NO140938B - METHOD AND DEVICE FOR FORMING A CONTINUOUS MATERIAL PATH OF FIBROSE PARTICLES - Google Patents
METHOD AND DEVICE FOR FORMING A CONTINUOUS MATERIAL PATH OF FIBROSE PARTICLES Download PDFInfo
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- NO140938B NO140938B NO221571A NO221571A NO140938B NO 140938 B NO140938 B NO 140938B NO 221571 A NO221571 A NO 221571A NO 221571 A NO221571 A NO 221571A NO 140938 B NO140938 B NO 140938B
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- rice
- preparation
- parts
- compound
- reaction
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- 238000000034 method Methods 0.000 title description 5
- 239000002245 particle Substances 0.000 title description 4
- 206010016654 Fibrosis Diseases 0.000 title 1
- 239000000109 continuous material Substances 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims description 24
- 230000000749 insecticidal effect Effects 0.000 claims description 18
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 23
- 241000209094 Oryza Species 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 235000007164 Oryza sativa Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 235000009566 rice Nutrition 0.000 description 13
- 239000013543 active substance Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000426497 Chilo suppressalis Species 0.000 description 8
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 239000004563 wettable powder Substances 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000004495 emulsifiable concentrate Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000002917 insecticide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 241000699670 Mus sp. Species 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 235000013601 eggs Nutrition 0.000 description 4
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- 241001465754 Metazoa Species 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000013504 Triton X-100 Substances 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 231100001231 less toxic Toxicity 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000010152 pollination Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 206010058667 Oral toxicity Diseases 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241001249127 Scirpophaga Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000008029 eradication Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000001418 larval effect Effects 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- 231100000418 oral toxicity Toxicity 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 231100000925 very toxic Toxicity 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- PTHBKNSHSCMKBV-UHFFFAOYSA-N 4,6,8-trihydroxy-3-(2-hydroxyethyl)-2,3-dihydronaphtho[2,3-f][1]benzofuran-5,10-dione Chemical compound O=C1C2=CC(O)=CC(O)=C2C(=O)C2=C1C=C1OCC(CCO)C1=C2O PTHBKNSHSCMKBV-UHFFFAOYSA-N 0.000 description 1
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000426499 Chilo Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000400698 Elasmopalpus lignosellus Species 0.000 description 1
- 241000661279 Eldana Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000699666 Mus <mouse, genus> Species 0.000 description 1
- 241000257226 Muscidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001579307 Schoenobius Species 0.000 description 1
- 241000563489 Sesamia inferens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NZNRRXXETLSZRO-UHFFFAOYSA-N chlorthion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(Cl)=C1 NZNRRXXETLSZRO-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 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
- 239000010410 layer Substances 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ZHCAAFJSYLFLPX-UHFFFAOYSA-N nitrocyclohexatriene Chemical compound [O-][N+](=O)C1=CC=C=C[CH]1 ZHCAAFJSYLFLPX-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- TXKSMBDQKVGNIZ-UHFFFAOYSA-M sodium;4-cyanophenolate Chemical compound [Na+].[O-]C1=CC=C(C#N)C=C1 TXKSMBDQKVGNIZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- PTHBKNSHSCMKBV-ZETCQYMHSA-N versicol Natural products OCC[C@H]1COc2cc3C(=O)c4cc(O)cc(O)c4C(=O)c3c(O)c12 PTHBKNSHSCMKBV-ZETCQYMHSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/02—Head boxes of Fourdrinier machines
- D21F1/024—Details of the feed chamber
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/02—Head boxes of Fourdrinier machines
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/02—Head boxes of Fourdrinier machines
- D21F1/026—Details of the turbulence section
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/02—Head boxes of Fourdrinier machines
- D21F1/028—Details of the nozzle section
Landscapes
- Paper (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Description
Insekticid preparat. Insecticide preparation.
Den foreliggende oppfinnelse angår in-sekticide preparater som ineholder en ny, The present invention relates to insecticidal preparations which contain a new,
lite giftig organofosforsyreester. Organo-fosforsyreesteren som anvendes er 0,0-dimetyl-0-(4-cyanfenyl)-tionfosfat, som har slightly toxic organophosphoric acid ester. The organophosphoric acid ester used is 0,0-dimethyl-0-(4-cyanophenyl)-thiophosphate, which has
følgende formel: following formula:
Ovennevnte forbindelse kan fremstilles The above compound can be prepared
ved at 0,0-dimetyl-klortionfosfat kondenseres med 4-cyanfenol eller et alkalimetallsalt av denne. Preparatet ifølge oppfinnelsen kan anvendes for utrydding av agri-kulturelt skadelige insekter, spesielt risborere som f. eks. risstilkborer (Chilo sup-pressalis W ALKER), risskallborer (Schoe-nobius incertellus WALKER), risstilkborer in that 0,0-dimethylchlorothiophosphate is condensed with 4-cyanophenol or an alkali metal salt thereof. The preparation according to the invention can be used for the eradication of agriculturally harmful insects, especially rice borers such as e.g. rice stalk borer (Chilo sup-pressalis W ALKER), rice husk borer (Schoe-nobius incertellus WALKER), rice stalk borer
(Sesamia inferens WALKER), og andre (Sesamia inferens WALKER), and others
(som f. eks. CHILO plejadellus ZINK, Chi-lotra polychrysa MEYR., Scirpophaga albi-nella CRAMER, Scirpophaga innota WAL-KERS, Eldana dichromellus WALKER, og (such as CHILO plejadellus ZINK, Chi-lotra polychrysa MEYR., Scirpophaga albi-nella CRAMER, Scirpophaga innota WAL-KERS, Eldana dichromellus WALKER, and
Elasmopalpus lignosellus ZELLER), og sa-nitært skadelige insekter, særlig husfluer Elasmopalpus lignosellus ZELLER), and sanitary harmful insects, especially houseflies
(Musea domestica LINNE), og disses larver (Musea domestica LINNE), and their larvae
og lignende. and such.
