NO760777L - - Google Patents
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- Publication number
- NO760777L NO760777L NO760777A NO760777A NO760777L NO 760777 L NO760777 L NO 760777L NO 760777 A NO760777 A NO 760777A NO 760777 A NO760777 A NO 760777A NO 760777 L NO760777 L NO 760777L
- Authority
- NO
- Norway
- Prior art keywords
- dimethyl
- acid ester
- diethyl
- mol
- methanol
- Prior art date
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 101150067539 AMBP gene Proteins 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 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 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 4
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical class OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AWOYKRJEPKDQRB-UHFFFAOYSA-N 2,2-dichloroethenoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)OC=C(Cl)Cl AWOYKRJEPKDQRB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003434 Perkow synthesis reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AYKVWLVCPVEZHW-UHFFFAOYSA-N ethenoxy-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical class OP(O)(=S)OC=C AYKVWLVCPVEZHW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- LVFUWJLIDMSANU-UHFFFAOYSA-N methoxy(methylsulfanyl)phosphinous acid Chemical compound COP(O)SC LVFUWJLIDMSANU-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- -1 petrol Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Fremgangsmåte til fremstilling av 0,0-Process for the production of 0.0-
dimetyl- resp. ,'0,0-dietyl-O-(2,2-di-klorvinyl)-tionofosforsyreestere. dimethyl resp. ,'0,0-diethyl-O-(2,2-dichlorovinyl)-thionophosphoric acid esters.
Oppfinnelsen vedrører en ny, fordelaktig fremgangsmåte til fremstilling av 0,O-dimetyl- resp. 0,0-dietyl-0-(2,2-diklorvinyl)-tionofosforsyreestere, som som kjent anvendes som insekti cider. The invention relates to a new, advantageous method for the production of 0,O-dimethyl- or 0,0-diethyl-0-(2,2-dichlorovinyl)-thionophosphoric acid esters, which are known to be used as insecticides.
Det er allerede omtalt at 0, O-dimetyl-0-(2,2-di-klorvinyl)-tionofosforsyreestere kan fåes, når man omsetter 0-(2,2-diklorvinyl)-tionofosforsyreesterdiklorid med metanol. It has already been mentioned that O,O-dimethyl-O-(2,2-dichlorovinyl)-thiophosphoric acid esters can be obtained when O-(2,2-dichlorovinyl)-thiophosphoric acid ester dichloride is reacted with methanol.
Denne fremgangsmåte har imidlertid en rekke ulemper. Således fåes det som utgangsprodukt nødvendige 0-(2,2-diklorvinyl)-tionofosforsyreesterdiklorid av den tilsvarende oksygenforbind-else ved omsetning med fos forpentasulfid bare ved meget høye temperaturer (rundt 150°C) med dårlige utbytter (under 30% av det teoretiske). Dessuten er det en ytterligere reaksjon av dikloridet med metanol bare å gjennomføre med et utbytte på 50% av det teoretiske, således at det for begge trinn fremkommer et samlet<y>utbytte på ca. 15%. Anvendbarheten av denne fremgangsmåte er derfor begrenset (sammenlign DOS 2.150.108). However, this method has a number of disadvantages. Thus, the necessary 0-(2,2-dichlorovinyl)-thionophosphoric acid ester dichloride is obtained from the corresponding oxygen compound by reaction with phosphorus pentasulfide only at very high temperatures (around 150°C) with poor yields (below 30% of the theoretical) . Moreover, a further reaction of the dichloride with methanol can only be carried out with a yield of 50% of the theoretical, so that for both steps a total<y>yield of approx. 15%. The applicability of this method is therefore limited (compare DOS 2.150.108).
Videre er det kjent at de ved fremgangsmåten ifølge DAS 1.058.046 fremstilte forbindelser ikke har konstitusjonen av 0,O-dialkyl-0-(2,2-diklorvinyl)-tionofosforsyreestere (sammenlign'DOS 2.133-199). Furthermore, it is known that the compounds produced by the method according to DAS 1,058,046 do not have the constitution of 0,O-dialkyl-0-(2,2-dichlorovinyl)-thionophosphoric acid esters (compare DOS 2,133-199).
