SE178291C1

SE178291C1 -

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Publication number: SE178291C1
Authority: SE
Publication date: 1961-01-01

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Uppfinnare: E A Evieux Prioritet begeird frail den 11 lune och 18 december 1955 saint den maj 1957 (Frankrike) Foreliggande uppfinning hanfor sig till framstallningen av nya organiska tennforeningar. Inventor: E A Evieux Priority begird frail on 11 lune and 18 December 1955 saint on May 1957 (France) The present invention relates to the preparation of new organic tin compounds.

Dessa foreningar ha minst en osubstituerad vinylradikal, som ãr bunden direkt vid en tennatom i en monomer molekyl, och kunna representeras av foljande allmanna formel: RaSnR/(a_b)X(b_a) i vilken de oIika radikalerna R, R' och X arc bundna direkt vid tennatomen, varvid R betecknar en osubstituerad vinylradikal, R' betecknar en annan organisk radikal an vinyl, X betecknar en halogenatom eller en syreatom, som genom sin andra valens är bunden antingen till en vatentom eller till en andra radikal — [Ra Sn R'(b)] eller en organisk acylradikal (—COR") eller en svavelradikal (—SR"), samt a och b beteckna hela tal av hogst 4 och a hogst ãr lika med b. These compounds have at least one unsubstituted vinyl radical, which is attached directly to a tin atom in a monomeric molecule, and can be represented by the following general formula: RaSnR / (a_b) X (b_a) in which the various radicals R, R 'and X arc are bound directly at the tin atom, where R represents an unsubstituted vinyl radical, R 'represents another organic radical other than vinyl, X represents a halogen atom or an oxygen atom, which by its second valence is bound either to a water atom or to a second radical - [Ra Sn R '(b)] or an organic acyl radical (—COR ") or a sulfur radical (—SR"), and a and b denote integers of felling 4 and a felling is equal to b.

De organiska radikalerna R' kunna utgoras av mdttade eller omdttade, alifatiska, heterocykliska eller alicykliska radikaler eller av aromatiska, eventuellt substituerade radikaler. Da (4-b) Sr stbrre an 1, kunna radikalerna vara lika eller olika. The organic radicals R 'may consist of saturated or unsaturated, aliphatic, heterocyclic or alicyclic radicals or of aromatic, optionally substituted radicals. Since (4-b) is greater than 1, the radicals can be the same or different.

Den organiska radikalen R" kan vara alifa tisk, alicyklisk, aromatisk eller heterocyklisk samt eventuellt innehallande forestrade hydroxyleller karboxylgrupper. The organic radical R "may be aliphatic, alicyclic, aromatic or heterocyclic and optionally containing esterified hydroxyl or carboxyl groups.

Acylradikalen —COR" kan hdrrora fran en enbasisk eller flerbasisk, mattad, eller omattad, alifatisk eller aromatisk syra, vars andra syragrupper eventuellt aro forestrade. The acyl radical "COR "may be derived from a monobasic or polybasic, matt, or unsaturated, aliphatic or aromatic acid, the other acid groups of which may be esterified.

AI1L eller vardet pa a och b kunna de nya tennforeningarna innehalla: enbart vinylradikaler, tetravinyltenn, bade vinylradikaler och andra organiska radikaler an vinyl, exempelvis monovinyldietyltenn, dibutyldivinyltenn och trivinylmonoetyltenn, bade vinylradikaler och halogenatomer, eller syre- eller svavelhaltiga radikaler, exempelvis monovinyltriklortenn, divinyldiklortenn, trivinylmonoklortenn och monovinyltri-(lauroyloxi)-tenn, — bade vinylradikaler och andra organiska radikaler an vinylradikaler och halogenatomer eller syre- eller svavelhaltiga radikaler, exempelvis monovinyldietylklortenn, hydroxiden eller oxiden av monovinyldietyltenn, monovinyldietyllauroyloxi-tenn och monovinyldietyllauryltiotenn. AI1L or the value of a and b, the new tin compounds may contain: only vinyl radicals, tetravinyltin, both vinyl radicals and other organic radicals other than vinyl, for example monovinyldiethyltin, dibutyldivinyltin and trivinyl monoethyltin, both vinyl radicals or haloortyl or monoventyl or halovin atoms, , trivinyl monochlorotenn and monovinyltri- (lauroyloxy) -tin, - both vinyl radicals and other organic radicals other than vinyl radicals and halogen atoms or oxygen- or sulfur-containing radicals, for example monovinyldiethylchlorotenn, the hydroxide or oxide of monovinyldiethyltin, monovinyltinyl monovinyltinyl monovinyltinyl and monovinyldi.

