NO147603B - 1,3,3-TRIMETHYL-6-AZABICYCLO- (3,2,1) -OCTAN-6-THIOCARBOXYLIC ACID S-ESTERS WITH HERBICIDE EFFECT - Google Patents
1,3,3-TRIMETHYL-6-AZABICYCLO- (3,2,1) -OCTAN-6-THIOCARBOXYLIC ACID S-ESTERS WITH HERBICIDE EFFECT Download PDFInfo
- Publication number
- NO147603B NO147603B NO772552A NO772552A NO147603B NO 147603 B NO147603 B NO 147603B NO 772552 A NO772552 A NO 772552A NO 772552 A NO772552 A NO 772552A NO 147603 B NO147603 B NO 147603B
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- Norway
- Prior art keywords
- trimethyl
- azabicyclo
- acid
- esters
- compounds
- Prior art date
Links
- 230000002363 herbicidal effect Effects 0.000 title claims description 8
- IOJSVCXNWBXHIU-UHFFFAOYSA-N 3,3,5-trimethyl-7-azabicyclo[3.2.1]octane-7-carbothioic s-acid Chemical compound C1C2CC(C)(C)CC1(C)CN2C(S)=O IOJSVCXNWBXHIU-UHFFFAOYSA-N 0.000 title claims description 4
- 230000000694 effects Effects 0.000 title description 8
- 239000004009 herbicide Substances 0.000 title description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 21
- 241000196324 Embryophyta Species 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- -1 8-Naphthyl anhydride Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FRAKHUZTNLUGPB-UHFFFAOYSA-N 3,3,5-trimethyl-7-azabicyclo[3.2.1]octane Chemical compound C1C2NCC1(C)CC(C)(C)C2 FRAKHUZTNLUGPB-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000192043 Echinochloa Species 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000005775 Setaria Nutrition 0.000 description 2
- 241000232088 Setaria <nematode> Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical group CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000005781 Avena Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 1
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YRMLFORXOOIJDR-UHFFFAOYSA-N Dichlormid Chemical compound ClC(Cl)C(=O)N(CC=C)CC=C YRMLFORXOOIJDR-UHFFFAOYSA-N 0.000 description 1
- 235000017896 Digitaria Nutrition 0.000 description 1
- 241001303487 Digitaria <clam> Species 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000209219 Hordeum Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241000209082 Lolium Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001300479 Macroptilium Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000209048 Poa Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- IXWIAFSBWGYQOE-UHFFFAOYSA-M aluminum;magnesium;oxygen(2-);silicon(4+);hydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] IXWIAFSBWGYQOE-UHFFFAOYSA-M 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 229940075522 antidotes Drugs 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical group COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 231100001184 nonphytotoxic Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 210000002741 palatine tonsil Anatomy 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical class ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Foreliggende oppfinnelse angår nye 1,3,3-trimethyl-6-azabicyclo- (3,2,1)-octan-6-thiocarboxylsyre-S-estere med herbi- The present invention relates to new 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-esters with herbi-
cid virkning. cid effect.
Det er allerede kjent at alkyleniminocarbothiolater er aktive herbicide midler (US patentskrift 3 198 786) . Disse for- . bindelser utvikler imidlertid bare i bestemte nyttevekster ut- It is already known that alkyleneiminocarbothiolates are active herbicidal agents (US patent 3,198,786). These for- . bonds, however, only develop in certain useful increments
merkede selektiv-herbicide egenskaper, som f.eks. i riskulturer til bekjempelse av Echinochloa spp. marked selective-herbicidal properties, such as in rice crops to control Echinochloa spp.
Fra CH patent 525 609 og US patent 3 820 974 er det ennvidere kjent beslektede forbindelser som er angitt å ha en bred selektiv-herbicid virkning. En sammenligning av virkningen av enkelte forbindelser kjent fra disse publikasjoner og represen-tative forbindelser ifølge oppfinnelsen er foretatt i etterfølg- From CH patent 525 609 and US patent 3 820 974 there are further known related compounds which are indicated to have a broad selective herbicidal effect. A comparison of the effect of certain compounds known from these publications and representative compounds according to the invention has been made subsequently
ende eksempel 5. end example 5.