Formålet med den foreliggende opp-finelse består altså i å skaffe et nytt insekticid preparat som er egnet for agrikul-turell og sanitær anvendelse, som er meget The purpose of the present invention therefore consists in obtaining a new insecticidal preparation which is suitable for agricultural and sanitary use, which is very
lite giftig like overfor varmblodige dyr, slightly toxic towards warm-blooded animals,
men har meget stor insekticid aktivitet, sammenlignet med vanlige insekticider. but has very high insecticidal activity, compared to ordinary insecticides.
Det er kjent at organiske forforsyre-estere som inneholder et 4-nitrofenylradi-kal, f. eks. paration og metylparation, har betydelig insektisid aktivitet og følgelig kan utgjøre nyttige, virksomme bestand-deler i agrikulturelle kjemikalier. Men samtidig er de meget giftige for varmblodige dyr, og det er derfor av amerikanske og tyske forskere blitt gjortmangeforsøk på å finne liknende forbindelser som er mindre giftige og har større insektisid aktivitet, og det er som resultat herav blitt funnet stoffer som «Chlorthion» og dikapton. Men disse såkalt lite giftige insektisidforbindel-ser er virkelig så lite giftige at også deres insektiside virksomhet er nedsatt i noen grad. It is known that organic forphosphoric acid esters containing a 4-nitrophenyl radical, e.g. parathion and methyl parathion, have significant insecticidal activity and can therefore form useful, effective constituents in agricultural chemicals. But at the same time they are very toxic to warm-blooded animals, and therefore many attempts have been made by American and German scientists to find similar compounds that are less toxic and have greater insecticidal activity, and as a result substances such as "Chlorthion" and dicaptone. But these so-called low-toxic insecticide compounds are really so low-toxic that their insecticidal activity is also reduced to some extent.
En forsker hos Farbenfabriken Bayer A. G. har gitt meddelelser om syntese av et tiofosfat som inneholder et cyanfenyl-radikal, nemlig 0,0-dietyl-O-(4-cyanfenyl) tionfosfat, samt om resultater av insektiside forsøk med denne forbindelse (G. Schrader: Die Entwicklung neuer Insek-tizide auf Grundlage organischer Fluor und Phosphor-Verbindungen, side 59, 1952). Denne forbindelse har imidlertid like overfor varmblodige dyr en stor oral giftighet som ikke avviker meget fra parations, mens dens insektiside aktivitet like overfor skadeinsektene er lavere enn parations. Det er ikke blitt gitt underretning om videre forsøk med denne forbindelse. A researcher at the Farbenfabriken Bayer A. G. has given notices of the synthesis of a thiophosphate containing a cyanophenyl radical, namely 0,0-diethyl-O-(4-cyanophenyl) thionephosphate, as well as of the results of insecticidal trials with this compound (G. Schrader : Die Entwicklung neuer Insectizide auf Grundlage organischer Fluor und Phosphor-Verbindungen, page 59, 1952). However, this compound has a high oral toxicity towards warm-blooded animals which does not differ much from parations, while its insecticidal activity towards harmful insects is lower than parations. No notification has been given of further attempts in this connection.
Nærværende oppfinnere har gjort forskjellige studier for å finne en forbindelse som er lite giftig, men samtidig har stor insektisid aktivitet; en slik forbndelse er sterkt ønsket i risproduserende distrikter. De fant derved den type av forbindelser som patentet angår og som oppfyller de nevnte fordringer. Stoffer som paration, metylparation «EPN» og «Dipterex» er blitt anvendt som utryddelsesmiddel for risborere. Riktignok er de tre førstnevnte stoffer meget aktive mot risborere, men samtidig er de meget giftige for varmblodige vesener, deri iberegnet mennesker. Eksempelvis er parations LDr„,-verdi for oral anvendelse hos mus 6—10 mg/kg legemsvekt, hvorfor det kreves meget stor forsiktighet ved bruk av preparater som inneholder disse forbindelser. «Dipterex» er riktignok betydelig mindre giftig for varmblodige vesener, men stoffet har mindre insektisid aktivitet, sammenlignet med de ovennevnte tre forbindelser. Stort sett kan man si, at det be-høves 2 eller 3 ganger så meget av de først-nevnte forbindelser for å oppnå samme resultat mot risborere, som ved bruk av den sistnevnte forbindelse. Et slikt stort forbruk vil være uøkonomisk. Følgen er at til tross for meget stor giftighet like overfor varmblodige vesener er paration hittil blitt almindelig anvendt som utryddelsesmiddel for risborere. Den forbindelse som den foreliggende oppfinnelse angår, har som meget nøyaktig forklart nedenfor, ca. 100 ganger mindre giftvirkning enn paration, og flere ganger mindre enn giftvirk-ningen av «Dipterex» (eksempelvis for oral giftighet mot mus er LDr„,-verdien 900— 1000 mg/kg legemsvekt) slik at det kan sies at forbindelsen er praktisk talt ikke giftig. Men som nedenfor forklart i forbindelse med tallmessige angivelser, er forbindel-sens effektivitet like overfor risborere slett ikke mindre enn parations, hvorfor det må sies at den foreliggende oppfinnelse gir en god løsning på spørsmålet om å motarbeide risborere. The present inventors have made various studies to find a compound that is low in toxicity but at the same time has great insecticidal activity; such a connection is strongly desired in rice-producing districts. They thereby found the type of compounds to which the patent relates and which fulfill the aforementioned requirements. Substances such as parathion, methyl parathion "EPN" and "Dipterex" have been used as exterminators for rice borers. Admittedly, the first three substances are very active against rice borers, but at the same time they are very toxic to warm-blooded creatures, including humans. For example, paration's LDr„, value for oral use in mice is 6-10 mg/kg body weight, which is why great caution is required when using preparations containing these compounds. "Dipterex" is indeed significantly less toxic to warm-blooded creatures, but the substance has less insecticidal activity compared to the above three compounds. Broadly speaking, it can be said that 2 or 3 times as much of the first-mentioned compounds are needed to achieve the same result against rice borers as when using the latter compound. Such a large consumption would be uneconomical. The consequence is that, despite its very high toxicity towards warm-blooded creatures, parathion has so far been commonly used as an extermination agent for rice borers. The compound to which the present invention relates has, as very precisely explained below, approx. 100 times less toxic than parathion, and several times less than the toxic effect of "Dipterex" (for example for oral toxicity to mice the LDr„ value is 900-1000 mg/kg body weight) so that it can be said that the compound is practically not toxic. But as explained below in connection with numerical indications, the compound's effectiveness against rice borers is not at all less than that of parations, which is why it must be said that the present invention provides a good solution to the question of counteracting rice borers.