De nya foreningarna erhallas genom inverkan av en -vinylmagnesiumhalogenid pa en tennhalogenid, som kan vara substituerad med organiska radikaler, enligt foliande allmanna reaktionsformel: a R Mg Hal + Halb Sn Sn R'(4_13) Hal(b_a, + a Mg Hal 2 eventuellt foljd av nagon kand reaktion, som gbr det mojligt att helt eller delvis ersaLLa halogenatomerna med de ovan angivna, syre- eller svavelhaltiga radikalerna. The new compounds are obtained by the action of a -vinylmagnesium halide on a tin halide, which may be substituted by organic radicals, according to the following general reaction formula: a R Mg Hal + Halb Sn Sn R '(4_13) Hal (b_a, + a Mg Hal 2 optionally followed by any known reaction which makes it possible to completely or partially replace the halogen atoms with the above-mentioned oxygen- or sulfur-containing radicals.

DS en vinylmagnesiumhalogenid omsattes med en tennhalogenid, som icke Sr substituerad med organiska radikaler, erhaller man alltefter de inbordes proportionerna mellan vinylmagnesiumforeningen och tennhalogeniden antingen tetravinyltenn eller mer eller mindre starkt halogenerat vinyltenn. When a vinylmagnesium halide is reacted with a tin halide which is not substituted by organic radicals, either the tetravinyltin or more or less strongly halogenated vinyltin is obtained according to the inboard proportions between the vinylmagnesium compound and the tin halide.

Med organiska radikaler substituerade tennhalogenider ge blandade vinyltennforeningar, vilka arc substituerade med andra radikaler och eventuellt Sven innehalla halogener. Tin halides substituted with organic radicals give mixed vinyl tin compounds, which arc substituted with other radicals and possibly Sven contain halogens.

Den vinylmagnesiumhalogenid, som anvandes f8r reaktionerna, utgores lampligen av kloriden eller bromiden. Den framstalles ph kant satt, exempelvis genom inverkan av en vinylhalogenid pa magnesium i en cyklisk eter, sasom tetrahydrofuran eller en polyetenglukoleter. The vinyl magnesium halide used for the reactions is suitably composed of the chloride or bromide. It is prepared by, for example, the action of a vinyl halide on magnesium in a cyclic ether, such as tetrahydrofuran or a polyethylene glucol ether.

Omsattningen av vinylmagnesiumforeningen med tennhalogeniden kan genomforas antingen genom att halogenforeningen eller en losning av densamma halles i en losning av magnesiumderivatet eller genom att en losning av magnesiumderivatet Mlles i en losning av halogenderivatet. 2— — vissa fall kan det ena fOrfarandet vara fordelaktigare an det andra och det ãr lfitt att genom enkla lorsok faststalla de forhallanden, som Ora det mojligt att genomfOra forfarandet enligt uppfinmingen pa det fordelaktigaste sattet. Vid omsattming av tenntetraklorid är den metod, som bestar att satta denna tetraklorid till en losning av -vinylmagnesiumforenino-ben i tetrahydrofuran, be-hl taad med den oldgenlieten, att den beframjar bildningen av ett voluminost dubbelsalt av magnesiumhalogeniden och tetrahydrofuran, varigenom reaktionen hindras. Pet har visat sig, att man kan undvika denna olagenhet genom att hdlla vinylmagnesiumlosningen i en suspension av ett etertenntetrakloridkomplex i eter. Detta komplex erhalles genom °mitring av tenntetrakloriden med etern. Pet bildas en vit, kristalliserad fi5rening, som dr olOslig i eter och har sammansattningen 1 mol tenntetraklorid och 2 moler eter och reagerar som tenntetraklorid. The reaction of the vinylmagnesium compound with the tin halide can be carried out either by pouring the halogen compound or a solution thereof into a solution of the magnesium derivative or by dissolving a solution of the magnesium derivative Mlles in a solution of the halogen derivative. In some cases, one procedure may be more advantageous than the other, and it is difficult to determine by simple means the conditions which make it possible to carry out the procedure according to the invention in the most advantageous manner. In the reaction of tin tetrachloride, the method which consists in adding this tetrachloride to a solution of vinylmagnesium forenino-bone in tetrahydrofuran is, in particular, to promote the formation of a bulky double salt of the magnesium halide and tetrahydrofuran, thereby inhibiting the reaction. It has been found that this inaccuracy can be avoided by pouring the vinylmagnesium solution into a suspension of an ethereal tetrachloride complex in ether. This complex is obtained by miteration of the tin tetrachloride with the ether. Pet is formed a white, crystallized compound, which is soluble in ether and has the composition 1 mole of tin tetrachloride and 2 moles of ether and reacts as tin tetrachloride.

