt 1 trinn 1 1 8 ml diethylether, ble det tilsatt 29,3 mg [1,1<1->bis(difenylfosfino)ferrocen]palladium(II)klorid og 11 ml 1 M hexylmagnesiumbromid, fremstilt fra hexylbromid og magnesium, (Step 2) To a solution of 0.68 g of the crystals obtained in step 1 in 1 8 ml of diethyl ether, 29.3 mg of [1,1<1->bis(diphenylphosphino)ferrocene]palladium(II) chloride was added and 11 ml of 1 M hexyl magnesium bromide, prepared from hexyl bromide and magnesium,
oppdelt i seks like store deler, og den resulterende blanding ble omrørt ved romtemperatur i 47 timer Etter tilsetning av 2 N saltsyre til reaksjonsblandingen ble katalysatoren filtrert fra, og filtratet ble ekstrahert med diethylether Ekstrakten ble suksessivt vasket med en vandig løsning av natriumbicarbonat og en mettet, vandig løsning av natriumklorid og tørket over natriumsulfat Etter avdestillering av løsningsmidlet ble residuet renset ved kromatografi gjennom silikagel og deretter D-ODS-5, YMC-pakket kolonne under dannelse av 316 mg av den ønskede forbindelse som hvite krystaller i et utbytte på 52,8% divided into six equal parts, and the resulting mixture was stirred at room temperature for 47 hours. After addition of 2 N hydrochloric acid to the reaction mixture, the catalyst was filtered off, and the filtrate was extracted with diethyl ether. The extract was successively washed with an aqueous solution of sodium bicarbonate and a saturated , aqueous solution of sodium chloride and dried over sodium sulfate After distilling off the solvent, the residue was purified by chromatography through silica gel and then D-ODS-5, YMC packed column to give 316 mg of the desired compound as white crystals in a yield of 52, 8%
Smp 71,5-72,0 °C Mp 71.5-72.0 °C
<X>H NMR (CDC13) 5 ppm <X>H NMR (CDCl 3 ) 5 ppm
7,45 (1H, m), 7,35 (1H, ra), 7,25 (1H, b), 7,22 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (2H, m), 2,55 (3H, s), 2,25 (3H, s), 1,7-1,5 (2H, m) , 1,4-1,2 (6H, m), 0,85 (3H, t, J=7Hz) 7.45 (1H, m), 7.35 (1H, ra), 7.25 (1H, b), 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.5 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.7-1.5 (2H, m) , 1.4-1.2 (6H, m), 0.85 (3H, t, J=7Hz)
IR (KBr) cm"<1> 3310, 1643, 1077, 788 IR (KBr) cm"<1> 3310, 1643, 1077, 788
Elementæranalyse (%) Beregn for C19H25NO2 C 76,22, H 8,42, Elemental analysis (%) Calculate for C19H25NO2 C 76.22, H 8.42,
N 4,68 Funnet C 76,15, H 8,54, N 4,55 N 4.68 Found C 76.15, H 8.54, N 4.55
Ved å følge en lignende prosedyre som beskrevet ovenfor, men ved anvendelse av et egnet Grignard-reagens istedenfor hexylmagnesiumbromid, ble følgende forbindelser erholdt By following a similar procedure as described above, but using a suitable Grignard reagent instead of hexylmagnesium bromide, the following compounds were obtained
Referanseeksempel 6 Reference example 6
3'- butyl- 2, 5- dimethylfuran- 4- carboxanilid 3'-butyl-2,5-dimethylfuran-4-carboxanilide
