CS199739B2 - Process for preparing new organic esters of phosphoric acid - Google Patents
Process for preparing new organic esters of phosphoric acid Download PDFInfo
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- CS199739B2 CS199739B2 CS79160A CS16079A CS199739B2 CS 199739 B2 CS199739 B2 CS 199739B2 CS 79160 A CS79160 A CS 79160A CS 16079 A CS16079 A CS 16079A CS 199739 B2 CS199739 B2 CS 199739B2
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- Czechoslovakia
- Prior art keywords
- carbon atoms
- phosphoric acid
- organic esters
- new organic
- preparing new
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 title 1
- 150000002895 organic esters Chemical class 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- -1 thiophosphoryl halide Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 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
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
Vynález se týká způsobu výroby nových organických esterů kyseliny fosforečné, vykazujících vznikající insekticidní, akaricidní a nematocidní účinek.The invention relates to a process for the production of novel organic phosphoric esters having an insecticidal, acaricidal and nematicidal effect.
Sloučeniny vyráběné způsobem podle vynálezu odpovídají obecnému vzorci IThe compounds produced by the process according to the invention correspond to the general formula I
RlO O X Y \ll I IR 10 O X Y I II
P—O—CH—C—Y (lj,P — O — CH — C — Y (1j,
Z IZ I
R2S Y ve kterém znamenáR 2 SY in which denotes
R1 alkylovou skupinu s 1 až 3 atomy uhlíku,R 1 is alkyl having 1 to 3 carbon atoms,
R2 alkylovou skupinu se 3 nebo 4 atomy uhlíku nebo alkoxyalkylovou skupinu se 3 až 6 atomy uhlíku,R ( 2) is alkyl of 3 or 4 carbon atoms or alkoxyalkyl of 3 to 6 carbon atoms,
X atom vodíku, trihalogenmethylovou skupinu nebo alkoxyskupinu s 1 až 4 atomy uhlíku,X is hydrogen, trihalomethyl or C1-C4alkoxy,
Y atom fluoru nebo chloru.Y is fluorine or chlorine.
V souhlase s vynálezem se nové sloučeniny obecného vzorce I vyrábějí tak, že se thiofosforylhalogenid obecného vzorce IIIn accordance with the invention, the novel compounds of formula I are prepared by the formation of a thiophosphoryl halide of formula II
Hal O X Y \ll I !Hal O X Y!
P—O—CH—C—Υ (II),P — O — CH — C — Υ (II),
Z IZ I
R2S Y ve kterémR 2 SY in which
R2, X a Y mají shora uvedený význam aR 2, X and Y have the above meanings and
Hal znamená atom halogenu, nechá reagovat s alkoholem nebo alkoxidem, obecného vzorce IIIHal is a halogen atom, reacted with an alcohol or alkoxide of formula III
M—O—R1 (III), ve kterémM - O - R 1 (III) in which
R1 má shora uvedený význam aR 1 has the abovementioned meaning and
M znamená atom vodíku nebo alkalický kov.M represents a hydrogen atom or an alkali metal.
Jako příklady thiofosforylhalogenidů obecného vzorce II, které jsou vhodné jako výchozí látky při práci způsobem podle vynálezu, se uvádějíExamples of thiophosphoryl halides of the formula II which are suitable as starting materials in the process according to the invention are:
0-2,2,2-trifluorethyl-S-n-propylfosforochloridothioát,0-2,2,2-trifluoroethyl-S-n-propylphosphorochloridothioate,
O-2,2,2-trichlorethyl-S-n-propylfosforochloridothioát,O-2,2,2-trichloroethyl-S-n-propylphosphorochloridothioate,
O-l,l,l,3,3,3-hexafluor-2-propyl-S-n-propylfosforochloridothioát,O-1,1,1,3,3,3-hexafluoro-2-propyl-S-n-propylphosphorochloridothioate,
O-l,l,l,3,3,3-hexachlor-2-propyl-S-n-propylfosforochloridothioát,O-1,1,1,3,3,3-hexachloro-2-propyl-S-n-propylphosphorochloridothioate,
O-2,2,2-trifluorethyl-S-n-butylfosforochloridothioát,O-2,2,2-trifluoroethyl-S-n-butylphosphorochloridothioate,