Den. vid omsattning av vinylmagnesiumforeningen och det halogenerade temiderivatet bildade foreningen kan isoleras pa olika sat. Om man exempelvis framstaller ett ohalogenerat derivat b i den allmanna formeln), kan man behandla -u.ppslamningen med surgjort isvatten, varefter man dekanterar, torkar och indunstar det organiska skiktet, som innehaller det onskade derivatet. Om man liar framstullt ett halogenerat derivat, avskiljer man magnesiumhalogeniden genom filtering och isolerar sedan produkten genom indunstning av filtratet. Foljancle icke begransande exempel belysa uppfinningen ytterligare. The. in the reaction of the vinylmagnesium compound and the halogenated theme derivative the compound formed can be isolated in various ways. For example, if an unhalogenated derivative b is prepared in the general formula), the slurry can be treated with acidified ice water, after which the organic layer containing the desired derivative is decanted, dried and evaporated. If a halogenated derivative is eluted, the magnesium halide is separated by filtration and then the product is isolated by evaporation of the filtrate. The following non-limiting examples further illustrate the invention.

Foreningar med den allmanna formeln med X betecknande en hydroxylgrupp, erhallas genom hydrolys av motsvarande halogenerade, organiska tennderivat, exempelvis med baser. De dehydratiseras ldtt for att bilda oxider. For exempelvis hydroxiden av monovinyldietyltenn kan reaktionen skrivas pa folja.nde satt: 2 R.R',SnOH RR',Sn.OSnRR', + H20 De foreningar, i vilka X beteek.nar en acyloxiradikal, kunna under tillampning av kiinda fdrfaranden framstallas, antingen ur hydroxylerade derivat eller direkt genom inverkan av alkalisalter av organiska syror pa det halogenerade derivatet. Compounds of the general formula X representing a hydroxyl group are obtained by hydrolysis of the corresponding halogenated organic tin derivatives, for example with bases. They dehydrate slightly to form oxides. For example, for the monovinyldiethyltin hydroxide, the reaction can be written as follows: 2RR ', SnOH RR', Sn.OSnRR ', + H 2 O. The compounds in which X represents an acyloxy radical can be prepared by applying the following procedures. , either from hydroxylated derivatives or directly by the action of alkali salts of organic acids on the halogenated derivative.

De svavelhaltiga pro dukterna kunna erhallas genom inverkan av ett alkalisalt av en merkaptan pa motsvarande, halogenerade derivat, eller genom inverkan av en merkaptan pa det halogenerade derivatet, sdrskilt i narvaro av organiska baser, sasom pyridin. The sulfur-containing products can be obtained by the action of an alkali metal salt of a mercaptan on the corresponding halogenated derivatives, or by the action of a mercaptan on the halogenated derivative, especially in the presence of organic bases such as pyridine.

De enligt uppfinningen framstallda pro dukterna kunna bland annat anvandas som stabilisatorer for halogenerade plaster eller for gummi, som polymerisationskatalysatorer, som insekticider och funaicider samt som mellanprodukter vid organiska synteser. The products prepared according to the invention can be used, inter alia, as stabilizers for halogenated plastics or for rubber, as polymerization catalysts, as insecticides and funicicides and as intermediates in organic syntheses.

