NO118208B - - Google Patents
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- NO118208B NO118208B NO164226A NO16422666A NO118208B NO 118208 B NO118208 B NO 118208B NO 164226 A NO164226 A NO 164226A NO 16422666 A NO16422666 A NO 16422666A NO 118208 B NO118208 B NO 118208B
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- NO
- Norway
- Prior art keywords
- water
- phosphoric acid
- solution
- potassium permanganate
- esters
- Prior art date
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- 239000012286 potassium permanganate Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000003568 thioethers Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 2
- 150000007860 aryl ester derivatives Chemical class 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- -1 alkylene alkyl sulphides Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FZAJEGWDPOYEEC-UHFFFAOYSA-N 1-[ethoxy(ethylsulfonylmethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(OCC)CS(=O)(=O)CC FZAJEGWDPOYEEC-UHFFFAOYSA-N 0.000 description 1
- BULBBCFURGVLNZ-UHFFFAOYSA-N 1-diethoxyphosphorylpropane-1-thiol Chemical compound SC(CC)P(OCC)(OCC)=O BULBBCFURGVLNZ-UHFFFAOYSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- GGZSXNGEPOXZRP-UHFFFAOYSA-N sulfanyl dihydrogen phosphate Chemical class OP(O)(=O)OS GGZSXNGEPOXZRP-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D17/00—Rigid or semi-rigid containers specially constructed to be opened by cutting or piercing, or by tearing of frangible members or portions
- B65D17/42—Rigid or semi-rigid containers specially constructed to be opened by cutting or piercing, or by tearing of frangible members or portions with cutting, punching, or cutter accommodating means
- B65D17/46—Wires, strings or the like, e.g. rip cords
- B65D17/462—Tearing-strips or -wires
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Packages (AREA)
- Closures For Containers (AREA)
- Containers Opened By Tearing Frangible Portions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Fremgangsmåte til fremstilling av sulfonylgruppeholdige estere av fosforsyre. Process for the production of sulfonyl group-containing esters of phosphoric acid.
For fremstilling av alkylsulfonylalkyl-estere av fosforsyre eller tiofosforsyre fin-nes forskjellige muligheter. Således beskri-ver f. eks. det tyske patent nr. 876.692 reak-sjonen av tiofosforsyreklorid med oksyal-kylalkylsulfoner. Fra det tyske patent nr. 876 691 er det kjent å omsette tioltionofos-forsyreester med alkylenalkylusulfider og i det tyske patent nr. 871.448 beskrives reak-sjonen av underfosforsyredialkylestere med alkylsulfonylmerkaptoklorider. There are various possibilities for producing alkylsulfonyl alkyl esters of phosphoric acid or thiophosphoric acid. Thus describes e.g. the German patent no. 876,692 the reaction of thiophosphoric acid chloride with oxyalkylalkylsulfones. From German patent no. 876,691, it is known to react thiolthiophosphoric acid esters with alkylene alkyl sulphides and in German patent no. 871,448 the reaction of lower phosphoric acid dialkyl esters with alkylsulfonyl mercaptochlorides is described.
I det norske patent nr. 87.470 er det beskrevet en fremgangsmåte hvor alkylmer-kaptoalkylestere oksyderes med vannstoffsuperoksyd, hvorved det adderes et sur-stoffatom til svovelatomet i merkapto-gruppen, slik at det dannes sulfenylforbindelser. I patentet nevnes videre at ved be-handling med selv et stort overskudd av vannstoffsuperoksyd får man de tilsvarende sulfenylforbindelser sammen med en blanding av oksydasjonsproduktet. Det lar seg altså ikke på denne måte innføre to surstoffatomer, slik at man kan komme fram til sulfonylforbindelsene. In the Norwegian patent no. 87,470, a method is described in which alkyl mercaptoalkyl esters are oxidized with hydrogen peroxide, whereby an oxygen atom is added to the sulfur atom in the mercapto group, so that sulfenyl compounds are formed. The patent also mentions that when treated with even a large excess of hydrogen peroxide, the corresponding sulfenyl compounds are obtained together with a mixture of the oxidation product. It is therefore not possible to introduce two oxygen atoms in this way, so that one can arrive at the sulphonyl compounds.