Et mål med foreliggende oppfinnelse er derfor å til-veiebringe et middel av den omtalte art som utviser et bredt selektivitetsspektrum overfor nyttevekster og en meget god herbi- An aim of the present invention is therefore to provide an agent of the type mentioned which exhibits a broad spectrum of selectivity towards useful crops and a very good herbicide
cid virkning overfor ugress. cid effect against weeds.
Foreliggende oppfinnelse angår således 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octan-6-thiocarboxylsyre-S-estere med herbi- The present invention thus relates to 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-esters with herbicide
cid virkning som er kjennetegnet ved at de har. den generelle formel: cid effect which is characterized by the fact that they have the general formula:
hvori R betegner en C^-C-^-alkylres t, en 2-propenyl eller en benzylrest. wherein R denotes a C₁-C₄-alkyl residue, a 2-propenyl or a benzyl residue.
De foreliggende forbindelser utmerker seg ved den fremragende herbicide virkning i særdeleshet overfor énfrøbladede ugress, slik som f.eks. Avena, Alipecurus, Echinochloa cg., Setaria, Digitaria, Poa, Hordeum og Triticum. The present compounds are distinguished by their excellent herbicidal action, in particular against monocotyledonous weeds, such as e.g. Avena, Alipecurus, Echinochloa cg., Setaria, Digitaria, Poa, Hordeum and Triticum.
På grunn av deres fremragende selektive egenskaper kan de anvendes på jordbrukskulturer slik som f.eks. blomkål, sukker-roer, såtomat-, buskbønner, bomull og ris. Due to their outstanding selective properties, they can be used on agricultural crops such as e.g. cauliflower, sugar beet, seed tomato, bush beans, cotton and rice.
Foreliggende forbindelser kan også anvendes på mais og durra, hvorved fortrinnsvis motgifter slik som f.eks. 8-nafthyl-syreanhydrid eller N,N-diallyldikloracetamid blandes med frøene eller sprøytemiddel. The present compounds can also be used on maize and sorghum, whereby preferably antidotes such as e.g. 8-Naphthyl anhydride or N,N-diallyldichloroacetamide is mixed with the seeds or spray agent.
En ytterligere fordel med foreliggende forbindelser be-står i at disse også utviser vekstregulerende egenskaper. A further advantage of the present compounds is that they also exhibit growth-regulating properties.
Forbindelsene virker tilfredsstillende allerede i mengder på 1 kg aktivt stoff/ha, og kan på grunn av sine overraskende brede selektivitsspektrum uten skade på nyttevektstkulturer anvendes i mengder på 8 kg/ha før utseden ved innarbeidelse i jorden. The compounds already work satisfactorily in amounts of 1 kg of active substance/ha, and due to their surprisingly broad selectivity spectrum, can be used in amounts of 8 kg/ha before the outside when incorporated into the soil without harming useful weight crops.
Foreliggende forbindelser kan også anvendes enten alene eller i blanding med hverandre eller andre aktive bestanddeler. The present compounds can also be used either alone or in admixture with each other or other active ingredients.
Alt efter det ønskede mål kan eksempelvis følgende herbicide stoffer anvendes, som eventuelt kan tilsettes umiddelbart før anvendelse av foreliggende forbindelser: Depending on the desired goal, for example the following herbicidal substances can be used, which can optionally be added immediately before using the present compounds:
I tillegg kan andre tilsetningsstoffer anvendes, f.eks. ikke-fytotoksiske tilsetningsstoffer som gir herbicidene en synerg aktivitetsøkning slik som fuktemiddel, emulgatorer, oppløsnings-midler og oljeaktige tilsetningsstoffer. In addition, other additives can be used, e.g. non-phytotoxic additives that give the herbicides a synergistic increase in activity, such as wetting agents, emulsifiers, solvents and oily additives.
Hensiktsmessig anvendes foreliggende aktive stoffer eller blandinger av disse i form av tilberedelser slik som pulvere, strømidler, granulater, oppløsninger, emulsjoner eller suspensjo-ner, under tilsetning av flytende og/eller faste bærere, henholds-vis fortynningsmidler og eventuelt fukte-, hefte-, emulger- og/ eller dispergeringsmidler. Appropriate active substances or mixtures thereof are used in the form of preparations such as powders, emulsifiers, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers, respectively diluents and possibly wetting agents, adhesives , emulsifiers and/or dispersants.