Exempel 1. Man framstaller en losning av vinylmagnesiumbromid i tetrahydrofuran genom ornsattning av 17g vinylbromid med 39 g magnesium i 37g tetrahydrofuran. Man framstaller vidare en suspension av ett komplex av tenntetra klorid och eter genom mekanisk omroring av 50 g tenntetraklorid i 250 ml torr eter. Under varmeutvecklingen bildas komplexet av tenntetraklorid och eter, vilket forblir suspenderat i etern. Man. tillsatter sedan under °mitring och kylning till 35° C den. i varme dekanterade vinylmagnesiumlosningen, medan etern kondenseras och ledes tillbaka. Reaktionsmassan tjocknar och spddes, vid behov med en ringa mangd eter. Dt tillsattningen är avslutad, varmer man ytterligare en timme under aterflode. Den till 25° C avkylda uppslamningen Mlles pa is och surgores mot kongorott med saltsyra fOr neutralisering av magnesiumoidden. Eterskiktet tvattas, neutraliseras och torkas sedan Over kalciumklorid. Man driver av etern, som innehaller en ringa mangd tetrahydrofuran, varefter man rektifierar aterstoden vid ett tryck av 50 mm Hg. Man tar vara pa den fraktion, som gar Over vid 78-80° G/50 mm Hg, vilket svarar mot ett utbyte av tetravinyltenn pa 70 % av det teoretiskt mojliga raknat pa tenntetrakloriden. d" = 1,2; n7=1,49 Analys Sn: berdknat 52,30 % — funnet 51,6 % C: » 42,35 — » 42,3 H: > 5,30 — » 5,4 Exempel 2. Man hailer en losning av -vinylmagnesiumbromid, framstalld av 16 g magnesium och 70 g vinylbromid i 200 g tetrahydrofuran, i en losning av 100 g tetraetylklortenn, kpkt 130-132° C/60 mm Hg, i 300 ml eter. Harvid utfaller magnesiumkloridbromid. Reaktionen astadkommes genom kokning en timme under aterfkide. Man hailer reaktionsblandningen i isvatten, surgor med saltsyra och behandlar eterskiktet sasom enligt exempel 1. Med ett utbyte av 80 % erhaller man monovinyltrietyltenn i form av en ofargad och nastan luktfri vatska, kpkt 91-93° C/50 mm Hg, d24= 1,26; nt,3= 1,477. Analys Sn: berdknat 51,00 % — funnet 51,50 % C :»41,— * 41, H: » 7,74 — » 7,90 Exempel 3. Man fdrfar pa samma satt som enligt exempel 2 dock under ersdttning av trietylklortenn med dibutyldiklortenn. Man erhaller divinyldibutyltenn med ett utbyte av 80 % av det teoretiskt mOjliga rdknat pa dibutylklortenn. Example 1. A solution of vinyl magnesium bromide in tetrahydrofuran is prepared by reacting 17 g of vinyl bromide with 39 g of magnesium in 37 g of tetrahydrofuran. A suspension of a complex of tin tetrachloride and ether is further prepared by mechanical stirring of 50 g of tin tetrachloride in 250 ml of dry ether. During heat evolution, the complex of tin tetrachloride and ether is formed, which remains suspended in the ether. MAN. then add during tempering and cooling to 35 ° C it. in heat decanted the vinylmagnesium solution, while the ether is condensed and returned. The reaction mass thickens and is diluted, if necessary with a small amount of ether. When the addition is complete, heat for another hour under reflux. The slurry cooled to 25 ° C is milled on ice and acidified against congo root with hydrochloric acid to neutralize the magnesium oxide. The ether layer is washed, neutralized and then dried over calcium chloride. The ether, which contains a small amount of tetrahydrofuran, is driven off, after which the residue is rectified at a pressure of 50 mm Hg. Care is taken with the fraction passing over at 78-80 ° G / 50 mm Hg, which corresponds to a yield of tetravinyl tin of 70% of the theoretically possible shaving of the tin tetrachloride. d "= 1.2; n7 = 1.49 Analysis Sn: berdknat 52.30% - found 51.6% C:» 42.35 - »42.3 H:> 5.30 -» 5.4 Example 2 A solution of -vinylmagnesium bromide, prepared from 16 g of magnesium and 70 g of vinyl bromide in 200 g of tetrahydrofuran, in a solution of 100 g of tetraethylchlorotenn, cp. 130-132 ° C / 60 mm Hg, in 300 ml of ether is obtained. The reaction is effected by boiling for one hour under athercfide. The reaction mixture is heated in ice water, acidified with hydrochloric acid and the ether layer is treated as in Example 1. ° C / 50 mm Hg, d24 = 1,26; nt, 3 = 1,477. Analysis Sn: berdknat 51.00% - found 51.50% C: »41, - * 41, H:» 7.74 - » 7.90 Example 3 The procedure is the same as in Example 2, but replacing the triethyl chlorotin with dibutyldichlorotenn, divinyldibutyltin is obtained with a yield of 80% of the theoretically possible ratio of dibutylchlorotenn.