Det 0,0-dimetyl-O-(4-cyanfenyl)tionfosfat som oppfinnelsen dreier seg om, er et nytt stoff, som hittil ikke er blitt beskrevet i noen litteratur. Det kan fremstilles i henhold til følgende reaksjonsskjema The 0,0-dimethyl-O-(4-cyanophenyl)thiophosphate which the invention is about is a new substance, which has not been described in any literature so far. It can be produced according to the following reaction scheme
(hvor M betegner hydrogen eller et alkali-metallatom), 0,0-dimetyl-klortionfosfat (I) kondenseres altså med 4-cyanfenol eller et alkalimetallsalt av denne (II). (where M denotes hydrogen or an alkali metal atom), 0,0-dimethylchlorothiophosphate (I) is thus condensed with 4-cyanophenol or an alkali metal salt thereof (II).
Den i den foreliggende fremgangs-måte som utgangsmateriale anvendte 0,0-dimetyl-klortionfosfat er en kjent,flytende forbindelse, som koker ved 66° C ved 16 mm Hg. Det annet utgangsmateriale, 4-cyanfenol, kan også fremstilles ved kjente metoder, f. eks. den som er beskrevet i J. Chem. Soc, 1942, 113, og smelter ved 110° C, denne forbindelse kan lett omdannes til et salt ved reaksjon med f. eks. kaustisk alkali, alkalikarbonet, alkalimetall og alkali-metallalkoholat, i vann eller i et organisk oppløsningsmiddel. Det foretrekkes å an- The 0,0-dimethylchlorothione phosphate used as starting material in the present process is a known liquid compound which boils at 66° C. at 16 mm Hg. The other starting material, 4-cyanophenol, can also be prepared by known methods, e.g. that described in J. Chem. Soc, 1942, 113, and melts at 110° C, this compound can easily be converted into a salt by reaction with e.g. caustic alkali, alkali carbonate, alkali metal and alkali metal alcoholate, in water or in an organic solvent. It is preferable to an-
vende natrium eller kalium som alkali. turn sodium or potassium as alkali.
Kondensasjonen av utgangsmateri-alene kan med hell foregå ved at man blan-der dem i molekylært forhold eller even-tuelt med et overskudd av 0,0-dimetyl-klortionfosfat. I dette tilfelle er det som regel å foretrekke å utføre reaksjonen i et inert organisk oppløsningsmiddel under anvendelse av omtrent ekvimolare mengder av de to stoffer. Det vil si at når 0,0-dimetyl-klortionfosfat blandes med alkalimetall-4-cyanfenolat i et inert organisk oppløsnings-middel og deretter ophetes, kan den forbindelse som nærværende oppfinnelse gjel-der fås som produkt. Hvis fri 4-cyanfenol anvendes i stedet for det nevnte alkalimetall-4-cyanfenolat, foregår reaksjonen etter den såkalte dehydrogenkloridreaksjon, og i så tilfelle blir denne reaksjon fortrinnsvis utført i nærvær av et i og for seg kjent avsyringsmiddel, f. eks. organiske baser som pyridin og dietylamin eller alkalime-tallkarbonater eller -bikarbonater. Det inerte organiske oppløsningsmiddel som anvendes kan være av en hvilken som helst i og for seg kjent art, hvis det bare ikke påvirker reaksjonen, f. eks. et hydrokarbon, et klorert hydrokarbon, en alkohol, et keton eller lignende. Reaksjonen kan foregå bare ved at reaksjonsblandingen får henstå ved romtemperatur i lang tid, men som regel er det å foretrekke å opphete blandingen, f. eks. til en viss temperatur under oppløsningsmidlets kokepunkt. Ennvidere foretas reaksjonen fortrinnsvis i nærvær av en katalysator som f. eks. kobberpulver eller kuprosalter, og gir da godt utbytte. Condensation of the starting materials can be successfully carried out by mixing them in a molecular ratio or possibly with an excess of 0,0-dimethylchlorothione phosphate. In this case, it is generally preferable to carry out the reaction in an inert organic solvent using approximately equimolar amounts of the two substances. That is to say, when 0,0-dimethylchlorothione phosphate is mixed with alkali metal 4-cyanophenolate in an inert organic solvent and then heated, the compound to which the present invention applies can be obtained as a product. If free 4-cyanophenol is used instead of the aforementioned alkali metal 4-cyanophenolate, the reaction takes place after the so-called dehydrogen chloride reaction, and in that case this reaction is preferably carried out in the presence of a deacidifying agent known per se, e.g. organic bases such as pyridine and diethylamine or alkali metal carbonates or bicarbonates. The inert organic solvent used can be of any kind known per se, as long as it does not affect the reaction, e.g. a hydrocarbon, a chlorinated hydrocarbon, an alcohol, a ketone or the like. The reaction can only take place by allowing the reaction mixture to stand at room temperature for a long time, but as a rule it is preferable to heat the mixture, e.g. to a certain temperature below the boiling point of the solvent. Furthermore, the reaction is preferably carried out in the presence of a catalyst such as e.g. copper powder or copper salts, and then gives a good yield.