Egnede flytende bærere er f.eks. vann, alifatiske og aromatiske hydrocarboner, som benzen, toluen, xylen, cyclohexanon, isoforon, dimethylsulfoxyd, dimethylformamid og ennvidere mineral-olj efraksjoner. Suitable liquid carriers are e.g. water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide and further mineral oil fractions.
Som faste bærere egner mineraljord seg, f.eks. "Tonsil", silicagel, talkum, kaolin, attapulgusleire, kalksten, kiselsyre og planteprodukter, f.eks. mel. As solid carriers, mineral soil is suitable, e.g. "Tonsil", silica gel, talc, kaolin, attapulgus clay, limestone, silicic acid and plant products, e.g. flour.
Som overflateaktive stoffer kan nevnes: F.eks. kalsium-ligninsulfonat, polyoxyethylenalkyl-fenylether, nafthalinsulfon-syrer og deres salter, fenolsulfonsyrer og deres salter, formal-dehydkondensater, fettalkoholsulfater såvel som substituerte ben-zensulfonsyrer og deres salter. Surface-active substances can be mentioned: E.g. calcium lignin sulfonate, polyoxyethylene alkyl phenyl ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzene sulfonic acids and their salts.
Andelen av de respektive aktive bestanddeler i de for-skjellige tilberedelser kan variere innen vide grenser. Eksempelvis inneholder midlet 10 - 80 vekt% aktiv bestanddel, 90 - 20 vekt% flytende eller faste bærere såvel som eventuelt opp til 20 vekt% av overflateaktive midler. The proportion of the respective active ingredients in the various preparations can vary within wide limits. For example, the agent contains 10 - 80% by weight active ingredient, 90 - 20% by weight liquid or solid carriers as well as possibly up to 20% by weight of surfactants.
Utspredning av midlet kan kan skje på vanlig måte, f.eks. med vann som bærer i sprøytemengder på ca. 100 - 1000 li-ter/ha. En anvendelse av midlet i såkaldt "Low-volume-" og "Ultra-Low-volume-metode" er likeledes mulig, og anvendelse i form av såkaldte mikrogranulater. Dissemination of the agent can take place in the usual way, e.g. with water that carries in spray quantities of approx. 100 - 1000 litres/ha. Application of the agent in so-called "Low-volume" and "Ultra-Low-volume methods" is also possible, and application in the form of so-called microgranules.
De tidligere ikke kjente forbindelser lar seg eksempelvis fremstille ved at 1,3,3-trimethyl-6-azabicyclo (3 . 2.1)-octan av formelen: The previously unknown compounds can be prepared, for example, by 1,3,3-trimethyl-6-azabicyclo (3 . 2.1)-octane of the formula:
eventuelt oppløst i et oppløsningsmiddel, optionally dissolved in a solvent,
a) omsettes med halogenthiomaursyreester av den generelle formel: a) is reacted with halothiomauric acid ester of the general formula:
eventuelt i nærvær av et syrebindende middel, eller optionally in the presence of an acid-binding agent, or
b) med carbondisulfid av formelen: b) with carbon disulphide of the formula:
i nærvær av en base B til saltet av denne base med den generelle formel: og at derne, behandles med et alkyleringsmiddel av generell formel: in the presence of a base B to the salt of this base of the general formula: and that therein, treated with an alkylating agent of the general formula:
eller' or'
c) med thiofosgenforbindelser av formelen: til 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octan-6-carboxylsyrehalo-genider av formelen: og at disse derefter omsettes med thioforbindelser av den generelle formel: c) with thiophosgene compounds of the formula: to 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane-6-carboxylic acid halides of the formula: and that these are then reacted with thio compounds of the general formula:
hvorefter fremgangsmåteproduktet isoleres på i og for seg kjent måte, after which the process product is isolated in a manner known per se,
i hvilke formler R har de ovenfor angitte betydninger, B in which formulas R has the meanings given above, B
betegner en base og Z et halogen, en alkylsvovelsyirerest eller en toluensulfonsyrerest. denotes a base and Z a halogen, an alkylsulphuric acid residue or a toluenesulfonic acid residue.