O-2,2,2-trichlorethyl-S-n-butylfosforochloridothioát,O-2,2,2-trichloroethyl-S-n-butylphosphorochloridothioate,
O-l,l,l,3,3,3-hexafluor-2-propyl-S-n-butylfosforochloridothioát,O-1,1,1,3,3,3-hexafluoro-2-propyl-S-n-butylphosphorochloridothioate,
0-2,2,2-trif luorethyl-S-isobutylfosforochloridothioát,0-2,2,2-trifluoroethyl-S-isobutylphosphorochloridothioate,
O-2,2,2-trichlorethyl-S-isobutylfosforochloridothioát,O-2,2,2-trichloroethyl-S-isobutylphosphorochloridothioate,
O-l,l,l,3,3,3-hexafluor-2-propyl-S-sek.butylfosforochloridothioát,O-1,1,1,3,3,3-hexafluoro-2-propyl-S-sec-butylphosphorochloridothioate,
0-2,2,2-trif luorethyl-S-sek.butylfosforochloridothioát,0-2,2,2-Trifluoroethyl-S-sec-butylphosphorochloridothioate
O-2,2,2-trichlorethyl-S-sek.butylfosforochloridothioát,O-2,2,2-trichloroethyl-S-sec-butylphosphorochloridothioate,
0-2,2,2-trif luorethyl-S-2-methoxyethylfosforochloridothioát,0-2,2,2-trifluoroethyl-S-2-methoxyethylphosphorochloridothioate,
O-2,2,2-trifluorethyl-S-2-ethoxyethylfosforochloridothioát,O-2,2,2-trifluoroethyl-S-2-ethoxyethylphosphorochloridothioate,
O-2,2,2-trichlorethyl-S-2-ethoxyethylfosforochloridothioát,O-2,2,2-trichloroethyl-S-2-ethoxyethylphosphorochloridothioate,
O-l,l,l,3,3,3-hexafluor-2-propyl-S-2-ethoxyethylfosforochloridothioát,O-1,1,1,3,3,3-hexafluoro-2-propyl-S-2-ethoxyethylphosphorochloridothioate,
0-2,2,2-trif luorethyl-S- (2-n-propoxyethyl) fosforochloridothioát,0-2,2,2-trifluoroethyl-S- (2-n-propoxyethyl) phosphorochloridothioate,
0-2,2,2-trif luorethyl-S-2-isopropoxyethylfosforochloridothioát,0-2,2,2-trifluoroethyl-S-2-isopropoxyethylphosphorochloridothioate,
O-2,2,2-trichlorethyl-S-2-isopropoxyethylfosforochloridothioát aO-2,2,2-trichloroethyl-S-2-isopropoxyethyl phosphorochloridothioate and
0-2,2,2-trif luorethyl-S-(2-n-butoxyethyl )fosforochloridothioát, jakož i odpovídající bromidy.O-2,2,2-trifluoroethyl-S- (2-n-butoxyethyl) phosphorochloridothioate, as well as the corresponding bromides.
Jako příklady alkoholů a alkoxidů obecného vzorce III, které jsou vhodné jako výchozí látky při práci způsobem podle vynálezu, se uvádějí methanol, ethanol a n-propanol, a sodné a draselné alkoxidy odvozené od těchto alkoholů.Examples of alcohols and alkoxides of formula III which are useful as starting materials in the process of the invention are methanol, ethanol and n-propanol, and sodium and potassium alkoxides derived from these alcohols.
Použijí-li se při práci způsobem podle vynálezu jako výchozí látky 0-2,2,2-trifluorethyl-S-n-butylfosforochloridothioát a ethanol, je možno průběh této reakce popsat následujícím reakčním schématem:When O-2,2,2,2-trifluoroethyl-S-n-butylphosphorochloridothioate and ethanol are used as starting materials in the process according to the invention, the following reaction scheme can be described:
Cl O \llCl O \ ll
P—O—CH2CF3 -|ZP - O - CH 2 CF 3 - | Z
CH3CH2CH2CH2S + C2H5OH----—CH3CH2CH2CH2S + C2H5OH ----—
C2H5O o \llC2H5O
----> P—O—CH2CF3 + HCl z----> P — O — CH2CF3 + HCl z
CH3CH2CH2CH2SCH3CH2CH2CH2S
Reakci podle vynálezu je možno provádět v přítomnosti činidla vázajícího kyselinu. Jako příklady vhodných činidel vázajících kyselinu je možno uvést hydroxidy, uhličitany, hydrogenuhličitany a alkoxidy alkalických kovů, jakož i terciární aminy, například triethylamin, diethylanilin nebo pyridin.The reaction of the invention may be carried out in the presence of an acid binding agent. Examples of suitable acid binding agents are alkali metal hydroxides, carbonates, bicarbonates and alkoxides, as well as tertiary amines, for example triethylamine, diethylaniline or pyridine.