Kpkt = 76-80° C/1-2 mm Hg D2, = 1,13i4 = 1,482 Analys Sn: berdknat 41,40 % — funnet 41,8 % C : » 50,—» 50, H: » 8,37 —» 8,47 Exempel 4. I en losning av vinylmagnesiumbromid, som har framstdllts av 28 g magnesium och 129 g vinylbromid i 129 g tetrahydrofuran och som halles vid 50° G, hailer man under 1,5 h och °mitring 51 g monoetyltriklortenn (d25 kpkt 100-102° C/35 mm Hg) lost i 200 ml eter. Harvid utfaller magnesiumkloridbromid. Man hailer i isvatten, surgor med saltsyra och behandlar eterskiktet sasom enligt exempel 1. Med ett utbyte av 61 % erhaller man trivinylmono- - -a etyltenn i form av en neutral, nastan luktfri olja, kpkt 73-74° 0/35 mm Hg d.24 = 1,25 ny =1,49 Analys Sn: berdknat 51,80 % - funnel 51,3 % C e 42,10 - » 41,4 H: » 6,15 - e 5,3 Exempel 5. I en kolv forsedd med aterflOdeskylare inf Ores 80 g tenntetraklorid (teoretiskt 78 g) och 22,6 g tetravinyltenn (0,1 moler). Man varmer pa ett oljebad under 4,5 h till 100-110° C, varefter man rektifierar under ett tryck av 5 mm Hg. Man erhaller 77 g hjartfraktion (kpkt 49-53° C), som efter ytterligare rektifiering ger rent monovinyltriklortenn. Detta utgor en ofargad vdtska med stickande lukt, kpkt 33-35° 0/2 mm Hg, d„ = 2,0, klorhalt, berdknat 42,19 %, funnet 42,0 %. Kpkt = 76-80 ° C / 1-2 mm Hg D2, = 1,13i4 = 1,482 Analysis Sn: berdknat 41.40% - found 41.8% C: »50, -» 50, H: »8.37 8.47 Example 4. In a solution of vinylmagnesium bromide, which has been prepared from 28 g of magnesium and 129 g of vinyl bromide in 129 g of tetrahydrofuran and which is kept at 50 ° C, 51 g of monoethyltrichlorotene are heated for 1.5 hours and tempered. (d25 bp 100-102 ° C / 35 mm Hg) dissolved in 200 ml of ether. Magnesium chloride bromide precipitates. Hail in ice water, acidify with hydrochloric acid and treat the ether layer as in Example 1. With a yield of 61%, trivinyl mono- - a ethyl tin is obtained in the form of a neutral, almost odorless oil, bp 73-74 ° 0/35 mm Hg d.24 = 1.25 ny = 1.49 Analysis Sn: berdknat 51.80% - funnel 51.3% C e 42.10 - »41.4 H:» 6.15 - e 5.3 Example 5. In a flask equipped with a reflux condenser, 80 g of tin tetrachloride (theoretically 78 g) and 22.6 g of tetravinyl tin (0.1 moles) are introduced. Heat an oil bath for 4.5 hours to 100-110 ° C, then rectify under a pressure of 5 mm Hg. 77 g of heart fraction (b.p. 49-53 ° C) are obtained, which after further rectification gives pure monovinyl trichlorotin. This is an undyed liquid with a pungent odor, mp 33-35 ° 0/2 mm Hg, d „= 2.0, chlorine content, berdknat 42.19%, found 42.0%.