Som baser, hensholdsvis syrebindende middel kan anvendes alle vanlige protonakseptorer. Eksempelvis kan anvendes organiske baser, slik som tertiære aminer, f.eks. triethylamin eller N,N-dimethylanilin eller pyridinbaser og egnede uorganiske baser, som oxyd, hydroxyd og carbonat av alkali- og jordalkalimetaller. Flytende baser kan likeledes tjene som oppløsningsmiddel. Et overskudd av den anvendte flytende base kan eventuelt fungere som syrebindende middel. All common proton acceptors can be used as bases or acid-binding agents. For example, organic bases can be used, such as tertiary amines, e.g. triethylamine or N,N-dimethylaniline or pyridine bases and suitable inorganic bases, such as oxides, hydroxides and carbonates of alkali and alkaline earth metals. Liquid bases can also serve as a solvent. An excess of the liquid base used can possibly function as an acid-binding agent.
Som alkyleringsmiddel anvendes fortrinnsvis klorid, bro-mid og jodid. Chloride, bromide and iodide are preferably used as alkylating agents.
Omsetningen av reaktantene skjer mellom 0 og 120°C, vanligvis ved romtemperatur. The reaction of the reactants takes place between 0 and 120°C, usually at room temperature.
Ved fremstilling av de nye forbindelser anvendes reaktantene i ca. ekvimolare mengder. When producing the new compounds, the reactants are used in approx. equimolar amounts.
Egnede reaksjonsmedia overfor reaktantene er inerte opp-løsningsmidler, eller i blanding med vann. Som slike kan følgende nevnes: alifatiske og aromatiske hydrocarboner, som petrolether, cyclohexan, benzen, toluen og xylen, halogenerte hydrocarboner, slik som methylenklorid, kloroform, tetraklorcarbon og halogenerte ethylener, etherf orbi.ndelser, slik som diethy.lether, diisopropylether, tetrahydrofuran og dioxan, ketoner, slik som aceton, methyl-isobutylketon og isoforon, estere, slik som eddiksyremethyl- og ethylester, syreamider, slik som dimethylformamid og hexamethylfos-forsyretriamid, carbonsyrenitriler, slik som acetonitril og mange andre. Suitable reaction media for the reactants are inert solvents, or in a mixture with water. As such, the following can be mentioned: aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, benzene, toluene and xylene, halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride and halogenated ethylenes, ether compounds, such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl isobutyl ketone and isophorone, esters, such as acetic acid methyl and ethyl ester, acid amides, such as dimethylformamide and hexamethylphosphoric acid triamide, carboxylic acid nitriles, such as acetonitrile and many others.
Isoleringen av de nye forbindelser skjer ved avdestille-ring av det egnede oppløsnings- eller ekstraksjonsmiddel ved nor-malt eller forminsket trykk, eventuelt efter behandling med syre eller basiske midler for fjernelse av uønskede biprodukter. Om nødvendig kan forbindelsene destilleres i vakuum. The isolation of the new compounds takes place by distilling off the suitable solvent or extraction agent at normal or reduced pressure, possibly after treatment with acid or basic agents to remove unwanted by-products. If necessary, the compounds can be distilled in vacuum.
Utgangsmaterialene for fremstilling av de nye forbindelser er i og for seg kjente, eller kan fremstilles efter kjente me-toder . The starting materials for the production of the new compounds are known in and of themselves, or can be produced according to known methods.
De følgende eksempler illustrerer fremstillingen av de nye forbindelser. The following examples illustrate the preparation of the new compounds.
Eksempel 1 Example 1
Til en oppløsning av 61,3 g 1,3,3-trimethyl-6-azabicyc-lo-(3.2.1)-octan i 150 ml diisopropylether ble ved romtemperatur under omrøring dråpevis tilsatt 24,9 g klorthiomaursyre-S-methyl-ester. Efter en times omrøring ble reaksjonsblandingen utrystet med vann, derefter med fortynnet saltsyre og igjen med vann, den organiske fase ble tørket over magnesiumsulfat, oppløsningsmidlet ble destillert fra i vakuum og tilslutt befridd for oppløsnings-middelrester i høyvakuum. 24.9 g of chlorothiomauric acid-S-methyl- ester. After stirring for one hour, the reaction mixture was shaken with water, then with dilute hydrochloric acid and again with water, the organic phase was dried over magnesium sulfate, the solvent was distilled off in vacuo and finally freed of solvent residues in high vacuum.
Ved tilsetning til det første vannekstrakt med natronlut ble det i overskudd anvendte utgangsmateriale gjenvunnet. By adding caustic soda to the first water extract, the starting material used in excess was recovered.