Při práci způsobem podle vynálezu je možno finální produkt získat v dobrém výtěžku a ve vysoké čistotě i v případě, že se pracuje bez použití činidla vázajícího kyselinu. V takovém případě se thiofosforylhalogenid obecného vzorce II podrobuje reakci s alkoxidem alkalického kovu obecného vzorce III.In the process according to the invention, the final product can be obtained in good yield and high purity even when operated without the use of an acid binding agent. In this case, the thiophosphoryl halide of formula II is reacted with an alkali metal alkoxide of formula III.
Reakce podle vynálezu se s výhodou provádí za použití rozpouštědla nebo ředidla. Jako příklady vhodných rozpouštědel nebo ředidel lze uvést vodu a inertní organická rozpouštědla, jako alifatické, alicyklické a aromatické uhlovodíky (které mohou být popřípadě chlorované), jako například hexan, cyklohexan, petrolether, ligroin, benzen, toluen, xylen, methylenchlorid, trichlorethylen a chlorbenzen, dále ethery, jako například diethylether, methylethylether, diisopropylether, dibutylether, propylenoxid, dioxán a tetrahydrofuran, ketony, jako například aceton, methylethylketon, methylisopropylketon a methylisobutylketon, nltrily, jako například acetonitril, propionitril a akrylonitril, alkoholy, jako například methanol, ethanol, isopropanol, butanoly a ethylenglykol, estery, jako například ethylacetát a amylacetát, amidy kyselin, jako například dimethylformamid a dimethylacetamid, sulfony a sulfoxidy, jako například dimethylsulfoxld a dimethylsulfon, a organické báze, jako například pyridin.The reaction of the invention is preferably carried out using a solvent or diluent. Examples of suitable solvents or diluents include water and inert organic solvents such as aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, trichlorethylene and chlorobenzene and ethers such as diethyl ether, methylethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile, propionitrile and methanol, alcohols, isopropanol, butanols and ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfones and sulfoxides such as dimethylsulfoxide and dimethylsulfone, and organic bases such as pyridine.
Reakci podle vynálezu je možno provádět v širokém teplotním rozmezí. Obecně se pracuje při teplotě od — 20 °C do teploty varu reakční směsi, s výhodou při teplotě 0 až 100 °C. Reakce se účelně provádí za atmosférického tlaku, lze ji však uskutečnit i za tlaku zvýšeného nebo sníženého.The reaction according to the invention can be carried out over a wide temperature range. In general, the reaction is carried out at a temperature of from -20 ° C to the boiling point of the reaction mixture, preferably at a temperature of 0 to 100 ° C. The reaction is conveniently carried out at atmospheric pressure, but can also be carried out at elevated or reduced pressure.
Jak již bylo uvedeno výše, vykazují sloučeniny podle vynálezu vynikající insekticid199739 ní, akarlcidní a nematocidní účinek. Tyto látky lze proto nasazovat k potírání škůdců rostlin a škůdců vyskytujících se v oblasti hygieny a při ochraně zásob, popřípadě materiálů. Zmíněné látky přitom vykazují kombinaci nízké fytotolxicity s dobrým účinkem proti bodavému a kousavému hmyzu a roztočovitým.As noted above, the compounds of the present invention exhibit excellent insecticide, acarlide and nematicide activity. These substances can therefore be used to combat plant pests and pests occurring in the field of hygiene and to protect stocks or materials. Said substances show a combination of low phytotolxicity with good action against stinging, biting insects and mites.
Testy účinnosti sloučenin vyrobených způsobem podle vynálezu, jakož i popis složení a přípravy vhodných prostředků obsahujících sloučeniny obecného vzorce I jako účinné látky, jsou uvedeny v čs. patentu čís. 199 738.Tests for the efficacy of the compounds produced by the process of the invention, as well as a description of the composition and preparation of suitable compositions containing the compounds of formula I as active ingredients, are given in U.S. Pat. No. 5,638,949; 199 738.
Vynález ilustrují následující příklady provedení, jimiž se však rozsah vynálezu v žádném směru neomezuje.The invention is illustrated by the following non-limiting examples.