Exempel 6. I en kolv forsedd med omrorare hailer man 43 g tenntetraklorid lost i 200 ml bensen och sedan under en timme vid c:a 60° C en lOsning ay vinylmagnesiumbromid framstalld ay 53,5 g vinylbromid, 12 g magnesium och 123,5 g tetrahydrofuran. Man spdder sedan med bensen for utfallning av stone delen magnesiumkloridbromid. Man filtrerar, tvattar med bensen och destillerar. Vid 60-63° C/2 mm Hg erhaller man divinyldiklortenn, som Or lattlosligt i vatten och losligt i organiska losningsmedel. d„ = 1,7 46 = 1,553 Analys Sn: berdknat 48,5 % - funnet 45 % Cl: » 29,2 - » 29 Exempel 7. Man hailer vid 50° C en losning av vinylmagnesiumbromid, framstalld av 53,g vinylbromid och 12 g magnesium i 128,5 g tetrahydrofuran, i en losning av 43 g tenntetraklorid i 200 ml bensen. Man kyler sedan, spader med bensen, filtrerar och destillerar. Trivinylmonoklortenn gar Over vid 50-53° C/1 mm Hg. Det Or lattlosligt i vatten samt losligt i organiska lOsningsmedel. = 1,48 Analys Sn: beraknat 50,3 % - funnet 48,6 % Cl: » 15,1 - s 13,8 Exempel 8. Man haller vid 60° C och en timme en lOsning av vinylmagnesiumbromid, framstalld av 14 g magnesium och 70 g vinylbromid i 19g tetrahydrofuran, i en omrOrd losning av 168 g dietyldiklortenn i 350 ml bensen. Magnesiumkloridbromiden utfaller. Man kyler, hailer Over is, surgor mot kongorott och extraherar med bensen. Efter dekantering torkas bensenen Over kalciumklorid och destilleras. Vid 70-75° C/3 mm Hg destilleras sedan monovinyldietylklortennet med ett utbyte av c:a 60 %. d„ = 1,60 Analys Sn: beraknat 49,0 % - funnet 49,4 % Cl: » 14,8 - » 14,7 Exempel 9. Man framstaller en losning ay 9,4 g kaliumhydroxid i 175 ml etanol och hailer i denna losning mid 20° G under omroring 40 g monovinyldietylklortenn i 25 ml etanol. Harvid utfalles kaliumklorid. Reaktionsblandningen bor vara mycket svagt basisk mid reaktionens slut. Man filtrerar i vakuum, indunstar filtratet yid lag temperatur, sugfiltrerar den erhallna, fasta massan, tvattar filterkakan med eter for att avlagsna en ringa mangd illaluktande olja och torkar sedan vid 40° C. Man erhaller en blandning av hydroxiden och o3d den av monovinyldietyltenn i form av ett icke smaltbart, vitt pulver, vilket antandes vid 3° C, Or olosligt eller mycket svarlosligt i vatten, alkohol, aceton, bensen, kloroform, eter och tetrahydrofuran samt lattlosligt i amyloxid och tetrahydropyran. Pulvret loser sig langsamt i syror. Example 6. In a flask equipped with a stirrer, haul 43 g of tin tetrachloride dissolved in 200 ml of benzene and then for one hour at about 60 ° C a solution of vinyl magnesium bromide prepared of 53.5 g of vinyl bromide, 12 g of magnesium and 123.5 g tetrahydrofuran. It is then diluted with benzene to precipitate the stone portion of magnesium chloride bromide. It is filtered, washed with benzene and distilled. At 60-63 ° C / 2 mm Hg, divinyl dichlorotene is obtained, which is easily soluble in water and soluble in organic solvents. d „= 1.7 46 = 1.553 Analysis Sn: berdknat 48.5% - found 45% Cl:» 29.2 - »29 Example 7. A solution of vinylmagnesium bromide, prepared from 53 g of vinyl bromide, is obtained at 50 ° C. and 12 g of magnesium in 128.5 g of tetrahydrofuran, in a solution of 43 g of tin tetrachloride in 200 ml of benzene. You then cool, spade with benzene, filter and distill. Trivinyl monochlorite ignites at 50-53 ° C / 1 mm Hg. It is readily soluble in water and soluble in organic solvents. = 1.48 Analysis Sn: calculated 50.3% - found 48.6% Cl: »15.1 - s 13.8 Example 8. A solution of vinyl magnesium bromide, prepared from 14 g, is kept at 60 ° C for one hour. magnesium and 70 g of vinyl bromide in 19 g of tetrahydrofuran, in a stirred solution of 168 g of diethyl dichlorotene in 350 ml of benzene. The magnesium chloride bromide fails. One cools, hails Over ice, surges against Congo root and extracts with benzene. After decantation, the benzene is dried over calcium chloride and distilled. At 70-75 ° C / 3 mm Hg, the monovinyl diethyl chlorotene is then distilled in a yield of about 60%. d „= 1.60 Analysis Sn: calculated 49.0% - found 49.4% Cl:» 14.8 - »14.7 Example 9. A solution of 9.4 g of potassium hydroxide in 175 ml of ethanol and hailer is prepared in this solution at 20 ° C with stirring 40 g of monovinyl diethyl chlorotene in 25 ml of ethanol. Potassium chloride precipitates. The reaction mixture should be very weakly basic at the end of the reaction. Filter in vacuo, evaporate the filtrate at low temperature, suction filter the resulting solid mass, wash the filter cake with ether to remove a small amount of malodorous oil and then dry at 40 ° C. in the form of a non-digestible white powder, which ignites at 3 ° C, or insoluble or very unresponsive in water, alcohol, acetone, benzene, chloroform, ether and tetrahydrofuran and readily soluble in amyloxide and tetrahydropyran. The powder slowly dissolves in acids.