Utbytte: 46,0 g (95,29 % av teoretisk) 1,3,3-trimethyl-6-azabi-cyclo-(3.2.1)-octan-6-thiocarboxylsyre-S-ethylester Yield: 46.0 g (95.29% of theory) 1,3,3-trimethyl-6-azabi-cyclo-(3.2.1)-octane-6-thiocarboxylic acid-S-ethyl ester
20 20
n£<u> = 1,5123. n£<u> = 1.5123.
Eksempel 2 Example 2
I en blanding av 34 ml 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octan, 5o ml acetonitril og 8 g natriumhydroxyd oppløst i 50 ml vann ble der under omrøring ved mellom 10 og 15°C dråpevis tilsatt 15,2 g svovelcarbon. For dannelse av dithiocarbaminsyre-salter ble blandingen omrørt ytterligere 2 timer. Derefter ble der til reaksjonsblandingen dråpevis tilsatt 24,5 g allylbromid, og alandingen ble omrørt 1 time til esterdannelse. Efter tilsetning av 500 ml methylenklorid ble den organiske fase utristet med fortynnet saltsyre, tørket over magnesiumsulfat, behandlet med aktivt carbon og inndampet i høyvakuum.' Der ble tilbake 52 g (96,4 % av teoretisk) 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octan-20 In a mixture of 34 ml of 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane, 50 ml of acetonitrile and 8 g of sodium hydroxide dissolved in 50 ml of water, while stirring at between 10 and 15°C, was added dropwise added 15.2 g sulfur carbon. To form dithiocarbamic acid salts, the mixture was stirred for a further 2 hours. Then 24.5 g of allyl bromide was added dropwise to the reaction mixture, and the mixture was stirred for 1 hour until ester formation. After adding 500 ml of methylene chloride, the organic phase was shaken out with dilute hydrochloric acid, dried over magnesium sulphate, treated with active carbon and evaporated under high vacuum. There remained 52 g (96.4% of theoretical) 1,3,3-trimethyl-6-azabicyclo-(3.2.1)-octane-20
6,dithiocarboxylsyre allylester med n^ = 1,5810. 6,dithiocarboxylic acid allyl ester with n^ = 1.5810.
På analog måte kan følgende forbindelser fremstilles: In an analogous way, the following compounds can be prepared:
De nye forbindelser er farveløse eller svakt gulfarvede, svakt aromatisk-duftende oljer som er uoppløselige i vann, men godt oppløselige i alle organiske oppløsningsmidler, slik som f.eks. i hydrocarboner, halogenerte hydrocarboner, ethere, ketoner, carboxylsyreestere, carboxylsyreamider, carboxylsyrenitriler, alkoholer, carboxylsyrer, sulfoxyder og flere andre. The new compounds are colorless or slightly yellow-coloured, slightly aromatic-scented oils which are insoluble in water, but well soluble in all organic solvents, such as e.g. in hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters, carboxylic acid amides, carboxylic acid nitriles, alcohols, carboxylic acids, sulfoxides and several others.
De følgende eksempler illustrerer anvendelsesmuligheten for de foreliggende forbindelser. The following examples illustrate the utility of the present compounds.
Eksempel 3 Example 3
I drivhus ble de i tabellen anførte nye forbindelser på-sprøytet i en mengde på 5 kg aktivt stoff/ha, suspendert i 500 li-ter vann/ha, før utsåing av Lolium og Setaria, og innarbeidet i jorden. Tre uker efter behandlingen ble behandlingsresultatet vurdert, hvorved; 0=ingen virkning, 4=tilintetgjørelse av plantene. In greenhouses, the new compounds listed in the table were sprayed on in a quantity of 5 kg of active substance/ha, suspended in 500 liters of water/ha, before sowing Lolium and Setaria, and incorporated into the soil. Three weeks after the treatment, the treatment result was assessed, whereby; 0=no effect, 4=destruction of the plants.