Utbytte 36,4% Dividend 36.4%
Smp 77,0-80,0 °C Mp 77.0-80.0 °C
<X>H NMR (CDCI3) 5 ppm <X>H NMR (CDCl 3 ) 5 ppm
7,45 (1H, m), 7,35 <1H, m), 7,25 (1H, b), 7,22 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,55 (2H, m), 2,55 (3H, s), 2,25 (3H, s), 1,6 (2H, m), 1,35 (2H, m), 0,92 (1H, t, J=7Hz) IR (KBr) cm"<1> 3285, 1646, 1075, 702 7.45 (1H, m), 7.35 <1H, m), 7.25 (1H, b), 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.55 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.6 (2H, m ), 1.35 (2H, m), 0.92 (1H, t, J=7Hz) IR (KBr) cm"<1> 3285, 1646, 1075, 702
Elementæranalyse (%) Beregn for C17H2iN02 C 75,25, H 7,80, Elemental analysis (%) Calculate for C17H2iN02 C 75.25, H 7.80,
N 5,16 Funnet 75,13, H 7,87, N 5,13 N 5.16 Found 75.13, H 7.87, N 5.13
Referanseeksempel 7 Reference example 7
3'- sek - butyl- dimethylfuran- 3- carboxanilid 3'-sec-butyl-dimethylfuran-3-carboxanilide
Utbytte 38,1% Dividend 38.1%
Smp 80,0-81,0 °C Mp 80.0-81.0 °C
<X>H NMR (CDCI3) 5 ppm <X>H NMR (CDCl 3 ) 5 ppm
7,4 (1H, m), 7,38 (1H, ra), 7,25 (1H, b), 7,22 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (1H, m), 2,55 (3H, s), 2,25 (3H, s), 1,68-1,5 (2H, m), 1,25 {3H, d, J=7Hz), 0,85 (3H, t, J=7Hz) 7.4 (1H, m), 7.38 (1H, ra), 7.25 (1H, b), 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.5 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 1.68-1.5 (2H, m), 1.25 {3H, d, J=7Hz), 0.85 (3H, t, J=7Hz)
IR (KBr) cm"<1> 3255, 1647, 1078, 791 IR (KBr) cm"<1> 3255, 1647, 1078, 791
Elementæranalyse (%) Beregn for Ci7H2iN02 C 75,25, H 7,80, Elemental analysis (%) Calculate for Ci7H2iN02 C 75.25, H 7.80,
N 5,16 Funnet C 75,19, H 7,68, N 5,14 N 5.16 Found C 75.19, H 7.68, N 5.14
Referanseeksempel 8 Reference example 8
3'- pentyl- 2, 5- dimethylfuran- 3- carboxamlid 3'-pentyl-2,5-dimethylfuran-3-carboxamide
Utbytte 18,3% Dividend 18.3%
Smp 97,0-97,5 °C Mp 97.0-97.5 °C
<X>H NMR (CDCI3) S ppm <X>H NMR (CDCl 3 ) S ppm
7,45 (1H, m), 7,35 (1H, rn), 7,28 (1H, b), 7,25 (1H, t, J=8Hz), 6,95 (1H, d, J=8Hz), 6,1 (1H, s), 2,65-2,5 (2H, ra), 2,55 (3H, s), 2,25 (3H, s) , 1,7-1,5 (2H, m) , 1,4-1,2 (4H, rn), 0,88 (3H, t, J=7Hz) 7.45 (1H, m), 7.35 (1H, rn), 7.28 (1H, b), 7.25 (1H, t, J=8Hz), 6.95 (1H, d, J= 8Hz), 6.1 (1H, s), 2.65-2.5 (2H, ra), 2.55 (3H, s), 2.25 (3H, s), 1.7-1.5 (2H, m) , 1.4-1.2 (4H, rn), 0.88 (3H, t, J=7Hz)
IR (KBr) cm"<1> 3304, 1644, 1077, 710 IR (KBr) cm"<1> 3304, 1644, 1077, 710
Elementæranalyse (%) Beregn for Ci8H23N02 C 75,76, H 8,12, Elemental analysis (%) Calculate for Ci8H23N02 C 75.76, H 8.12,
N 4,91 Funnet C 75,77, H 8,18, N 5,06 N 4.91 Found C 75.77, H 8.18, N 5.06
Testeksempler på trekonservering Test examples of wood preservation
Effektiviteten av trekonserveringsmidlene ifølge foreliggende oppfinnelse illustreres konkret ved følgende eksempler. The effectiveness of the wood preservatives according to the present invention is concretely illustrated by the following examples.