Příklad 1Example 1
C2H5O O \llC2H5O
P—O—CH2CCI3 ZP — O — CH2Cl3 Z
CH3CH2CH2CH2SCH3CH2CH2CH2S
20,7 g S-n-butylfosforodichloridothioátu se rozpustí ve 150 ml toluenu, roztok se ochladí na —50 °C, přidá se k němu 14,9 gDissolve 20.7 g of S-n-butylphosphorododichloridothioate in 150 ml of toluene, cool the solution to -50 ° C and add 14.9 g of it
2,2,2-trichlorethanolu a pak za míchání při teplotě —5 až 0°C 11 g triethylaminu. Směs se nechá přes noc stát, triethylamin-hydrochlorid se odfiltruje a k filtrátu se při teplotě 0 až 5 °C přikape směs 5 g ethanolu a 11 g triethylaminu. Po skončeném přikapávání se teplota pozvolna zvýší na 60 °C a směs se při této teplotě 4 hodiny míchá.2,2,2-trichloroethanol and then with stirring at -5 to 0 ° C 11 g of triethylamine. The mixture is allowed to stand overnight, the triethylamine hydrochloride is filtered off and a mixture of 5 g of ethanol and 11 g of triethylamine is added dropwise to the filtrate at 0-5 ° C. After completion of the dropwise addition, the temperature was gradually raised to 60 ° C and the mixture was stirred at this temperature for 4 hours.
Po ochlazení se reakční směs promyje 1% vodným roztokem kyseliny chlorovodíkové, 2% vodným roztokem hydroxidu draselného a vodou, vysuší se bezvodým síranem sodným, toluen se odpaří a zbytek se destiluje za sníženého tlaku. Získá se 16,8 g O-ethyl-S-n-butyl-O-2,2,2-trichlorethylfosforothioátu o teplotě varu 134 až 136 °C/80 Pa a indexu lomu nD 20 = 1,4885.After cooling, the reaction mixture was washed with 1% aqueous hydrochloric acid, 2% aqueous potassium hydroxide solution and water, dried over anhydrous sodium sulfate, the toluene was evaporated and the residue was distilled under reduced pressure. There were obtained 16.8 g of O-ethyl-Sn-O-butyl-2,2,2-trichlorethylfosforothioátu b.p. 134-136 ° C / 80 mm Hg and the refractive index n D 20 = 1.4885.
Analogickým způsobem je možno připravit rovněž následující sloučeniny shrnuté do níže uvedené tabulky:The following compounds, summarized in the table below, can also be prepared in an analogous manner:
txtx
O) cn in no tn <Ji t)< r-l CM O -si Ml rfO) cn in no tn <Ji t) <r-1 CM 0 -si Ml rf
O=fa / \O = fa / \
RiQ ti ti •4—* wRiQ ti ti • 4— * w
ti oti o
Λ3 'ti'3 'ti
4«3 •pH4 «3 • pH
N >N>
fa cn eí Xfa cn eí X
PíPi
PíPi
CO >oCO> o
Ό tiΌ ti
Q ti tiQ to you
CM tx co oCM tx co o
o >N ti tn cmo> N ti tn cm
S S R α a o fi fi fi ce ce p< fa c- i> CO CMS S R α and fi cation f p <fa c- i> CO CM
O o co o cm oo eoAbout o o o cm oo eo
Q Q Q ·fi fi fi fi _fa <0 O Cí N fa fa fa co β β β ca fa t·»Q Q · 0 0 0 0 0 0 0 »» »» »»
CMCM
O oO o
o co oo ino co oo in
O U o o CO r-l bs OíO U o CO r-1 bs Oi
CM οσCM οσ
.. Ό< eo cm 00 ΓΗ.. Ό <eo cm 00 ΓΗ
titi
II o,5 ω o rt fi r—I »—1 ^“1 o O ft ft ft a«Q CD 01 Q) 0) O 4—I rt rt rt fiII o, 5 ω o rt fi r — I »—1 ^“ 1 o O ft ft ft a Q Q 01 Q) 0) O 4 — I rt rt rt fi
CM O -χ, o Pio 0 Ml rH r-l (X >N ti >N tiCM 0 -χ, o P 10 0 Ml rH rl (X> N ti> N ti
COWHAT
O (X r-l ti ti řXj CtiO (X r-l ti ti xX Hon
IDID
U £> 0 r-l o 00 rt >N >N e0 coU £> 0 rl o 00 rt>N> N e0 co
O) co l> OíO) co l> Oi
LT CO CO Q. fa t> t>- CMLT CO CO Q. fa t> t> - CM