Videre er det i litteraturen omtalt at en fremstilling av 0,O-dimetyl-0-(2,2-diklorvinyl)-tionofosforsyreesteren, idet det gåes ut fra dimetyltiolfosfit og kloral ikke er mulig, da reaksjonen tar et annet forløp (sammenlign belgisk patent nr. 623,551 og Pelchowicz, J. Chem. Soc. 196l, side 24l og følgende). Man får som sluttprodukt den isomere forbindelse med formel I Furthermore, it is mentioned in the literature that a preparation of the 0,O-dimethyl-0-(2,2-dichlorovinyl)-thionophosphoric acid ester, starting from dimethylthiolphosphite and chloral, is not possible, as the reaction takes a different course (compare Belgian patent No. 623,551 and Pelchowicz, J. Chem. Soc. 1961, page 241 et seq.). The final product is the isomeric compound of formula I
Det er kjent at for fremstillingen av den tilsvarende tionoforbindelse med formel II svikter de vanlige metoder til fremstilling av vinylfosfater og bestemte tiofosfater (se DOS 2.150.108, side 3 og 4). Ifølge dette fører den klassiske Perkow-reaksjon, som anvendes til fremstilling av finylfosfater ikke til de tilsvarende vinyltiofos-fater. Når man omsetter et trialkyltiofosfit (trialkylfosforo-tioit) med kloral, så er det fra denne omsetning resulterende produkt et 0,S-dialkyl-0-halogenvinyltiolfosfat. Andre vanlige fremgangsmåter viser seg likeledes som ikke egnet (sammenlign DOS 2.150.108, side 3 og 4). It is known that for the production of the corresponding thiono compound of formula II, the usual methods for the production of vinyl phosphates and certain thiophosphates fail (see DOS 2.150.108, pages 3 and 4). According to this, the classical Perkow reaction, which is used for the production of vinyl phosphates, does not lead to the corresponding vinyl thiophosphates. When a trialkylthiophosphite (trialkylphosphorothioite) is reacted with chloral, the resulting product from this reaction is an 0,S-dialkyl-0-halovinylthiol phosphate. Other common methods also prove not to be suitable (compare DOS 2.150.108, pages 3 and 4).
Videre er det kjent at man får forbindelsene med formel II ifølge DOS 2.238.921, når mån på dimetyltiofosfit i nærvær av en base som katalysator lar det innvirke kloral og alkalialkoholat. Også denne fremgangsmåte har vissenvanskelig-heter, for det er kjent at tiofosforsyrling-0,0-dialkylestere i inerte oppløsningsmidler danner alkalisalter som forsåpes ved fuktighet eller ved behandling med vann i løpet av kort tid til salter av tiofosforsyrling-O-monoalkylestere, Alkalisaltene oppstår også i overskytende alkohol ved tilsetning av alkoholat (se Houben Weyl, bind XII/2, side 97). Furthermore, it is known that one obtains the compounds of formula II according to DOS 2,238,921, when dimethylthiophosphite is treated in the presence of a base as a catalyst by allowing chloral and alkali alcoholate to act. This method also has certain difficulties, because it is known that thiophosphoric acid-0,0-dialkyl esters in inert solvents form alkali salts which are saponified by moisture or by treatment with water within a short time to salts of thiophosphoric acid-O-monoalkyl esters. The alkali salts are formed also in excess alcohol by adding alcoholate (see Houben Weyl, volume XII/2, page 97).
I alle tilfeller unndras ved denne bireaksjon resp. unnvikningsreaksjon en del av tiofosforsyrling-O,O-dialkylesteren for den egentlige reaksjon. In all cases, side reactions or evasion reaction a part of the thiophosphoric acid-O,O-dialkyl ester for the actual reaction.
Det foreligger derfor stor interesse for en fremgangsmåte som ikke har disse mangler og som utkopler de bestående vanskeligheter. There is therefore great interest in a method which does not have these shortcomings and which eliminates the existing difficulties.
Det er funnet at man får 0,0-dimetyl- resp, 0,0-dietyl-0-(2,2-diklorvinyl)-tionofosforsyreestere, når 0,0-dimety1-resp. 0,0-dietyl-l-hydroksy-2,2,2-trikloretan-tionofosfonsyre-estere med formel III It has been found that 0,0-dimethyl- or 0,0-diethyl-0-(2,2-dichlorovinyl)-thionophosphoric acid esters are obtained when 0,0-dimethyl- or 0,0-diethyl-1-hydroxy-2,2,2-trichloroethane-thionophosphonic acid esters of formula III
hvori R betyr en metyl- eller etylrest, in which R means a methyl or ethyl residue,
behandles med oppløsningen av en ekvivalent mengde av et alkalialkoholat og oppløsningen av et alkalihydroksyd eller -karbonat i en alkohol, idet man hensiktsmessig arbeider med metanol eller etanol for å unngå omforestringer, treated with the solution of an equivalent amount of an alkali alcoholate and the solution of an alkali hydroxide or carbonate in an alcohol, suitably working with methanol or ethanol to avoid transesterifications,
Det må sees på som meget overraskende at fremgangsmåten ifølge oppfinnelsen fører til den ønskede ester,. It must be seen as very surprising that the method according to the invention leads to the desired ester.