(1) Ifølge testmetoden for trekonservering beskrevet 1 the Japan Industrial Standards [JIS A-9201 (1991)] ble hver av testforbindelsene oppløst til en definert konsentrasjon 1 methanol. Løsningen ble impregnert under redusert trykk 1(1) According to the test method for wood preservation described 1 the Japan Industrial Standards [JIS A-9201 (1991)], each of the test compounds was dissolved to a defined concentration 1 methanol. The solution was impregnated under reduced pressure 1
Sugi (japansk seder) splintved (2x2x1) cm og ble deretter lufttørket. Enhver test ble gjentatt 10 ganger hvori én syklus av behandlingen var omrøring 1 vann 1 8 timer og deretter oppvarming 1 16 timer til 60° C. Testmaterialet ble anbragt på floraen av Serpula lacrymans som på forhånd var blitt dyrket Sugi (Japanese cedar) sapwood (2x2x1) cm and was then air dried. Each test was repeated 10 times in which one cycle of the treatment was stirring 1 water 1 8 hours and then heating 1 16 hours at 60° C. The test material was placed on the flora of Serpula lacrymans which had previously been cultivated
på et kvartssandmedium (2 % maltekstrakt, 1 % glukose, 0,3 % pepton og 0,2 % gjær) og ble påtvunget forråtnelse ved 20° C on a quartz sand medium (2% malt extract, 1% glucose, 0.3% peptone and 0.2% yeast) and was forced to putrefy at 20°C
i 12 uker. Fra forskjellen mellom tørrvekten av testmaterialet før testen og etter testen ble graden av vektreduksjon erholdt. Tabell 2 viser resultatene. Testen ble utført ved anvendelse av 9 prøver for hver betingelse, og verdiene vist i Tabell 2 er de midlere verdier beregnet fra 9 prøver. for 12 weeks. From the difference between the dry weight of the test material before the test and after the test, the degree of weight reduction was obtained. Table 2 shows the results. The test was carried out using 9 samples for each condition, and the values shown in Table 2 are the mean values calculated from 9 samples.
Kontrollforbindelse 1: 4-klorfenyl-3-jodpropargylformal Produkt fra Nagase Co.f Ltd.: IF-1000 Control compound 1: 4-chlorophenyl-3-iodopropargylformal Product of Nagase Co.f Ltd.: IF-1000
Fra de ovenfor viste data forhindret forbindelsen av generell formel (I) forråtnelse av treprøvene på grunn av tre-råtnende fungi i en signifikant grad. (2) Hver av 0,1 w/v % methanolløsninger av forbindelsen ifølge oppfinnelsen og kontrollmidlet ble impregnert i testmaterialet (en Sugi (japansk seder) splintved, 2 x 2 x 0,5 cm) under redusert trykk og ble deretter lufttørket. Hver test ble gjentatt to ganger, hvori én syklus av behandlingen var vasking (ca. 2 liter tilført pr. minutt) med vann i 5 timer, og deretter oppvarming i 19 timer ved 60° C. Etter tørr luftsterili-sering ble testprøvene fremstilt. From the data shown above, the compound of general formula (I) prevented decay of the wood samples due to wood-rotting fungi to a significant extent. (2) Each of 0.1 w/v% methanol solutions of the compound of the invention and the control agent were impregnated into the test material (a Sugi (Japanese cedar) sapwood, 2 x 2 x 0.5 cm) under reduced pressure and then air dried. Each test was repeated twice, in which one cycle of the treatment was washing (about 2 liters added per minute) with water for 5 hours, and then heating for 19 hours at 60° C. After dry air sterilization, the test samples were prepared.
Testmaterialene ble anbragt på en flora av The test materials were placed on a flora of
Coriolus versicolor som er en lignm-dekomponerende fungus, Coriolus versicolor which is a lignm-decomposing fungus,
og av Tyromyces palustris som er en cellulose-dekomponerende fungus, og hvor begge er anerkjente fungalarter for utprøvning av trekonserverende effekt. Begge fungi var på forhånd blitt and of Tyromyces palustris, which is a cellulose-decomposing fungus, and where both are recognized fungal species for testing the wood preservative effect. Both fungi had previously become
dyrket på et agarmedium (2 % maltekstrakt, 1 % glukose og 0,5 % pepton). Etter at treprøvene var påtvunget en svekkelse ved 26° C i 3 uker ble effektiviteten bestemt fra graden av hyfevekst på testmaterialet, og nærværet eller fraværet av nedsatt maksimal knusestyrke. Tabell 3 viser resultatene. grown on an agar medium (2% malt extract, 1% glucose and 0.5% peptone). After the wood samples were forced to weaken at 26°C for 3 weeks, the effectiveness was determined from the degree of hyphal growth on the test material, and the presence or absence of reduced maximum crushing strength. Table 3 shows the results.