Når reaksjonen er ferdig blir det utfelte alkalimetallklorid eller hydrokloridet av den organiske base filtrert fra, eller even-tuelt tilsetter man nok vann til å løse opp biproduktsaltene, hvoretter det vandige lag skilles fra, og det organiske lag inndampes i vakuum, så den ønskede forbindelse fåes som rest. På den ovennevnte måte kan man få et produkt som er tilstrekkelig renset for de fleste praktiske formål, men om nødvendig kan produktet renses videre ved destillasjon i vakuum, ved kromatografe-ring i søyler, og/eller ved omkrystallise-ring ved en lavere temperatur. Da de forbindelser oppfinnelsen angår som regel spaltes noe ved oppheting, anvendes den helst uten sådan rensing. When the reaction is finished, the precipitated alkali metal chloride or the hydrochloride of the organic base is filtered off, or possibly enough water is added to dissolve the by-product salts, after which the aqueous layer is separated, and the organic layer is evaporated in vacuo, so the desired compound available as leftovers. In the above-mentioned manner, a product can be obtained that is sufficiently purified for most practical purposes, but if necessary, the product can be further purified by distillation in vacuum, by chromatography in columns, and/or by recrystallization at a lower temperature. As the compounds to which the invention relates usually decompose somewhat when heated, it is preferably used without such purification.
Det erholdte 0,0-dimetyl-O-(4-cyan-fenyl)tionfosfat) er et lysgult, oljeaktig produkt, med brytningsindeks n^'^- 1-5457 The obtained 0,0-dimethyl-O-(4-cyano-phenyl)thiophosphate) is a light yellow, oily product, with a refractive index n^'^- 1-5457
og kp. 119—120° C/0,09 mm Hg (ledsaget av noe spaltning) og denne forbindelse er meget oppløselig i alkoholer, etere, ketoner og aromatiske hydrokarboner, og meget lite oppløselig i alifatiske hydrokarboner og uoppløselig i vann. and kp. 119—120° C/0.09 mm Hg (accompanied by some decomposition) and this compound is very soluble in alcohols, ethers, ketones and aromatic hydrocarbons, and very slightly soluble in aliphatic hydrocarbons and insoluble in water.
I det følgende gis det en oversikt over giftigheten av 0,0-dimetyl-O-(4-cyanfenyl) tionfosfat som oppfinnelsen angår. Giftigheten (LD-„,-verdien) like overfor mus er her sammenlignet med parations, under forskjellige anvendelsesforhold, som angitt i tabell 1. In the following, an overview is given of the toxicity of 0,0-dimethyl-O-(4-cyanophenyl)thiophosphate to which the invention relates. The toxicity (LD-„, value) towards mice is here compared with parations, under different application conditions, as indicated in table 1.
Den følgende tabell 2 viser giftverdien og av EPN ved dermal anvendelse (LDr>(1, av stoff ifølge oppfinnelsen og av paration mg/mus). The following table 2 shows the toxic value and of EPN when applied dermally (LDr>(1, of substance according to the invention and of parathion mg/mouse).
At preparatet ifølge oppfinnelsen har giftighet like overfor mus og nyttevirkning-en fremtredende lav giftighet vil fremgå av stoff ifølge oppfinnelsen og av hittil av den følgende tabell 3, hvor det er angitt kjente og anvendte insektisider. That the preparation according to the invention has the same toxicity towards mice and a beneficial effect - a prominently low toxicity - will be apparent from the substance according to the invention and from the following table 3, where known and used insecticides are indicated.
0,0-dimetyl-O-(4-cyanfenyl) tiofosfat som anvendes i henhold til den foreliggende oppfinnelse, inntar en helt egenartet stilling blandt andre isomere, homologe og analoge av stoffet, på grunn av dets korrelasjon av giftighet og insekticid aktivitet, hvilket vil fremgå av den følgende tabell 4.<*>) Lokal prøvemetode ble utført ved å behandle overvintrende larver av risstilkborere på følgende måte: Hver enkelt forbindelse, som skulle undersøkes, ble løst opp i aceton, slik at man fikk en rekke acetonoppløsninger som inneholdt fra 0,067 til 2 % av vedkommende forbindelse (g/cm<3>). Porsjoner på hver 1/1000 cm<3> av vedkommende oppløsning ble påført på larvelegemet ved hjelp av en mikrosprøyte, og etter at preparatet var holdt i 3 dager ved 25° C ble det iakttatt hvor mange som var døde og hvor mange som var overlevende. De larver som ble anvendt i dette forsøk, hadde omtrent ens vekt, varierende fra 80 til 90 mg. og hver porsjon oppløsning ble tilført til en gruppe på 20 larver, for å bestemme den midlere prosent av drepte. Den følgende tabell 5 viser mer detal-jert effektiviteten av forbindelsen i henhold til oppfinnelsen like overfor risstilkborer, sammenlignet med paration. 0,0-Dimethyl-O-(4-cyanophenyl)thiophosphate used according to the present invention occupies a completely unique position among other isomers, homologues and analogues of the substance, due to its correlation of toxicity and insecticidal activity, which will appear from the following table 4.<*>) Local test method was carried out by treating overwintering larvae of rice stem borers in the following way: Each individual compound to be examined was dissolved in acetone, so that a series of acetone solutions containing from 0.067 to 2% of the compound in question (g/cm<3>). Portions of each 1/1000 cm<3> of the relevant solution were applied to the larval body using a microsyringe, and after the preparation had been kept for 3 days at 25° C, it was observed how many had died and how many had survived . The larvae used in this experiment had approximately the same weight, varying from 80 to 90 mg. and each portion of solution was added to a group of 20 larvae, to determine the mean percentage killed. The following table 5 shows in more detail the effectiveness of the compound according to the invention against the rice stem borer, compared to parathion.
Potteforsøk mot annen generasjon av larver av risstilkborer. Pot trial against second generation of rice stem borer larvae.
(dusjing av borere som borer seg inn i en risplante). (showering of borers that bore into a rice plant).
Den følgende tabell 7 viser effektiviteten av preparatet ifølge oppfinnelsen mot andre skadevesener enn de ovenfor nevnte. The following table 7 shows the effectiveness of the preparation according to the invention against pests other than those mentioned above.