fordi med hensyn til teknikkens stand ville det være å vente et produkt tilsvarende formel I, because with regard to the state of the art, a product corresponding to formula I would be to be expected,
Fremgangsmåten ifølge oppfinnelsen har en rekke for-deler og viser en ny, hittil ikke kjent og heller ikke som reali-serbar ansett vei til den tilstrebede 0,0-dimetyl- resp, 0,0-diety1-0-(2,2-diklorvinyl)-tionofosforsyreester. Den nye fremgangsmåte krever ikke anvendelse av dyrt, .krystallinsk (fast) natriumalkoholat (sammenlign DOS 2.150.108, side 10). Den som utgangsprodukt nødvendige 0,0-dimetyl- resp. 0,0-dietyl-l-. hydroksy-2,2,2-trikloretan-tionofosfonsyreester kan fremstilles The method according to the invention has a number of advantages and shows a new, hitherto unknown and also not considered feasible route to the desired 0,0-dimethyl- or, 0,0-diethy1-0-(2,2- dichlorovinyl)-thionophosphoric acid ester. The new method does not require the use of expensive, crystalline (solid) sodium alcoholate (compare DOS 2.150.108, page 10). The starting product required 0,0-dimethyl- or 0,0-diethyl-1-. hydroxy-2,2,2-trichloroethane-thionophosphonic acid ester can be prepared
på teknisk enkel måte med høyt utbytte, mens det ifølge DOS 2.150.108 nødvendige forprodukt bare er oppnåelig i ca, 30%- ig utbytte og ved hjelp av en teknisk bare vanskelig beherskbar fremgangsmåte. Forproduktets tilgjengelighet er derfor usammen-lignbar gunstigere overfor det ifølge DOS 2.150.108 nødvendige. in a technically simple way with a high yield, while according to DOS 2.150.108 the required precursor can only be obtained in approx. 30% yield and with the help of a technically difficult-to-manage process. The availability of the preliminary product is therefore incomparably more favorable than that required according to DOS 2.150.108.
Dessuten har den nye fremgangsmåten ifølge oppfinnelsen den fordel at den ikke krever anvendelse av dyrt, fast natriumalkoholat og istedenfor dette kan det komme til anvendelse en oppløsning av natriummetylat resp, -etylat i metanol eller etanol, idet det ifølge DOS 2.150.108 kreves 2 mol natriummetylat pr, mol forprodukt, mens ifølge oppfinnelsen kreves det bare 1 mol natriumalkoholat oppløst i metanol eller etanol, hvilket betyr en betraktelig besparelse. Moreover, the new method according to the invention has the advantage that it does not require the use of expensive, solid sodium alcoholate and instead a solution of sodium methylate or ethylate in methanol or ethanol can be used, as according to DOS 2.150.108 2 mol is required sodium methylate per mole of precursor, while according to the invention only 1 mole of sodium alcoholate dissolved in methanol or ethanol is required, which means a considerable saving.
En ytterligere fordel ved fremgangsmåten ifølge oppfinnelsen består i at det ifølge en variant sees helt bort fra anvendelsen av natriumalkoholat og med samme resultat anvendes oppløsningen av et alkalihydroksyd eller -karbonat i metanol eller etanol. A further advantage of the method according to the invention is that, according to a variant, the use of sodium alcoholate is completely disregarded and with the same result the solution of an alkali hydroxide or carbonate in methanol or ethanol is used.
Anvender man som utgangsstoff 0,O-dimetyl-l-hydroksy-2,2,2-trikloretantionofosfonsyreester og en oppløsning av alkalihydroksyd eller -karbonat i metanol, så kan reaksjonsforløpet gjen-gis ved følgende formelskjerna: If 0,O-dimethyl-1-hydroxy-2,2,2-trichloroethanionophosphonic acid ester and a solution of alkali hydroxide or alkali carbonate in methanol are used as starting material, the course of the reaction can be reproduced by the following formula core:
"Ved overnevnte ligning er utgangs- og sluttproduktet entydig definert. "With the above-mentioned equation, the output and final product are unambiguously defined.