Den trepreventive virksomhet ble bedømt ved føl-gende kriterier. The three-preventive activity was judged by the following criteria.
+: Ingen hyfevekst ble observert på testmaterialet, og ingen forskjell ble funnet i den maksimale knusestyrke fra den friske treprøve. +: No hyphal growth was observed on the test material, and no difference was found in the maximum crushing strength from the healthy wood sample.
+: En liten hyfevekst ble observert på testmaterialet, eller en liten reduksjon ble funnet i den maksimale knusestyrke. +: A slight hyphal growth was observed on the test material, or a slight reduction was found in the maximum crushing strength.
Hyfevekst ble observert på testmaterialet, eller en klar reduksjon ble funnet i den maksimale knusestyrke. Hyphal growth was observed on the test material, or a clear reduction was found in the maximum crushing strength.
Koritrollforbindelse 2: 3-brom-2,3-dijod-2-propenylethyl-carbonat Coritrol compound 2: 3-bromo-2,3-diiodo-2-propenylethyl carbonate
Produkt fra Sankyo Co., Ltd.: "Sanplas" Product of Sankyo Co., Ltd.: "Sanplas"
Når preparatet ifølge oppfinnelsen skal anvendes kan kombmasjonsforholdet hensiktsmessig velges avhengig av typen av tre og typen av tremateriale som skal behandles med trekonservenngsmidlet, eller behandlingsmåte (for eksempel belegnmg, dypping, dispergering, impregnering, blanding og blanding med et adhesiv). Vanligvis kan kombmasjonsforholdet mellom dimethylfurancarboxyanilid og ethvert annet trekonserveringsmiddel være fra 240:1 til 1:35, fortrinnsvis fra 30:1 When the preparation according to the invention is to be used, the combination ratio can be suitably chosen depending on the type of wood and the type of wood material to be treated with the wood preservative, or treatment method (for example coating, dipping, dispersing, impregnation, mixing and mixing with an adhesive). Generally, the combination ratio between dimethylfurancarboxyanilide and any other wood preservative may be from 240:1 to 1:35, preferably from 30:1
til 1:10, og helst fra 5:1 til 1:5. to 1:10, and preferably from 5:1 to 1:5.
Innholdet av preparatet ifølge oppfinnelsen kan forandres innen et vidt område avhengig av formuleringen. Generelt kan innholdet være fra 0,1 til 95 %, fortrinnsvis The content of the preparation according to the invention can be changed within a wide range depending on the formulation. In general, the content may be from 0.1 to 95%, preferably
fra 0,2 til 60 %, i formuleringen. from 0.2 to 60%, in the formulation.