O o 0 CM co eo Ol r-l >N >N cd «3 i>O to 0 cm as EO Ol rl>N> N cd «i 3>
titi
CMCM
CO inCO in
O oO o
CM >N ti <XCM> N ti <X
O ti ti r-í ti k 5 <=> £ ti ti O) ti > > Sjl >O ti ti r-ti ti 5 <=> S ti ti>> Sjl>
a ft8_ a a a a« a λυ flí τ’ λ\ /ií λ» Λ\ Q flí .8 fiD“ β β *-i 3 cO β ► > ca co +4 rt o o γ—Ί ř—H ft řM φ Φ ti co ř-ι fi oo > Ml ti τ—I tj CO ti CM >a ft8_ aaaa «a λυ flí τ 'λ \ / ií λ» Λ \ Q flí .8 fi D “β β * -i 3 cO β ►> ca co +4 rt oo γ — Ί — — H ft M φ Φ ti co-ι fi oo> Ml ti τ — I ie CO ti CM>
ti r-T S II H.Sti r-T II H.S
QíQi
O fa O fa fa fa fa o fa fa U fafafaU fafafaU fa rt fa u X o o b- bX X to KS u u b- χΧ £ t? w o oO fa O fa fa fa o fa fa U fafafaU fafafaU fa rt fa u X oo b- bX X to KS uu b- χΧ £ t? woo
Um o X X X b- 03Um o X X X b-03
XX to 4JI u oXX to 4JI u
Cí β β β β β iaÍ β β β β β ia
ΚΗ -71ΚΗ -71
Hs o 1 o fi ΆHs o 1 o fi Ά
O? OíO? Oí
X XX X
Tt* TPTt * TP
O OO O
4tí 4tí Φ Φ (Λ M i 5 x g uoTí tí (Λ M i 5 x g uo)
U *9 ^XU * 9 ^ X
I ÍM ÍM NxxI N I N N xx
X X u ω o oX X u ω o o
ΙΛ IftΙΛ Ift
X X _ ¢4 «4X X _ ¢ 4 4 4
MtJUUMtJUU
X xX x
o oo o
io sio s
uat
C4 itXC4 itX
X § U wX § U w
CM l-UCM l-U
X ΰ u o o £X ΰ u o £
XX
XX
O oO o
b*b *
X toX it
OO
XX
X uX u
oO
OíOí
XX
TfiTfi
O fi .3 .3O fi .3 .3
I ikin^ÓmirtinuíwuíI ikin ^ Ómirtinuíwuí
4? E E X i χ X X X o o u ωcouuoou4? E E X i χ X X X o o u ωcouuoou
Lfi in irs mLfi in irs m
X X X XX X X X
CM CM CM CM a o u o m io io inCM CM CM CM o o o o m io io in
X X X XX X X X
CM CM CM CM o u ο uCM CM CM CM o u ο u
XX
CMCM
O (NcoMiincoi>eooiOr-icM coMiincoO (NcoMiincoi> eooiOr-icM coMiinco
S CO O) O r-lCO 2 O r-1
Η Η H CM CM >Í4CM CM H CM CM> 44
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS79160A CS199739B2 (en) | 1977-07-25 | 1979-01-05 | Process for preparing new organic esters of phosphoric acid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52088352A JPS6021159B2 (en) | 1977-07-25 | 1977-07-25 | Organophosphate ester compound, method for producing the compound, and insecticide, acaricide, and nematocidal agent containing the compound as an active ingredient |
| CS784917A CS199738B2 (en) | 1977-07-25 | 1978-07-24 | Insecticide,acaricide and nematocide and process for preparing effective compounds |
| CS79160A CS199739B2 (en) | 1977-07-25 | 1979-01-05 | Process for preparing new organic esters of phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS199739B2 true CS199739B2 (en) | 1980-07-31 |
Family
ID=25746081
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS79161A CS199740B2 (en) | 1977-07-25 | 1979-01-05 | Process for preparing new organic esters of phosphoric acid |
| CS79160A CS199739B2 (en) | 1977-07-25 | 1979-01-05 | Process for preparing new organic esters of phosphoric acid |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS79161A CS199740B2 (en) | 1977-07-25 | 1979-01-05 | Process for preparing new organic esters of phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| CS (2) | CS199740B2 (en) |
-
1979
- 1979-01-05 CS CS79161A patent/CS199740B2/en unknown
- 1979-01-05 CS CS79160A patent/CS199739B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS199740B2 (en) | 1980-07-31 |
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