Det ble nu funnet at overraskende kan sulfonylester med den generelle formel It was now found that, surprisingly, sulfonyl esters of the general formula can
hvor R betyr alkyl-, aralkyl- eller arylres-ter, n betyr 1—4, X betyr O eller S eller en direkte blanding av C—P, og R1 og R2 betyr lavere alkylester, lett fremstilles ved at tilsvarende sulfider oksyderes med kaliumpermanganat i vandig oppløsning. where R means alkyl, aralkyl or aryl residues, n means 1—4, X means O or S or a direct mixture of C—P, and R1 and R2 mean lower alkyl esters, easily produced by oxidizing corresponding sulfides with potassium permanganate in aqueous solution.
For fremstilling av de som utgangs-materiale egnede sulfidestere er det kjent forskjellige fremgangsmåter. Således kan man lett få merkaptofosforsyreestere (hvor X betyr den direkte C-P-binding) ved re-i aksjon av kloralkylalkylsulfider med na-triumdialkylfosfiter. Denne reaksjon for-løper etter følgende skjema: Various methods are known for the production of sulphide esters suitable as starting material. Thus mercaptophosphoric acid esters (where X means the direct C-P bond) can easily be obtained by reaction of chloroalkylalkyl sulphides with sodium dialkyl phosphites. This reaction proceeds according to the following scheme:
Merkaptoesteren av tiolfosforsyre er f eks. tilgjengelig ifølge fremgangsmåten det tyske patent nr. 830 508 fra kloralkylalkylsulfider og alkali- eller ammonium-i saltene av dialkyltiol-fosforsyre. The mercaptoester of thiolphosphoric acid is, for example, available according to the process of the German patent No. 830,508 from chloroalkylalkyl sulfides and the alkali or ammonium salts of dialkylthiol phosphoric acid.
Den «omvendte» merkaptoester av tio-nofosforsyre kan, slik som beskrevet i det tyske patent nr. 836.349, lett fremstilles. The "inverted" mercaptoester of thionophosphoric acid can, as described in German patent no. 836,349, be easily prepared.
At disse alkylmerkaptoralkylestere av fosfon, henholdsvis fosforsyre i meget godt utbytte lar seg oksydere med kaliumpermanganat til de tilsvarende sulfoner, er i betraktning av hydrolyseømfintligheten for den anvendte ester forbausende og kunne ikke på noen måte forutsees. I al-minnelighet forløper oksydasjonen av tio-eter-fosfon og fosforsyreester allerede ved romtemperatur eller endog ved 0° C. Oksydasjonen utføres med den teoretisk nødvendige mengde alkalipermanganat i nærvær av så meget syre, at det etter oksydasjonen foreligger en nøytral oppløs-ning. That these alkyl mercaptoalkyl esters of phosphonic or phosphoric acid can be oxidized with potassium permanganate to the corresponding sulfones in very good yield is, in view of the sensitivity to hydrolysis of the ester used, surprising and could not in any way have been predicted. In general, the oxidation of thio-ether-phosphone and phosphoric acid ester already takes place at room temperature or even at 0° C. The oxidation is carried out with the theoretically necessary amount of alkali permanganate in the presence of so much acid that a neutral solution is present after the oxidation.
Ved i vann tungt oppløselige tioester-forbindelser kan det også arbeides i vandig dioksan eller i vandig aceton. In the case of thioester compounds that are poorly soluble in water, it is also possible to work in aqueous dioxane or in aqueous acetone.
De ifølge foreliggende fremgangsmåte erholdte forbindelser egner seg f. eks. sær-lig som tilsetning til smøremidler og olje. Dessuten kan de finne anvendelse ved sin delvis lille toksiske egenskap som myk-gjører. De er også egnet som mellompro-dukter til fremstilling av insektisidvirk-somme stoffer. Andre forbindelser fra denne stoffklasse er verdifulle kontaktinsekt-isider, som delvis også omfatter en fremragende indreterapeutisk virkning mot in-sekter ved levende planter. De lavere ledd av noen forbindelser er fremragende vann-oppløselige og er på grunn av denne egenskap verdifulle for plantebeskyttelse. The compounds obtained according to the present method are suitable, e.g. especially as an additive to lubricants and oil. In addition, they can find use due to their partially toxic properties as softeners. They are also suitable as intermediate products for the production of insecticidally active substances. Other compounds from this substance class are valuable contact insecticides, which partly also include an outstanding internal therapeutic effect against insects on living plants. The lower members of some compounds are excellently water-soluble and, because of this property, are valuable for plant protection.