I tillegg til de publikasjoner som er tidligere nevnt, skal det henvises til JP-A-05112406 (D3) som beskriver 2,5-dimethylfurancarboxylanilidderivater som er angitt å ha trekonserverende egenskaper JP-A-5010376 (D4) beskriver substituerte 2,5-dimethylfurancarboxyanilidderivater som er angitt å være plantebeskyttere selv om deres aktivitet på treråtnende fungi ikke er beskrevet In addition to the publications previously mentioned, reference should be made to JP-A-05112406 (D3) which describes 2,5-dimethylfurancarboxylanilide derivatives which are stated to have wood preserving properties JP-A-5010376 (D4) describes substituted 2,5- dimethylfurancarboxyanilide derivatives indicated to be plant protectants although their activity on wood-rotting fungi has not been described
Det skal også vises til et ytterligere dokument, GB Reference must also be made to a further document, GB
l 592 837, som beskriver N-halogenalkylthioderivater av 2,5-dimethylfurancarboxyanilidforbmdelser som er angitt å ha trekonserverende aktivitet, så vel som mellomprodukter for deres fremstilling Enkelte av disse mellomprodukter er forbindelser som i foreliggende søknad er blitt vist å ha glimrende trekonserverende aktivitet Som poengtert nedenfor, finnes det intet i GB 1 592 837 som ville kunne lede fagmannen til å anta at de angjeldende forbindelser, som er 3<1->alkyl-2,5-dimethylfurancarboxyanilidderivater, ville kunne ha annen anvendelse enn mellomprodukter ved syntesen av N-halogenalkylthioforbindelsene beskrevet i angitte publikasjon 1 592 837, which describes N-haloalkylthio derivatives of 2,5-dimethylfurancarboxyanilide compounds which are indicated to have wood preservative activity, as well as intermediates for their preparation Some of these intermediates are compounds which in the present application have been shown to have excellent wood preservative activity As pointed out below, there is nothing in GB 1 592 837 which would lead the person skilled in the art to assume that the compounds in question, which are 3<1->alkyl-2,5-dimethylfurancarboxyanilide derivatives, could have other uses than intermediates in the synthesis of N- the haloalkylthio compounds described in the indicated publication
Den mest nærliggende publikasjon er uten tvil D3 Aktiviteten av forbindelsen 2,5-dimethylfuran-3-carboxyanilid beskrevet i D3, ble sammenlignet med hensyn til den trekonserverende aktivitet med enkelte av de nærmeste strukturelle analoger fra forbindelsene av formel (I) og formel (I<1>) The closest publication is without a doubt D3 The activity of the compound 2,5-dimethylfuran-3-carboxyanilide described in D3 was compared with respect to the wood preservative activity with some of the closest structural analogues from the compounds of formula (I) and formula (I <1>)
I et første forsøk ble den trekonserverende aktivitet av den kjente forbindelse 2,5-dimethylfuran-3-carboxyanilid sammenlignet med den av 3'-isopropyl-2,5-dimethylfuran-3-carboxy-anilid, hvor den sistnevnte forbindelse er en forbindelse av formel (I<1>) Deres aktivitet overfor Coriolous versicolor og Serupula lacrymans ble testet i henhold til den prosedyre som er angitt i beskrivelsen Resultatene er vist nedenfor Disse data viser klart at forbindelsene av formel (I') ifølge oppfinnelsen utviser en betydelig forbedret trekonserverende aktivitet sammenlignet med den kjente forbindelse, og at denne forbedrede aktivitet ikke på noen måte kan utledes fra den kjente teknikk In a first experiment, the wood preservative activity of the known compound 2,5-dimethylfuran-3-carboxyanilide was compared with that of 3'-isopropyl-2,5-dimethylfuran-3-carboxyanilide, where the latter compound is a compound of formula (I<1>) Their activity against Coriolous versicolor and Serupula lacrymans was tested according to the procedure indicated in the description The results are shown below These data clearly show that the compounds of formula (I') according to the invention exhibit a significantly improved wood preservative activity compared to the known compound, and that this improved activity cannot in any way be derived from the known technique
I det etterfølgende beskrives en ytterligere test med hensyn til trekonserverende aktivitet for forbindelser ifølge oppfinnelsen sammenlignet med den nærmeste kjente forbindelse, 2,5-dimethylfuran-3-carboxyanilid In the following, a further test is described with regard to wood preservative activity for compounds according to the invention compared to the closest known compound, 2,5-dimethylfuran-3-carboxyanilide