Exempel 10. Man loser under omroring i en kolv 64 g kaliumlaurat i 1200 ml etanol yid 60° C. Man kyler till 10° G och tillsatter under 1,5 h 21 g (1/12 mol) monovinyltriklortenn lost i 150 ml etanol. Man staller losningen neutral genom tillsats ay en ringa mangd laurat. Man later losningen sti i vila i 2 h, filtrerar bort kaliumkloriden och driver av alkoholen I vakuum vid 30° C. Det stelnande vinyltri-(lauroyloxi)-tennet (eller »trilauratet»), innehaller en ringa mangd illaluktande amnen, som avlagsnas genom tvattning med 20-pro centig alkohol, och en ringa mangd fri trilaurinsyra, som avlagsnas genom behandling av eterlOsningen ay trilauratet med natriumbikarbonat. Sedan etern har avdrivits, erhaller man 24 g trilaurat i form av vita kristaller. Smpkt 36-38°C. Trilauratet Or olosligt i vatten, losligt i vanliga organiska lOsningsmedel. Det fortvalas loft med natriumalkoholat. Example 10. With stirring in a flask, 64 g of potassium laurate in 1200 ml of ethanol at 60 ° C are dissolved. The mixture is cooled to 10 ° C and 21 g (1/12 mol) of monovinyl trichlorotene dissolved in 150 ml of ethanol are added over 1.5 hours. The solution is made neutral by the addition of a small amount of laurate. The solution is allowed to stand for 2 hours, the potassium chloride is filtered off and the alcohol is driven off in a vacuum at 30 ° C. The solidifying vinyl tri (lauroyloxy) tin (or "trilaurate") contains a small amount of odorous substances which are removed by washing with 20% alcohol, and a small amount of free trilauric acid, which is removed by treating the ether solution in the trilaurate with sodium bicarbonate. After the ether has been evaporated, 24 g of trilaurate in the form of white crystals are obtained. Mp 36-38 ° C. Trilaurate Or insoluble in water, soluble in common organic solvents. Loft with sodium alcoholate is preferred.

Analys Sn: beraknat 15,9 % - funnet 16,0 % C :e61,4 - e 58, H:9,98 - e 9,7 Exempel 11. Man lOser 48 g monovinyldietylklortenn i 500 ml etanol ()eh suspenderar 50 g kaliumlaurat i 11 etanol. Man hailer lauratet i en kolv fOrsedd med omrbrare och tillsatter sedan vid 25° C oat under 30 min lOsningen av tennderivatet. En latt varmning intrader. Kalinmkloriden utfaller. Man sugfiltrerar och indunstar sedan losningen i vakuum. Vid avkylning kristalliserar produkten. Man sugfiltrerar, tvattar med 50-procentig kall alkohol och torkar. Man erhaller monovinyldietyltennlauratet med ett utbyte av 80 %. Det Or lattlosligt i absolut etanol, aceton, bensen, kloroform och eter samt olosligt i vatten. Analysis Sn: calculated 15.9% - found 16.0% C: e61.4 - e 58, H: 9.98 - e 9.7 Example 11. 48 g of monovinyldiethyl chlorotene are dissolved in 500 ml of ethanol () and suspension 50 g potassium laurate in 11 ethanol. The laurate is heated in a flask equipped with a stirrer and then the solution of the tin derivative is added at 25 ° C for 30 minutes. A slight warming enters. The potassium chloride precipitates. The suction filter is then filtered and the solution is then evaporated in vacuo. Upon cooling, the product crystallizes. You suction filter, wash with 50% cold alcohol and dry. The monovinyl diethyltin laurate is obtained in a yield of 80%. It is readily soluble in absolute ethanol, acetone, benzene, chloroform and ether and insoluble in water.