Den som utgangsstoff anvendte 0,0-dimetyl- resp. 0,0-dietyl-l-hydroksy-2,2,2-trikloretantionofosfonsyreester er hittil ikke kjent, kan imidlertid fåes etter et forslag som ikke hører til teknikkens stand og som går mot den gjeldende oppfatning (Pelchlowicz ; J. Chem. Soc. 1961, side 241 og følgende) av dimetyl- resp. dietyl-tiolfosfit og kloral. The starting material used 0,0-dimethyl- or 0,0-diethyl-1-hydroxy-2,2,2-trichloroethanionophosphonic acid ester is not known to date, but can be obtained according to a proposal which does not belong to the state of the art and which goes against the current opinion (Pelchlowicz ; J. Chem. Soc. 1961, page 241 et seq.) of dimethyl- or diethyl thiol phosphite and chloral.
Fremgangsmåten ifølge oppfinnelsen er gjennomførbar uten eller under ekstraanvendelse av oppløsningsmidler, Som sådanne kommer det på tale alle inerte organiske oppløsnings-midler. Hertil hører fortrinnsvis hydrokarboner som bensin, benzen, toluen, etere som dietyleter, dioksan, klorerte hydrokarboner som metylenklorid, etylenklorid, ketoner som aceton, butanon, nitriler som acetonitril og benzonitril. Likeledes kan det som oppløsningsmiddel anvendes visse alkoholer som metanol, etanol, propanol og butanol. Man gir derved hensiktsmessig metanol eller etanol fordel, da det herved utelukkes omforestring. The method according to the invention can be carried out without or with the additional use of solvents. As such, we are talking about all inert organic solvents. These preferably include hydrocarbons such as petrol, benzene, toluene, ethers such as diethyl ether, dioxane, chlorinated hydrocarbons such as methylene chloride, ethylene chloride, ketones such as acetone, butanone, nitriles such as acetonitrile and benzonitrile. Likewise, certain alcohols such as methanol, ethanol, propanol and butanol can be used as solvents. Appropriate methanol or ethanol is thereby advantageous, as transesterification is thereby excluded.
Omsetningen gjennomføres ved temperaturer mellomThe turnover is carried out at temperatures between
-20 og +100°C, fortrinnsvis mellom 10 og 20°C og under normal-trykk. -20 and +100°C, preferably between 10 and 20°C and under normal pressure.
Ved gjennomføring av fremgangsmåten ifølge oppfinnelsen anvender man pr. mol 0,0-dimetyl- resp, 0,0-dietyl-l-hydroksy-2,2,2-trikloretantionofosforsyreester 1 mol alkalihydroksyd eller \ mol alkalikarbonat, Større avvikelse fra dette forhold har til følge et urent produkt og høyt utbyttetap. When carrying out the method according to the invention, one uses per mol 0,0-dimethyl- or, 0,0-diethyl-1-hydroxy-2,2,2-trichloroethanionophosphoric acid ester 1 mol alkali hydroxide or \ mol alkali carbonate, Larger deviation from this ratio results in an impure product and high loss of yield.
Som allerede nevnt ovenfor finner de ved fremgangsmåten fremstillbare 0,0-dimetyl- resp. 0,0-diety1-0-(2,2-diklor-vinyl ) -tionof osf orsyreestere på grunn av deres egenskaper anvendelse som skadedyrsbekjempelsesmiddel, fremfor alt som insekti-cider, spesielt i plantebeskyttelse samt på hygiene- og forråds-beskyttelsessektoren. As already mentioned above, the 0,0-dimethyl resp. 0,0-diety1-0-(2,2-dichloro-vinyl)-thiophosphoric acid esters due to their properties use as pest control agent, above all as insecticides, especially in plant protection as well as in the hygiene and storage protection sector.
Følgende eksempler forklarer fremgangsmåten nærmere. The following examples explain the procedure in more detail.
Eksempel 1. Example 1.
Til en oppløsning av 27,3 g (0,1 mol) 0,0-dimetyl-l-hydroksy-2,2, 2-trikloretantionof os'f onsyreester i 50 ml metanol drypper man ved 10 til 20°C 2,3 g natrium oppløst i metanol. To a solution of 27.3 g (0.1 mol) of 0,0-dimethyl-1-hydroxy-2,2,2-trichloroethanethiophenesophonic acid ester in 50 ml of methanol is added dropwise at 10 to 20°C 2,3 g of sodium dissolved in methanol.