Eksempel 4 Example 4
I drivhus ble de oppførte planter før spiring behandlet med de angitte midler i en mengde på 3 kg aktivt stoff/ha. Midlet ble for dette formål utsprøytet som vandig dispersjon med 500 l/ha på jorden, og derefter innarbeidet i jorden. Resultatet 3 uker efter behandlingen viser at det foreliggende middel er bedre enn sammenligningsmidlet. In greenhouses, the listed plants were treated before germination with the specified agents in a quantity of 3 kg of active substance/ha. For this purpose, the agent was sprayed as an aqueous dispersion at 500 l/ha on the soil, and then incorporated into the soil. The result 3 weeks after the treatment shows that the present remedy is better than the comparison remedy.
Eksempel 5 Example 5
A I veksthus ble de planter som er oppført i tabellen behandlet p-.reemergens med de oppførte virkestoffer i en mengde på 3 kg virkestoff/hektar.Midlet ble for dette formål påført som vandig dispersjon med 500 l/ha jevnt på jorden, og derpå innarbeidet i jorden. Vurderingen fant sted 3 uker efter behandlingen efter følgende skjema: A In the greenhouse, the plants listed in the table were treated pre-emergence with the active substances listed in a quantity of 3 kg active substance/hectare. The agent was applied for this purpose as an aqueous dispersion at 500 l/ha evenly on the soil, and then incorporated in the earth. The assessment took place 3 weeks after the treatment according to the following form:
Resultatene viser at forbindelsen ifølge oppfinnelsen utviser en sterkere herbicid virkning under skåning av nytteplan-tene enn sammenligningsmidlene kjent fra US patentskrift 3.820.974..<:>The results show that the compound according to the invention exhibits a stronger herbicidal effect while sparing the beneficial plants than the comparison agents known from US patent document 3,820,974..<:>
B Selek.tLv~pree:mergensf orsøk. med sådde testplanter B Selec.tLv~pre:mergensf trial. with sown test plants
Umiddelbart efter utsåing av testplantene i frøskåler ble virkestoffet som vandig suspensjon påført jordoverflaten, Deref ter ble frøskålene holdt ved 22 25°C og 50 - r 70 % relativ luftfiktighet under dagslys. Immediately after sowing the test plants in seed trays, the active substance was applied as an aqueous suspension to the soil surface. The seed trays were then kept at 22 25°C and 50 - r 70% relative humidity under daylight.
Bedømmelsen fant sted efter 28 dager ifølge 9er-indeksen. Som testplanter ble anvendt: The assessment took place after 28 days according to the 9er index. As test plants were used:
Resultatene viser at de nye forbindelser tilintetgjør ugress i bomull- og soyabønnekulturer uten beskadigelse av disse planter, mens sammenligningsmidlene ifølge sveitsisk patentskrift 525,609 delvis beskadiger disse kulturer eller utviser en utilstrekkelig ugressvirkning. The results show that the new compounds destroy weeds in cotton and soybean cultures without damaging these plants, while the comparative agents according to Swiss patent document 525,609 partially damage these cultures or exhibit an insufficient weeding effect.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762632915 DE2632915A1 (en) | 1976-07-19 | 1976-07-19 | 1,3,3-TRIMETHYL-6-AZABICYCLO- (3.2.1) -OCTAN-6-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THE HERBICIDES CONTAINING THEM |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO772552L NO772552L (en) | 1978-01-20 |
| NO147603B true NO147603B (en) | 1983-01-31 |
| NO147603C NO147603C (en) | 1983-05-11 |
Family
ID=5983626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO772552A NO147603C (en) | 1976-07-19 | 1977-07-18 | 1,3,3-TRIMETHYL-6-AZABICYCLO- (3,2,1) -OCTAN-6-THIOCARBOXYLIC ACID S-ESTERS WITH HERBICIDE EFFECT |