Følgende eksempler gir en oversikt over fremgangsmåten ifølge oppfinnelsen: The following examples provide an overview of the method according to the invention:
Eksempel 1: Example 1:
45 gr. |3-etylmerkapto-etyl-fosfonsyre-etylester og 50 ems vann tildryppes under avkjøling og omrøring ved 15—20° C en oppløsning av 42 gr. kaliumpermanganat i 500 cm» vann, som man har ansyret med 7,2 ems konsentrert svovelsyre. Inndryp-ningen varer ca. y2 time. Oppløsningen skal nu være tilnærmet nøytral og være fiolett- 45 gr. |3-Ethyl mercapto-ethyl-phosphonic acid ethyl ester and 50 ems water are added dropwise while cooling and stirring at 15-20° C. a solution of 42 gr. potassium permanganate in 500 cm" of water, which has been acidified with 7.2 ems of concentrated sulfuric acid. The instillation lasts approx. y2 hours. The solution should now be approximately neutral and be violet-
farget av noe uforbrukt permanganat. Det suges fra, brunstenslammet ettervaskes med litt vann og filtratet avfarves med natriumbisulfit. Den klare oppløsning met-tes ved ca. 25—30° C med natriumsulfat, hvorved det vannholdige reaksjonsprodukt utskilles oventil. Etter skilling av sjiktene utrystes den vandige fase to ganger med metylenklorid og metylenkloridoppløsnin-gen forenes med hovedmengden av produktet. Det atskilles fra noe uutskilt vann, tørkes med natriumsulfat og destillers. Man får et (3-etylsulfonylefosfonsyredietyl-ester med kokepunkt 0,01 mm/105° C i et utbytte på 80 pst. av det teoretiske. colored by some unused permanganate. It is sucked off, the brownstone sludge is washed with a little water and the filtrate is decoloured with sodium bisulphite. The clear solution is saturated at approx. 25-30° C with sodium sulphate, whereby the aqueous reaction product is separated above. After separation of the layers, the aqueous phase is shaken twice with methylene chloride and the methylene chloride solution is combined with the bulk of the product. It is separated from any unseparated water, dried with sodium sulphate and distilled. A (3-ethylsulfonylphosphonic acid diethyl ester) with a boiling point of 0.01 mm/105° C is obtained in a yield of 80 per cent of the theoretical.
Eksempel 2: Example 2:
i in
Man oksyderer, som ovenfor beskrevet, 42,5 gr. etylmerkaptometylfosfonsyredietyl-ester (kokepunkt ved 2 mm/102° C) ved 0 —10°C med en oppløsning av 43 gr. kaliumpermanganat og 7 cm3 konsentrert svovelsyre i 600 ems vann. Opparbeidelsen skjer på liknende måte som i eksempel 1. Man får etylsulfonylmetylfosfonsyredietyleste-ren i et utbytte på 38 gr. = 77 pst. av det teoretiske. Det er en meget lett vannopp-løselig viskos f arveløs olje med kokepunkt ved 0,01 mm/88° C. One oxidizes, as described above, 42.5 gr. ethyl mercaptomethylphosphonic acid diethyl ester (boiling point at 2 mm/102° C) at 0 -10° C with a solution of 43 gr. potassium permanganate and 7 cm3 of concentrated sulfuric acid in 600 ems water. The preparation takes place in a similar way as in example 1. The ethylsulfonylmethylphosphonic acid diethyl ester is obtained in a yield of 38 gr. = 77 percent of the theoretical. It is a very easily water-soluble viscous non-heritable oil with a boiling point of 0.01 mm/88° C.