Blandingen omrøres 15 minutter ved 30°C, avkjøles og innrøresThe mixture is stirred for 15 minutes at 30°C, cooled and stirred in
i isvann. Den vandige oppløsning ekstraheres to ganger med metylenklorid, de forenede metylenkloridekstrakter vaskes en gang med vann og tørkes deretter. Etter oppløsningsmidlets avdestillering under nedsatt trykk fåes 23,5 g av en olje, som har et gasskromatografisk bestemt innhold på 92,4% 0,0-dimetyl-0-(2,2-diklorvinyl)-tiofosforsyreester. Ved behov kan råproduktet destilleres. Det koker under et trykk på 2 torr ved 76 til 80°C; brytningsindeks utgjør nD 2 2: 1,4964. Konstitusjonen av forbind-elsen er sikret ved NMR-spektroskopi, in ice water. The aqueous solution is extracted twice with methylene chloride, the combined methylene chloride extracts are washed once with water and then dried. After the solvent has been distilled off under reduced pressure, 23.5 g of an oil are obtained, which has a gas chromatographically determined content of 92.4% 0,0-dimethyl-0-(2,2-dichlorovinyl)-thiophosphoric acid ester. If necessary, the raw product can be distilled. It boils under a pressure of 2 torr at 76 to 80°C; refractive index amounts to nD 2 2: 1.4964. The constitution of the compound is ensured by NMR spectroscopy,
Eksempel 2.Example 2.
I en oppløsning av 27,3 g (0,1 mol) 0,0-dimetyl-l-hydroksy-2,2,2-trikloretan-tionofosfonsyreester i 30 ml metanol drypper man ved 30°C en oppløsning bestående av 6,9 g kaliumkarbonat, 20 ml metanol og 20 ml vann. Deretter videre-arbeides som angitt i eksempel 1. Man får 23,6 g av en' olje med et gasskromatografisk bestemt innhold på 5&% av det teoretiske av 0,O-dimetyl-0-(2,2-diklorvinyl)-tiofosforsyreester, Eksempel 3. At 30°C, a solution consisting of 6.9 g of potassium carbonate, 20 ml of methanol and 20 ml of water. Work is then continued as indicated in example 1. 23.6 g of an oil are obtained with a gas chromatographically determined content of 5% of the theoretical amount of 0,O-dimethyl-0-(2,2-dichlorovinyl)-thiophosphoric acid ester, Example 3.
Til en blanding av 137,0 g (0,5 mol) 0,0-dimetyl-l-hydroksy-2,2,2-trikloretan-tiofosfonat og 200 ml toluen drypper man under omrøring og ytre avkjøling i løpet av 20 minutter oppløsningen av 21,6 g (0,54 mol) natriumhydroksyd i 100 g metanol, idet den indre temperatur holdes mellom 15 og 20°C, Etter 1 times omrøring ved 20°C utrystes reaksjonsblandingen fire til fem ganger med hver gang 200 til 250 ml vann, den organiske fase tørkes deretter med 25 g natriumsulfat og i rotasjonsfor-dampér under nedsatt trykk befris for oppløsningsmiddel, Residuet gir ved fraksjonert destillering 95,5 g (80,5% av det teoretiske) 0,O-dimetyl-0-2,2-diklorviny1-tiofosforsyreester som farveløs væske av kokepunkt 78°C/2 torr, Brytningsindeks utgjør n^: 1,4990. Innholdet ifølge gasskromatogram: 99,2%. To a mixture of 137.0 g (0.5 mol) 0,0-dimethyl-1-hydroxy-2,2,2-trichloroethane-thiophosphonate and 200 ml of toluene, the solution is added dropwise with stirring and external cooling over the course of 20 minutes of 21.6 g (0.54 mol) of sodium hydroxide in 100 g of methanol, keeping the internal temperature between 15 and 20°C. After 1 hour of stirring at 20°C, the reaction mixture is shaken four to five times, each time with 200 to 250 ml water, the organic phase is then dried with 25 g of sodium sulphate and freed of solvent in a rotary evaporator under reduced pressure. The residue gives, by fractional distillation, 95.5 g (80.5% of the theoretical) 0,O-dimethyl-0-2 ,2-dichloroviny1-thiophosphoric acid ester as a colorless liquid of boiling point 78°C/2 torr, Refractive index is n^: 1.4990. Content according to gas chromatogram: 99.2%.
Eksempel 4.Example 4.