Country Status (34)
| Country | Link |
|---|---|
| JP (1) | JPS5312855A (en) |
| AR (1) | AR216084A1 (en) |
| AT (1) | AT355861B (en) |
| AU (1) | AU511783B2 (en) |
| BE (1) | BE856933A (en) |
| BG (2) | BG27027A3 (en) |
| BR (1) | BR7704733A (en) |
| CA (1) | CA1100138A (en) |
| CH (1) | CH627920A5 (en) |
| CS (1) | CS192582B2 (en) |
| DD (1) | DD131070A5 (en) |
| DE (1) | DE2632915A1 (en) |
| DK (1) | DK324977A (en) |
| ES (1) | ES460737A1 (en) |
| FI (1) | FI772095A (en) |
| FR (1) | FR2359142A1 (en) |
| GB (1) | GB1588934A (en) |
| GR (1) | GR71649B (en) |
| HU (1) | HU178752B (en) |
| IE (1) | IE45359B1 (en) |
| IL (1) | IL52455A (en) |
| IT (1) | IT1113599B (en) |
| LU (1) | LU77781A1 (en) |
| MX (1) | MX4852E (en) |
| NL (1) | NL7707038A (en) |
| NO (1) | NO147603C (en) |
| PL (1) | PL103690B1 (en) |
| PT (1) | PT66822B (en) |
| RO (1) | RO71241A (en) |
| SE (1) | SE424868B (en) |
| SU (1) | SU656464A3 (en) |
| TR (1) | TR19833A (en) |
| YU (1) | YU164477A (en) |
| ZA (1) | ZA774346B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES303195A1 (en) * | 1963-08-19 | 1965-03-16 | Ciba Geigy | Procedure for the obtaining of N- (n, N-bicicloalquilenoimino) -ditiocarbonic acids. (Machine-translation by Google Translate, not legally binding) |
| US3820974A (en) * | 1970-08-05 | 1974-06-28 | Ciba Geigy Corp | Control of weeds with n carbenyl derivatives of azabicyclooctanes |
| US3705165A (en) * | 1970-08-05 | 1972-12-05 | Elmar Sturm | N-carbonyl derivatives of azabicyclooctanes |
-
1976
- 1976-07-19 DE DE19762632915 patent/DE2632915A1/en not_active Withdrawn
-
1977
- 1977-06-24 NL NL7707038A patent/NL7707038A/en unknown
- 1977-07-01 YU YU01644/77A patent/YU164477A/en unknown
- 1977-07-04 CS CS774434A patent/CS192582B2/en unknown
- 1977-07-04 MX MX77100800U patent/MX4852E/en unknown
- 1977-07-05 FI FI772095A patent/FI772095A/fi not_active Application Discontinuation
- 1977-07-05 IL IL52455A patent/IL52455A/en unknown
- 1977-07-07 TR TR19833A patent/TR19833A/en unknown
- 1977-07-11 CA CA282,400A patent/CA1100138A/en not_active Expired
- 1977-07-14 AU AU27008/77A patent/AU511783B2/en not_active Expired
- 1977-07-14 ES ES460737A patent/ES460737A1/en not_active Expired
- 1977-07-15 CH CH880877A patent/CH627920A5/en not_active IP Right Cessation
- 1977-07-15 LU LU77781A patent/LU77781A1/xx unknown
- 1977-07-15 BG BG7736916A patent/BG27027A3/en unknown
- 1977-07-15 IE IE1472/77A patent/IE45359B1/en unknown
- 1977-07-15 DD DD7700200094A patent/DD131070A5/en unknown
- 1977-07-15 BG BG7736916D patent/BG28027A3/xx unknown
- 1977-07-16 PL PL1977199694A patent/PL103690B1/en unknown
- 1977-07-18 PT PT66822A patent/PT66822B/en unknown
- 1977-07-18 NO NO772552A patent/NO147603C/en unknown
- 1977-07-18 BR BR7704733A patent/BR7704733A/en unknown
- 1977-07-18 FR FR7721934A patent/FR2359142A1/en active Granted
- 1977-07-18 HU HU77SCHE615A patent/HU178752B/en unknown
- 1977-07-18 AR AR268467A patent/AR216084A1/en active
- 1977-07-18 RO RO7791078A patent/RO71241A/en unknown
- 1977-07-18 GR GR53987A patent/GR71649B/el unknown
- 1977-07-18 AT AT517477A patent/AT355861B/en not_active IP Right Cessation
- 1977-07-18 SE SE7708277A patent/SE424868B/en unknown
- 1977-07-18 DK DK324977A patent/DK324977A/en not_active Application Discontinuation
- 1977-07-19 IT IT25888/77A patent/IT1113599B/en active
- 1977-07-19 SU SU772504515A patent/SU656464A3/en active
- 1977-07-19 ZA ZA00774346A patent/ZA774346B/en unknown
- 1977-07-19 JP JP8657277A patent/JPS5312855A/en active Granted
- 1977-07-19 GB GB30241/77A patent/GB1588934A/en not_active Expired
- 1977-07-19 BE BE179455A patent/BE856933A/en not_active IP Right Cessation
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