Eksempel 3: Example 3:
På samme måte som beskrevet i de foregående eksempler oksyderes 52 gr. [ i-etylmerkaptoetyltiolfosforsyredietylester og 50 ems vann ved 0° C med en oppløsning av 43 gr. kaliumpermanganat og 7,2 ems konsentrert svovelsyre i 600 ems vann. Etter inndrypning er oppløsningen svakt kon-gosur. Ved innføring av 5—6 gr. finpulveri-sert kaliumpermanganat i reaksjonsopp-løsningen etteroksyderes inntil blivende rødfarvning hvor oppløsningen blir prak-tisk talt nøytral (typling på universalindi-katorpapir «Merck»). Det suges fra.avfarves med natriumbisulfit og tilsettes 100— 150 gr. natriumsulfat. Etter oppløsning av natriumsulfatet utskilles reaksjonsproduk-tet og isoleres som i de foregeånde eksempler. Det danner seg (3-etylsulfonyletyltiol-fosforsyredietylester som er farveløs, meget viskos olje med kokepunkt 0,01 mm/115° C. Utbyttet utgjør 34 gr. = 65 pst. av det teoretiske. Produktet er vannoppløselig. In the same way as described in the preceding examples, 52 gr. [ i-ethyl mercaptoethyl thiol phosphoric acid diethyl ester and 50 ems water at 0° C with a solution of 43 gr. potassium permanganate and 7.2 ems concentrated sulfuric acid in 600 ems water. After instillation, the solution is slightly concentrated. When introducing 5-6 gr. Finely pulverized potassium permanganate in the reaction solution is post-oxidised until a permanent red colouration, where the solution becomes practically neutral (typing on universal indicator paper "Merck"). It is sucked off, decolorized with sodium bisulphite and added 100-150 gr. sodium sulfate. After dissolving the sodium sulfate, the reaction product is separated and isolated as in the previous examples. It forms (3-ethylsulfonylethylthiol phosphoric acid diethyl ester which is a colourless, very viscous oil with a boiling point of 0.01 mm/115° C. The yield is 34 gr. = 65 per cent of the theoretical. The product is water soluble.
Eksempel 4: Example 4:
26 gr. etylmerkaptometyltiolfosforsyre-dietylester oksyderes ved 0° C som ovenfor med en oppløsning av 23 gr. kaliumpermanganat og 3,9 ems konsentrert svovelsyre i 350 cm</>i vann og etteroksyderes med 3—4 26 gr. ethyl mercaptomethylthiol phosphoric acid diethyl ester is oxidized at 0° C as above with a solution of 23 gr. potassium permanganate and 3.9 ems concentrated sulfuric acid in 350 cm</> of water and postoxidized with 3-4
gr. fast kaliumpermanganat inntil blivende rødfarving. Det opparbeides som i de foregående eksempler. Man får etylsulfo-nylmetyltiolfosforsyredietylester som en viskos, farve- og luktløs olje med kokepunkt ved 0,01 mm/106° C. Utbyttet utgjør 22 gr. = 75 pst. av det teoretiske. Gr. solid potassium permanganate until remaining red. It is processed as in the previous examples. Ethylsulfonylmethylthiol phosphoric acid diethyl ester is obtained as a viscous, colorless and odorless oil with a boiling point of 0.01 mm/106° C. The yield is 22 gr. = 75 percent of the theoretical.
Eksempel 5: Example 5:
46 gr. etylmerkaptoetyltiolfosforsyre-dimetylester oksyderes på samme måte som beskrevet ovenfor ved 0° C med en oppløsning av 43 gr. kaliummanganat og 7,1 cm» konsentrert svovelsyre i 600 cm» vann og etteroksyderes deretter med fast kaliumpermanganat (ca. 6 gr.). Etter fra-sugning av brunstensslammet utsaltes preparatet som vanlig med natriumsulfat, opptas med metylenklorid og tørkes med natriumsulfat. Etter avdestillering av opp-løsningsmidlet til slutt ved oljepumpe, stiv-ner etylsulfonyletyltiolfosforsyredimetyles-teren direkte til farveløse krystaller. Det kan ved destillasjon (kokepunkt 0,01 mm/ 115° C. eller ved gjentatt oppløsning i ben-zol lett renses. (Smeltepunkt 52° C). Rå-produktet er imidlertid allerede meget rent. Preparatet er blandbart med vann. 46 gr. ethyl mercaptoethylthiol phosphoric acid dimethyl ester is oxidized in the same way as described above at 0° C with a solution of 43 gr. potassium manganate and 7.1 cm" of concentrated sulfuric acid in 600 cm" of water and then oxidized with solid potassium permanganate (approx. 6 gr.). After suctioning off the brownstone sludge, the preparation is salted out as usual with sodium sulphate, taken up with methylene chloride and dried with sodium sulphate. After finally distilling off the solvent by oil pump, the ethyl sulfonyl ethyl thiol phosphoric acid dimethyl ester solidifies directly into colorless crystals. It can be easily purified by distillation (boiling point 0.01 mm/ 115° C.) or by repeated dissolution in benzene. (Melting point 52° C). The raw product is, however, already very pure. The preparation is miscible with water.