(«50.E.» betegner et emulgerbart konsentrat som inneholder 50 vekts pst. aktivt stoff ifølge oppfinnelsen, 10 vektdeler xylen og 40 vektdeler «Triton X-100» [en polye-tylen-glykol-nonylf enyl-eter]. ("50.E." denotes an emulsifiable concentrate containing 50% by weight of active substance according to the invention, 10 parts by weight of xylene and 40 parts by weight of "Triton X-100" [a polyethylene glycol nonyl phenyl ether].
For anvendelse av det stoff, altså 0,0-dimetyl-0-(4-cyanfenyl)tionfosfat som oppfinnelsen angår, i praksis, kan det med-an vendes forskjellige inerte bærere, slik at det fås et insektisid preparat, som inneholder en toksisk mengde av stoffet. Preparatet kan ha form av emulsjon, suspensjon, støv- eller oljepreparat. For the use of the substance, i.e. 0,0-dimethyl-0-(4-cyanophenyl)thiophosphate to which the invention relates, in practice, different inert carriers can also be used, so that an insecticidal preparation is obtained, which contains a toxic amount of the substance. The preparation can take the form of an emulsion, suspension, dust or oil preparation.
Et emulgert preparat kan f. eks. fremstilles ved å blande stoffet med et organisk oppløsningsmiddel og et overflateaktivt middel i passende forhold til at det fås et emulgerbart konsentrat, som så fortynnes passende med vann når det skal anvendes i praksis. Som oppløsningsmiddel kan det med fordel benyttes et aromatisk hydrokarbon, f. eks. benzen eller xylen, og som overflateaktivt stoff kan man anvende nesten alle slags ikke-ioniske overflateaktive stoffer. Blandingsforholdet mellom disse materialer kan velges fritt, alt etter mate-rialenes art og formålet med preparatet. Som regel vil 50 vektdeler aktivt stoff blandet med 10 vektdeler oppløsningsmiddel og 40 vektdeler av et overflateaktivt stoff gi et godt emulgerbart konsentrat. I enkelte tilfeller kan i henhold til oppfinnelsen det aktive stoff blandes bare med et ikke ionisk overflateaktivt materiale og gi et emulgerbart konsentrat. For bruk i praksis fortynnes konsentratet med en passende mengde vann, så det dannes en emulsjon som dusjes ut direkte. An emulsified preparation can e.g. is prepared by mixing the substance with an organic solvent and a surface-active agent in suitable proportions to obtain an emulsifiable concentrate, which is then diluted appropriately with water when it is to be used in practice. An aromatic hydrocarbon can advantageously be used as a solvent, e.g. benzene or xylene, and almost all kinds of non-ionic surfactants can be used as surfactants. The mixing ratio between these materials can be chosen freely, depending on the nature of the materials and the purpose of the preparation. As a rule, 50 parts by weight of active substance mixed with 10 parts by weight of solvent and 40 parts by weight of a surfactant will give a good emulsifiable concentrate. In some cases, according to the invention, the active substance can be mixed only with a non-ionic surface-active material and give an emulsifiable concentrate. For use in practice, the concentrate is diluted with a suitable amount of water, so an emulsion is formed which is showered out directly.
For fremstilling av fuktbart pulver blir stoffet blandet med et ikke-ionisk For the production of wettable powder, the substance is mixed with a non-ionic
overflateaktivt materiale, og videre med en pulverformet bærer. Som overflateaktivt materiale kan det også her benyttes nesten ethvert ikke-ionisk overflateaktivt stoff, og som pulverformet bærer kan det anvendes f. eks. talkum, kaolin, bentonit, diato-méjord og sur japansk leire. Det pulver-formede bæremateriale bør ha en partik-kelstørrelse på over 200 masker. Blandingsforholdet kan med fordel være 5—25 vekts pts. stoff ifølge oppfinnelsen, 5—10 vekts pst. overflateaktivt materiale og de reste-rende vekts pst. utgjøres av den pulverfor-mede bærer, men disse forhold kan ellers varieres fritt alt etter anvendelsesformålet. En egnet suspensjon for bruk i praksis fås lett ved bare å røre ut det fuktbare pulver i vann. surface-active material, and further with a powdered carrier. Almost any non-ionic surface-active substance can be used as a surface-active material here, and as a powdered carrier it can be used, e.g. talc, kaolin, bentonite, diatomaceous earth and acidic Japanese clay. The powdered carrier material should have a particle size of over 200 mesh. The mixing ratio can advantageously be 5-25 parts by weight. substance according to the invention, 5-10 weight percent surface-active material and the remaining weight percent is made up of the powdered carrier, but these ratios can otherwise be varied freely depending on the purpose of use. A suitable suspension for use in practice is easily obtained by simply stirring the wettable powder into water.
Ved å blande en passende mengde aktivt stoff med en pulverformet bærer, kan det fremstilles et bestøvningspreparax. Dette kan skje ved å blande bestanddelene direkte med hinannen, men fortrinnsvis blir det aktive stoffet løst opp i et oppløs-ningsmiddel som har lavt kokepunkt, og oppløsningen blandes med bæreren, hvoretter oppløsningsmidlet fjernes ved destillasjon. Det erholdte støvpreparat bør for-trinsvis inneholde 1—5 vekts pst. av stoffet ifølge oppfinnelsen. Som fast bærestoff anvendes med fordel slike materialer som allerede er nevnt for fremstilling av fuktbart pulver. By mixing a suitable amount of active substance with a powdered carrier, a pollination preparation can be prepared. This can be done by mixing the components directly with each other, but preferably the active substance is dissolved in a solvent that has a low boiling point, and the solution is mixed with the carrier, after which the solvent is removed by distillation. The dust preparation obtained should preferably contain 1-5% by weight of the substance according to the invention. As a solid carrier, such materials as have already been mentioned for the production of wettable powder are advantageously used.
Ennvidere kan det aktive stoffet løses opp i f. eks. deodorisert kerosen og derved gi et oljepreparat av passende konsentra-sjon. Det aktive stoff er som regel så lite oppløselig i kerosen at det samtidig må anvendes et hjelpeoppløsningsmiddel. Som sådant kan det med fordel anvendes benzen, xylen eller metylnaftalin. Furthermore, the active substance can be dissolved in e.g. deodorized the kerosene and thereby give an oil preparation of suitable concentration. The active substance is usually so poorly soluble in kerosene that an auxiliary solvent must be used at the same time. As such, benzene, xylene or methylnaphthalene can be used with advantage.