I en oppløsning av 1508 g (5 mol) 0,0-dietyl-l-hydroksy-2,2,2-trikloretan-tionofosfonat i 2 liter toluen lar man det under omrøring og ytre avkjøling ved en indre temperatur på 15 til 20°C i løpet av en time strømme inn en 5 mol natrium-etylatholdig etanolisk oppløsning. Etter 1 times omrøring av blandingen vaskes denne med vann, tørkes og oppløsningsmidlet fjernes under nedsatt trykk. Det blir tilbake 994,1 g (75,0% In a solution of 1508 g (5 mol) of 0,0-diethyl-1-hydroxy-2,2,2-trichloroethane-thionophosphonate in 2 liters of toluene, it is allowed to stir and externally cool at an internal temperature of 15 to 20° C during one hour pour in a 5 mol sodium ethylate-containing ethanolic solution. After stirring the mixture for 1 hour, it is washed with water, dried and the solvent is removed under reduced pressure. 994.1 g (75.0%
av det teoretiske) 0,0-dietyl-2,2-diklorvinyl-tionofosforsyre-ester som svak gulfarvet væske med kokepunkt 89°C/2 torr og 18 of the theoretical) 0,0-diethyl-2,2-dichlorovinyl-thionophosphoric acid ester as a faint yellow liquid with a boiling point of 89°C/2 torr and 18
brytningsindeks n^ : 1,4875. refractive index n^ : 1.4875.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752512177 DE2512177A1 (en) | 1975-03-20 | 1975-03-20 | METHOD FOR THE PRODUCTION OF O, O- DIMETHYL- OR. O, O-DIAETHYL-O- (2,2-DICHLORVINYL) -THIONOPHOSPHORIC ACID ESTER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO760777L true NO760777L (en) | 1976-09-21 |
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ID=5941884
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO760777A NO760777L (en) | 1975-03-20 | 1976-03-05 |
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| JP (1) | JPS51115422A (en) |
| AT (1) | AT338289B (en) |
| AU (1) | AU504691B2 (en) |
| BE (1) | BE839712A (en) |
| BG (1) | BG27237A3 (en) |
| BR (1) | BR7601678A (en) |
| CA (1) | CA1058631A (en) |
| CH (1) | CH601330A5 (en) |
| CS (1) | CS191211B2 (en) |
| DD (1) | DD125683A5 (en) |
| DE (1) | DE2512177A1 (en) |
| DK (1) | DK121476A (en) |
| EG (1) | EG12366A (en) |
| ES (1) | ES446181A1 (en) |
| FI (1) | FI760723A (en) |
| FR (1) | FR2304616A1 (en) |
| GB (1) | GB1501786A (en) |
| GR (1) | GR59318B (en) |
| HU (1) | HU173955B (en) |
| IE (1) | IE42660B1 (en) |
| IL (1) | IL49230A (en) |
| KE (1) | KE2872A (en) |
| LU (1) | LU74593A1 (en) |
| MY (1) | MY7800372A (en) |
| NL (1) | NL7602928A (en) |
| NO (1) | NO760777L (en) |
| OA (1) | OA05276A (en) |
| PL (1) | PL100904B1 (en) |
| PT (1) | PT64914B (en) |
| RO (1) | RO69116A (en) |
| SE (1) | SE7602119L (en) |
| SU (1) | SU569292A3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2636786A1 (en) * | 1976-08-16 | 1978-02-23 | Bayer Ag | Process for the preparation of O, O-DIMETHYL-O- (2,2-DICHLORVINYL) -THIONOPHOSPHORIC ACID ESTER |
| US7576301B2 (en) | 2004-09-28 | 2009-08-18 | Freegen Research Limited | Building incorporating a thermal insulation assembly and method of conserving energy |
-
1975
- 1975-03-19 ZA ZA761709A patent/ZA761709B/en unknown
- 1975-03-20 DE DE19752512177 patent/DE2512177A1/en active Pending
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1976
- 1976-02-20 DD DD191392A patent/DD125683A5/xx unknown
- 1976-02-23 SE SE7602119A patent/SE7602119L/en unknown
- 1976-03-05 NO NO760777A patent/NO760777L/no unknown
- 1976-03-11 AU AU11853/76A patent/AU504691B2/en not_active Expired
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- 1976-03-17 IL IL49230A patent/IL49230A/en unknown
- 1976-03-17 EG EG161/76A patent/EG12366A/en active
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- 1976-03-18 ES ES446181A patent/ES446181A1/en not_active Expired
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- 1976-03-19 GB GB11163/76A patent/GB1501786A/en not_active Expired
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