Utbytter utgjør 42 gr. = 80 pst. av det teoretiske. Dividends amount to 42 gr. = 80 percent of the theoretical.
Eksempel 6: Example 6:
45 gr. p-fenylmerkaptoetyltiolfosfor-syredietylester oksyderes ved 0° C med en oppløsning som inneholder 31 gr. kaliumpermanganat og 5,2 cm^ konsentrert svovelsyre i 450 ems vann. Det etteroksyderes som ovenfor beskrevet med fast kaliumpermanganat og frasuges. Ifølge den lille vannoppløselighet for preparatet utskiller en del av dette seg oljeaktig i filtratet. Filterresten ettervaskes med metylenklorid eller aceton. Av det med natriumbisulfit avfarvede filtrat utrystes p-fenylsulfonyl-etyltiolfosforsyredietylester med metylenklorid og destilleres etter tørkning med natriumsulfat. Kokepunktet for stoffet lig-ger ved 0,01 mm/148<0> C (Bad 180° C). Det er en høyviskos olje og lite vannoppløse-lig. Utbytte 26 gr. — 52 pst. av det teoretiske. 45 gr. p-Phenyl mercaptoethyl thiol phosphoric acid diethyl ester is oxidized at 0° C with a solution containing 31 gr. potassium permanganate and 5.2 cm^ of concentrated sulfuric acid in 450 ems of water. It is postoxidized as described above with solid potassium permanganate and aspirated. According to the low water solubility of the preparation, a part of this separates out as an oil in the filtrate. The filter residue is washed with methylene chloride or acetone. From the sodium bisulphite-decoloured filtrate, p-phenylsulfonyl-ethyl thiol phosphoric acid diethyl ester is shaken off with methylene chloride and distilled after drying with sodium sulphate. The boiling point of the substance is at 0.01 mm/148<0> C (Bath 180° C). It is a high-viscosity oil and poorly water-soluble. Yield 26 gr. — 52 percent of the theoretical.
Eksempel 7: Example 7:
24 gr. p-merkaptoetyl-etylfosforsyre-dietylester oksyderes ved 0° C med en opp-løsning av 22 gr. kaliumpermanganat i 300 cm'! vann og 3,5 cm» konsentrert svovelsyre, slik som beskrevet i de foregående eksempler. Etter den vanlige opparbeidelse får man 22 gr. = 80 pst. av det teoretiske av sulfonester med kokepunkt 0,01 mm/ 100° C. 24 gr. p-mercaptoethyl ethyl phosphoric acid diethyl ester is oxidized at 0° C with a solution of 22 gr. potassium permanganate in 300 cm'! water and 3.5 cm" of concentrated sulfuric acid, as described in the previous examples. After the usual preparation, you get 22 gr. = 80 percent of the theoretical of sulphonic esters with a boiling point of 0.01 mm/ 100° C.
Eksempel 8: Example 8:
26 gr. p-merkaptoetyl-etyltionofosfor-syredietylester oppløses i 300 cm^ aceton og til oppløsningen dryppes under kraftig omrøring ved en temperatur på -=-10° C 23 gr. kaliumpermanganat oppløst i 300 cm« 26 gr. p-Mercaptoethyl-ethylthiophosphoric acid diethyl ester is dissolved in 300 cm^ of acetone and to the solution is dripped with vigorous stirring at a temperature of -=-10° C 23 gr. potassium permanganate dissolved in 300 cm«
vann og 3,5 cm^ konsentrert svovelsyre. water and 3.5 cm^ of concentrated sulfuric acid.