For fremstilling av insektiside preparater i henhold til oppfinnelsen, kan det, foruten de foran nevnte fremstillingsme-toder, anvendes enhver annen kjent frem-gangsmåte for fremstilling av organiske fosforinsektisider. Ennvidere kan insektiside preparater i henhold til den- foreliggende oppfinnelse blandes med annet materiale f. eks. med en aktiv insektisid bestanddel av en annen type, en fungisid eller herbisid type, alt etter forholdene. For the production of insecticidal preparations according to the invention, in addition to the aforementioned production methods, any other known method for the production of organic phosphorus insecticides can be used. Furthermore, insecticidal preparations according to the present invention can be mixed with other material, e.g. with an active insecticidal component of a different type, a fungicide or herbicide type, depending on the conditions.
Når et insektisid preparat i henhold til oppfinnelsen benyttes i praksis for å drepe skadeinsekter blir preparatet tilført insektene på en slik måte at en insektisid mengde, av 0,0-dimetyl-O-(4-cyanfenol) - tionfosfat bringes i berøring med de skadelige insekter. Hvis det for eksempel anvendes et 50 pst. emulgerbart konsentrat, kan det for fullstendig utryddelse av risborere være tilstrekkelig å anvende 70—80 liter av en til 1/2000 fortynnet emulsjon på 10 ar mot de først utviklede larver og deretter benytte 90—180 liter av 1/1000 fortynnet emulsjon pr. 10 ar mot den annen generasjon av larver. Hvis det benyttes et støv-preparat i henhold til oppfinnelsen som inneholder 1,5 pst. aktivt stoff kan med fordel 3—4 kg av dette støv påføres pr. 10 ar over de først utviklede larver av risborere, og deretter kan fra 5 til 6 kg pr. 10 ar være tilstrekkelig for behandling av den annen larvegenerasjon. Hvis det benyttes fuktbart pulver i henhold til oppfinnelsen som inneholder 25 pst. aktivt stoff, kan 70—80 liter 1/1000 vandig suspensjon pr. 10 ar være egnet til bruk mot de først genererte larver og 90—180 liter 1/500 vandig suspensjon pr. 10 ar mot den annen generasjon av risborerlarver. When an insecticidal preparation according to the invention is used in practice to kill harmful insects, the preparation is added to the insects in such a way that an insecticidal quantity of 0,0-dimethyl-O-(4-cyanophenol)-thiophosphate is brought into contact with the harmful insects. If, for example, a 50% emulsifiable concentrate is used, for complete eradication of rice borers it may be sufficient to use 70-80 liters of an emulsion diluted to 1/2000 in 10 years against the first developed larvae and then use 90-180 liters of 1/1000 diluted emulsion per 10 years against the second generation of larvae. If a dust preparation according to the invention is used which contains 1.5% active substance, 3-4 kg of this dust can be applied with advantage per 10 years above the first developed larvae of rice borers, and then from 5 to 6 kg per 10 years should be sufficient for treatment of the second larval generation. If wettable powder according to the invention is used which contains 25% active substance, 70-80 liters of 1/1000 aqueous suspension per 10 years be suitable for use against the first generated larvae and 90-180 liters of 1/500 aqueous suspension per 10 years against the second generation of rice borer larvae.
Oppfinnelsen belyses nærmere ved de etterfølgende eksempler. Hvis intet annet er nevnt, betegner alle angitte deler vektdeler. The invention is explained in more detail by the following examples. Unless otherwise stated, all parts given are parts by weight.
Eksempel 1 Example 1
Til en blanding av 32,8 g 4-cyanfenol og 27,6 g vannfritt kaliumkarbonat i 200 ml isobutylketon ble det ved 60° C og under omrøring dråpevis tilsatt 32,2 g 0,0-dimetyl-klortionfosfat. Etter tildryppingen ble blandingen omrørt videre i 8 timer ved 60—80° C, for å fullføre reaksjonen. Vann ble tilsatt for å løse opp den utfelte anor-ganiske forbindelse, det organiske lag ble skilt fra, vasket med vann og tørket over vannfritt natriumsulfat. Etter avdestille-ring av metylisobutylketonet i vakuum, ble det tilbake et rødbrunt oljeaktig produkt, som veiet 45,2 g. For videre rensing ble dette rå produkt kromatografert i en søyle under anvendelse av aktivt kull og aktivt aluminiumoksyd, hvorved man fikk et lyse-gult oljeaktig produkt, hvis brytningskoef-fisient var nD ' = 1,5457. To a mixture of 32.8 g of 4-cyanophenol and 27.6 g of anhydrous potassium carbonate in 200 ml of isobutyl ketone, 32.2 g of 0.0-dimethylchlorothiophosphate was added dropwise at 60° C. and with stirring. After the addition, the mixture was further stirred for 8 hours at 60-80° C, to complete the reaction. Water was added to dissolve the precipitated inorganic compound, the organic layer was separated, washed with water and dried over anhydrous sodium sulfate. After distilling off the methyl isobutyl ketone in vacuum, a reddish-brown oily product was left, which weighed 45.2 g. For further purification, this crude product was chromatographed in a column using activated carbon and activated aluminum oxide, whereby a light- yellow oily product, the refractive index of which was nD' = 1.5457.
21 2 21 2
Analyse Analysis
Beregnet (for CH.JSKXPS): Calculated (for CH.JSKXPS):
P = 12,8; S = 13,2; N = 5,76 pst. P = 12.8; S = 13.2; N = 5.76 percent.
Funnet: Found:
P = 12,7; S = 13,0; N= 5,68 pst. P = 12.7; S = 13.0; N= 5.68 percent.