I forsøkene i henhold til testmetoden for trekonservering beskrevet i Japan Industrial Standards [JIS A-9201 (1991)] ble hver av testforbindelsene oppløst til en definert konsentrasjon i metanol Løsningen ble impregnert under redusert trykk i Sugi (Japanese cedar) flintved (2x2x1 cm) og ble deretter lufttørket En værtest ble gjentatt 10 ganger i hvilken én be-handl ingssyklus var omrøring i vann i 8 timer og deretter oppvarming i 16 timer til 60 °C In the experiments according to the test method for wood preservation described in Japan Industrial Standards [JIS A-9201 (1991)], each of the test compounds was dissolved to a defined concentration in methanol. The solution was impregnated under reduced pressure in Sugi (Japanese cedar) flint wood (2x2x1 cm) and was then air-dried A weather test was repeated 10 times in which one treatment cycle was stirring in water for 8 hours and then heating for 16 hours at 60 °C
Testmaterialet ble anbrakt på floraen av Conolus versicolor eller Tyromyces palustns som begge er fungale arter for utprøvning av trekonserveringseffekt Begge fungi var på forhånd blitt dyrket på et kvartssandmedium (maltekstrakt 2%, glukose 1%, peptid 0,3% og gjær 0,2%) eller et agarmedium (maltekstrakt 2%, glukose 1% og pepton 0,5%) Etter at treprøvene ble tvangssvekket ved 2 6 °C i 8 uker ble effektiviteten av testfor-bindelsen bestemt fra forskjellen mellom tørrvekt av testmaterialet før testen og den etter testen, hvor graden av vektreduksjon ble erholdt De etterfølgende tabeller viser resultatene Testen ble utført på 9 prøver av hver testforbindelse, og verdiene vist i tabellene, er middelverdiene beregnet fra de 9 prøver The test material was placed on the flora of Conolus versicolor or Tyromyces palustns, both of which are fungal species for testing the wood preservation effect. Both fungi had previously been grown on a quartz sand medium (malt extract 2%, glucose 1%, peptide 0.3% and yeast 0.2% ) or an agar medium (malt extract 2%, glucose 1% and peptone 0.5%) After the wood samples were forcibly weakened at 26 °C for 8 weeks, the effectiveness of the test compound was determined from the difference between the dry weight of the test material before the test and that after the test, where the degree of weight reduction was obtained The subsequent tables show the results The test was carried out on 9 samples of each test compound, and the values shown in the tables are the mean values calculated from the 9 samples
I de etterfølgende tabeller er forbindelse A 2,5-dimethylfuran-3-carboxyanilid In the following tables, compound A is 2,5-dimethylfuran-3-carboxyanilide
Claims (7)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP1994/000631 WO1995010511A1 (en) | 1993-10-15 | 1994-04-15 | Dimethylfurancarboxanilide derivative |
Publications (3)
Publication Number | Publication Date |
---|---|
NO964369D0 NO964369D0 (en) | 1996-10-14 |
NO964369L NO964369L (en) | 1996-12-16 |
NO316446B1 true NO316446B1 (en) | 2004-01-26 |
Family
ID=14098327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO19964369A NO316446B1 (en) | 1994-04-15 | 1996-10-14 | Dimethyl furanecarboxyanilide derivatives and wood preservative |
Country Status (8)
Country | Link |
---|---|
AT (1) | ATE203239T1 (en) |
CA (1) | CA2187879C (en) |
DE (1) | DE69427775T2 (en) |
DK (1) | DK0755927T3 (en) |
FI (1) | FI964111A (en) |
HK (1) | HK1011982A1 (en) |
NO (1) | NO316446B1 (en) |
RU (1) | RU2120442C1 (en) |
-
1994
- 1994-04-15 AT AT94912688T patent/ATE203239T1/en not_active IP Right Cessation
- 1994-04-15 RU RU96121397/04A patent/RU2120442C1/en not_active IP Right Cessation
- 1994-04-15 DK DK94912688T patent/DK0755927T3/en active
- 1994-04-15 DE DE69427775T patent/DE69427775T2/en not_active Expired - Fee Related
- 1994-04-15 CA CA002187879A patent/CA2187879C/en not_active Expired - Fee Related
-
1996
- 1996-10-14 FI FI964111A patent/FI964111A/en not_active IP Right Cessation
- 1996-10-14 NO NO19964369A patent/NO316446B1/en unknown
-
1998
- 1998-12-11 HK HK98113195A patent/HK1011982A1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69427775T2 (en) | 2002-04-18 |
CA2187879A1 (en) | 1995-04-20 |
CA2187879C (en) | 2004-08-10 |
ATE203239T1 (en) | 2001-08-15 |
DK0755927T3 (en) | 2001-10-29 |
RU2120442C1 (en) | 1998-10-20 |
HK1011982A1 (en) | 1999-07-23 |
NO964369D0 (en) | 1996-10-14 |
FI964111A (en) | 1996-12-05 |
DE69427775D1 (en) | 2001-08-23 |
FI964111A0 (en) | 1996-10-14 |
NO964369L (en) | 1996-12-16 |
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