Reaksjonsblandingen er til 'slutt nøytral. The reaction mixture is finally neutral.
Man suger fra de vannuoppløselige salter, One sucks from the water-insoluble salts,
spyler filterresten med aceton og inndam-per filtratet på vannbad så meget inntil rinses the filter residue with acetone and evaporates the filtrate on a water bath as much as possible
det ikke lenger går over noe aceton. Bad-temperaturen skulle ikke overstige 40° C. it no longer passes over any acetone. The bath temperature should not exceed 40° C.
Den nye sulfonester har utskilt seg som The new sulfonester has been separated as
tung olje fra destillasjonsresten. Det skil-les fra i skilletrakt, den vandige fase ettervaskes med metylklorid og den med hovedmengden av preparatet forenede metylén-kloridoppløsning destilleres etter tørkning heavy oil from the distillation residue. It is separated in a separatory funnel, the aqueous phase is washed with methyl chloride and the methylene chloride solution combined with the bulk of the preparation is distilled after drying
med natriumsulfat. Man får den nye sulfonester som f arveløs olje med kokepunkt with sodium sulfate. The new sulfonester is obtained as a pure oil with a boiling point
0,01 mm/104° C i et utbytte på 21 gr. = 72 pst. av det teoretiske. 0.01 mm/104° C in a yield of 21 gr. = 72 percent of the theoretical.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CH1115865A CH426617A (en) | 1965-08-09 | 1965-08-09 | Container with zip fastener |
Publications (1)
Publication Number | Publication Date |
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NO118208B true NO118208B (en) | 1969-11-24 |
Family
ID=4370654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO164226A NO118208B (en) | 1965-08-09 | 1966-08-08 |
Country Status (9)
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US (1) | US3362571A (en) |
BE (1) | BE685217A (en) |
CH (1) | CH426617A (en) |
DE (1) | DE1536304B2 (en) |
DK (1) | DK114114B (en) |
GB (1) | GB1091387A (en) |
NL (1) | NL151949B (en) |
NO (1) | NO118208B (en) |
SE (1) | SE305178B (en) |
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SE334842B (en) * | 1967-12-06 | 1971-05-03 | Foervaltnings Ab Acta | |
BE791552R (en) * | 1971-11-19 | 1973-03-16 | Alusuisse | CONTAINER WITH WIRE CLOSURE |
US5251758A (en) * | 1991-07-15 | 1993-10-12 | Liblan & Co., Ltd. | Food container with grippable portion having sense of touch indicia |
US8708344B2 (en) | 2012-10-02 | 2014-04-29 | GM Global Technology Operations LLC | Sealed assemblies and methods of unsealing same |
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US2739732A (en) * | 1950-10-30 | 1956-03-27 | Bogner Peter | Rip-wire can closures |
US2903179A (en) * | 1957-04-24 | 1959-09-08 | John F Vanhoof | Self-contained opener for containers |
-
1965
- 1965-08-09 CH CH1115865A patent/CH426617A/en unknown
-
1966
- 1966-07-22 DK DK379366AA patent/DK114114B/en unknown
- 1966-07-27 SE SE10237/66A patent/SE305178B/xx unknown
- 1966-08-02 US US569627A patent/US3362571A/en not_active Expired - Lifetime
- 1966-08-03 GB GB34831/66A patent/GB1091387A/en not_active Expired
- 1966-08-04 DE DE1966SC039358 patent/DE1536304B2/en active Granted
- 1966-08-08 NO NO164226A patent/NO118208B/no unknown
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- 1966-08-09 NL NL666611195A patent/NL151949B/en unknown
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Publication number | Publication date |
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US3362571A (en) | 1968-01-09 |
NL151949B (en) | 1977-01-17 |
NL6611195A (en) | 1967-02-10 |
DK114114B (en) | 1969-05-27 |
DE1536304A1 (en) | 1970-01-08 |
SE305178B (en) | 1968-10-14 |
DE1536304B2 (en) | 1976-10-07 |
BE685217A (en) | 1967-01-16 |
CH426617A (en) | 1966-12-15 |
GB1091387A (en) | 1967-11-15 |
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