Eksempel 2 Example 2
Til en blanding av 23,8 g 4-cyanfenol, 32,2 g 0,0-dimetyl-klortionfosfat og 0,1 g kuproklorid i 100 ml toluen, som var opp-varmet til 60° C, ble det i små porsjoner tilsatt 27,6 g vannfritt kaliumkarbonat. Det ved reaksjonen dannede vann ble fjernet azeotropisk sammen med toluenet, og dess-uten unnvek det dannede kulldioksyd. Etter at reaksjonen var fullført ble reaksjons-produktet behandlet på samme måte som i eksempel 1, og ga omtrent den samme mengde effektivt produkt. To a mixture of 23.8 g of 4-cyanophenol, 32.2 g of 0.0-dimethylchlorothiophosphate and 0.1 g of cuprous chloride in 100 ml of toluene, which had been heated to 60° C, was added in small portions 27.6 g anhydrous potassium carbonate. The water formed by the reaction was removed azeotropically together with the toluene, and in addition the carbon dioxide formed escaped. After the reaction was complete, the reaction product was treated in the same manner as in Example 1, yielding approximately the same amount of effective product.
Eksempel 3 Example 3
Fremgangsmåten i eksempel 1 ble gjentatt, med den forskjell at det i stedet for 4-cyanfenol og vannfritt kaliumkarbonat ble benyttet den tilsvarende mengde av natrium-4-cyanfenolat, og at klorben-zen ble brukt som oppløsningsmiddel i stedet for metylisobutylketon. Det ble opp-nådd samme resultat som i de ovenstående eksempler. The procedure in example 1 was repeated, with the difference that instead of 4-cyanophenol and anhydrous potassium carbonate, the corresponding amount of sodium 4-cyanophenolate was used, and that chlorobenzene was used as solvent instead of methyl isobutyl ketone. The same result was achieved as in the above examples.
Eksempel 4 Example 4
50 deler 0,0-dimetyl-0-(4-cyanfenyl.i-tionfosfat ble forenet med 40 deler «Triton X-100» (en polyetylenglykolnonylfenyleter) og 10 deler xylen, i den angitte rekkefølge, hvorved det fåes et jevnt,emulgerbart,konsentrat. Risplanter ble, 20 dager etter deres utsåing, overført til Wagner-potter med overflate 1/50 000 av 10 ar, med 4 planter i hver potte. Etter 2 måneders forløp ble disse planter infisert med risstilkborere, og 3 dager etter at disse skadevesener var blitt utviklet ble der på hver potte dusjet 10 ml av en til 1/1000 fortynnet emulsjon 50 parts of 0,0-dimethyl-0-(4-cyanophenyl.i-thiophosphate) were combined with 40 parts of "Triton X-100" (a polyethylene glycol nonylphenyl ether) and 10 parts of xylene, in the order indicated, whereby a smooth, emulsifiable ,concentrate. Rice plants were, 20 days after their sowing, transferred to Wagner pots with a surface area of 1/50,000 of 10 ar, with 4 plants in each pot. After 2 months these plants were infested with rice stem borers, and 3 days after these pests had developed, 10 ml of an emulsion diluted to 1/1000 was showered on each pot
av det ovennevnte 50 pst.s konsentrat. Praktisk talt 100 pst. av borerne som for-søkte å krype inn i stilkene ble drept i løpet av 3 dager. of the above-mentioned 50 percent concentrate. Practically 100 per cent of the borers that tried to crawl into the stems were killed within 3 days.
Eksempel 5 Example 5
1 1/2 del 0,0-dimetyl-O-(4-cyanfenyl)-tionfosfat ble løst opp i aceton og oppløs-ningen ble grundig blandet med 98,5 deler talkum av 200 maskers partikkelstørrelse Ved fordampning av oppløsningsmidlet fikk man et bestøvningspreparat som inneholdt 1,5 pst. virksomt stoff. På risplanter ble det påført risboreregg under de samme be-tingelser som i eksempel 1 og 3 dager etter eggenes utvikling ble potten anbragt i be-støvningsapparatet, dusjet med 0,2 g av vedkommende støv, tatt ut igjen etter 30 minutters forløp, og fikk så henstå. Praktisk talt 100 pst av larvene som forsøkte å krype inn i stilken ble drept i løpet av 3 dager. Eksempel 6 30 deler 0,0-dimetyl-O-(4-cyanfenyl)-tionfosfat og 10 deler «Triton X-100» ble blandet grundig og blandingen ble dråpe vis tilsatt til 60 deler talkum av 200 maskers partikkelstørrelse i en kulemølle, hvorved man fikk et fuktbart pulver. På lignende måte som i eksempel 1 ble egg av risstilkborer påført på risplanter, og 3 dager etter at eggene var utviklet ble det pr. potte på-dusjet 10 ml av en 1/600 vandig suspensjon av det nevnte fuktbare pulver. Praktisk talt 100 pst. av borerne, som forsøkte å krype inn i stilkene, ble drept i løpet av 3 dager. Eksempel 7 1 1/2 del 0,0-dimetyl-O-(4-cyanfenyl)-tionfosfat ble løst opp i 20 deler «Versicol AR-50» (et aromatisk hydrokarbonoppløs-ningsmiddel) og til blandingen ble det satt 78,3 deler «Deobase» (deodorisert hydro-karbonoppløsningsmiddel) hvorved man fikk et oljeaktig preparat. Når 66 ml av denne olje ble dusjet på 1 m2 av et gunstig flueut-klekningssted, f. eks. på en avfallsdynge, ble nesten 100 pst. av fluelarvene på dette sted drept i løpet av 48 timer. 1 1/2 parts of 0,0-dimethyl-O-(4-cyanophenyl)-thiophosphate was dissolved in acetone and the solution was thoroughly mixed with 98.5 parts of talc of 200 mesh particle size. By evaporating the solvent, a pollination preparation was obtained which contained 1.5 percent active substance. On rice plants, rice borer eggs were applied under the same conditions as in example 1 and 3 days after the development of the eggs, the pot was placed in the pollination apparatus, showered with 0.2 g of the relevant dust, taken out again after 30 minutes, and given then hold off. Practically 100 percent of the larvae that tried to crawl into the stem were killed within 3 days. Example 6 30 parts of 0,0-dimethyl-O-(4-cyanophenyl)-thiophosphate and 10 parts of "Triton X-100" were mixed thoroughly and the mixture was added dropwise to 60 parts of talc of 200 mesh particle size in a ball mill, whereby a wettable powder was obtained. In a similar way as in example 1, eggs of the rice stem borer were applied to rice plants, and 3 days after the eggs had developed, per pot on-showered 10 ml of a 1/600 aqueous suspension of the aforementioned wettable powder. Practically 100 per cent of the borers, which tried to crawl into the stems, were killed within 3 days. Example 7 1 1/2 parts of 0,0-dimethyl-O-(4-cyanophenyl)-thiophosphate was dissolved in 20 parts of "Versicol AR-50" (an aromatic hydrocarbon solvent) and to the mixture was added 78.3 parts "Deobase" (deodorized hydrocarbon solvent) whereby an oily preparation was obtained. When 66 ml of this oil was showered on 1 m2 of a favorable fly hatching site, e.g. on a waste heap, almost 100 per cent of the fly larvae at this site were killed within 48 hours.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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SE826070A SE355615B (en) | 1970-06-15 | 1970-06-15 |
Publications (2)
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NO140938B true NO140938B (en) | 1979-09-03 |
NO140938C NO140938C (en) | 1979-12-12 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO221571A NO140938C (en) | 1970-06-15 | 1971-06-11 | METHOD AND DEVICE FOR FORMING A CONTINUOUS MATERIAL PATH OF FIBROSE PARTICLES |
Country Status (12)
Country | Link |
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JP (1) | JPS5529198B1 (en) |
AT (1) | AT322350B (en) |
CA (1) | CA945413A (en) |
DE (1) | DE2129717C3 (en) |
ES (1) | ES392224A1 (en) |
FI (1) | FI51116C (en) |
FR (1) | FR2097903A5 (en) |
GB (1) | GB1338518A (en) |
NL (2) | NL167485C (en) |
NO (1) | NO140938C (en) |
SE (1) | SE355615B (en) |
SU (2) | SU562209A3 (en) |
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CA1320860C (en) * | 1988-10-12 | 1993-08-03 | Luc Y. Fortier | Headbox |
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GB469203A (en) * | 1936-03-21 | 1937-07-21 | Samuel Milne | Improvements in and relating to paper-making machines |
US2506678A (en) * | 1944-07-06 | 1950-05-09 | Warren S D Co | Apparatus for use in making paper |
US2920699A (en) * | 1956-12-14 | 1960-01-12 | Sandy Hill Iron And Brass Work | Paper making apparatus |
NO119299B (en) * | 1962-04-12 | 1970-04-27 | Karlstad Mekaniska Ab | |
US3220919A (en) * | 1962-10-05 | 1965-11-30 | Beloit Corp | Shaped rod turbulence generators for use in a flowing stream of paper pulp |
US3298905A (en) * | 1964-05-14 | 1967-01-17 | Scott Paper Co | Tapered manifold type stock distributor for a papermaking machine |
GB1069957A (en) * | 1964-08-27 | 1967-05-24 | Krofta Milos | Apparatus for producing webs of paper-like fibrous materials |
US3471368A (en) * | 1966-02-24 | 1969-10-07 | Nicolas M Reitzel | Headbox for papermaking machine |
DE1511246A1 (en) * | 1966-07-23 | 1969-07-24 | Voith Gmbh J M | Headbox for paper machines |
US3514372A (en) * | 1966-11-29 | 1970-05-26 | Beloit Corp | Headbox method and means for blending of multiple jets |
US3652392A (en) * | 1969-11-24 | 1972-03-28 | Kimberly Clark Co | Contracting pre-slice flow distributor for papermaking machine headbox |
-
1970
- 1970-06-15 SE SE826070A patent/SE355615B/xx unknown
-
1971
- 1971-06-11 NO NO221571A patent/NO140938C/en unknown
- 1971-06-14 FI FI166871A patent/FI51116C/en active
- 1971-06-14 ES ES392224A patent/ES392224A1/en not_active Expired
- 1971-06-14 CA CA115,543A patent/CA945413A/en not_active Expired
- 1971-06-15 SU SU1716306A patent/SU562209A3/en active
- 1971-06-15 SU SU1672344A patent/SU458138A3/en active
- 1971-06-15 DE DE19712129717 patent/DE2129717C3/en not_active Expired
- 1971-06-15 GB GB2807671A patent/GB1338518A/en not_active Expired
- 1971-06-15 NL NL7108181A patent/NL167485C/en not_active IP Right Cessation
- 1971-06-15 FR FR7121740A patent/FR2097903A5/fr not_active Expired
- 1971-06-15 JP JP4288871A patent/JPS5529198B1/ja active Pending
- 1971-06-15 AT AT517271A patent/AT322350B/en not_active IP Right Cessation
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1981
- 1981-03-27 NL NL8101516A patent/NL8101516A/en active Search and Examination
Also Published As
Publication number | Publication date |
---|---|
ES392224A1 (en) | 1974-02-16 |
SE355615B (en) | 1973-04-30 |
DE2129717B2 (en) | 1974-09-12 |
AT322350B (en) | 1975-05-12 |
DE2129717C3 (en) | 1981-12-17 |
NL7108181A (en) | 1971-12-17 |
SU458138A3 (en) | 1975-01-25 |
SU562209A3 (en) | 1977-06-15 |
NL167485C (en) | 1981-12-16 |
CA945413A (en) | 1974-04-16 |
FI51116C (en) | 1976-10-11 |
DE2129717A1 (en) | 1972-01-27 |
NL167485B (en) | 1981-07-16 |
FI51116B (en) | 1976-06-30 |
NL8101516A (en) | 1981-08-03 |
GB1338518A (en) | 1973-11-28 |
JPS5529198B1 (en) | 1980-08-01 |
NO140938C (en) | 1979-12-12 |
FR2097903A5 (en) | 1972-03-03 |
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