Analys Sn: beraknat 29,3 % - funnet 28,8 % C :»53,7 - » 53,7 H: » 8,9 - » 9,2 Exempel 12. I en kolv forsedd med aterflodeskylare hailer man successivt: 20 g monovinyldietylklortenn, 24 g dodekantiol och g pyridin. Man varmer till 50° C pa vattenbad. Pyridinklorhydratet utfaller. Man later reaktionsblandningen sta. 0,5 h vid 50° C, spader sedan med 100 ml bensen, kyler, filtrerar av klorhydratet och tvattar med bensen. BensenlOsningen tvattas med vatten och torkas Over kalciumklorid. Man driver ay bensenen och eliminerar de flyktiga anmena genom att halla reaktionsblandningen vid 150° C och ett tryck ay 1 mm Hg. Ett utbyte av 78 % monovinyldietyl- — — dodecyltiotenn, corn har formen av en ofargad och praktiskt taget luktfri olja erhdlles med ett utbyte av 78 %. c121 = 1,06 ng = 1,498. Denna forening itr Idttloslig i organiska losningsmedel och praktiskt taget olOslig i vatten. Analysis Sn: calculated 29.3% - found 28.8% C: »53.7 -» 53.7 H: »8.9 -» 9.2 Example 12. In a flask equipped with a backflow cooler, one successively hails: 20 g monovinyl diethyl chlorotin, 24 g dodecanethiol and g pyridine. Heat to 50 ° C in a water bath. The pyridine hydrochloride precipitates. The reaction mixture is allowed to stand. 0.5 h at 50 ° C, then spray with 100 ml of benzene, cool, filter off the hydrochloride and wash with benzene. The benzene solution is washed with water and dried over calcium chloride. The benzene is driven off and the volatile anemene is eliminated by keeping the reaction mixture at 150 ° C and a pressure of 1 mm Hg. A yield of 78% of monovinyldiethyl- - - dodecylthiote, corn in the form of a colorless and practically odorless oil is obtained with a yield of 78%. c121 = 1.06 ng = 1.498. This compound is soluble in organic solvents and practically insoluble in water.

Analys Sn: berdknat 29,20 % — funnet 26,6 % S: » 7,97 — a 8,3 Analysis Sn: berdknat 29.20% - found 26.6% S: »7.97 - a 8.3

Claims

A patent claim for the preparation of monomeric organic tin derivatives having at least one unsubstituted vinyl radical, which is attached directly to a tin atom and having the general formula: Ro.Snir (_b) Xcb,) in which R represents an unsubstituted vinyl radical, R 'represents a another organic radical other than vinyl, X represents a halogen atom or an oxygen atom, which by its second valence is attached to a hydrogen atom, to a second radical— [RaSnR '(4-b)] or to an organic acyl radical, or a radical —SR ", in which R" represents an organic radical, wherein a and b denote integers of at most 4, wherein a at least equal to b, denotes & ray, that a vinylmagnesium halide of the general formula RMg Hal, in which formula Hal a halogen atom, is reacted with a halogenated tin derivative of the formula SnHalbRi (4-b), to form a compound RaSnR1 (4_b) Hal (b,), and that this compound is optionally reacted with a. another compound by means of which the group Halcb-a) can be replaced by the oxygen or sulfur-containing groups indicated above in connection with the definition of the symbol X. Cited publications: American chemical society. Journal 79 (1957), pp. 515-17 (Seyferth, D. & Stone, F. G. A. Vinyl derivatives of the metals. I. Synthesis of vinyltin compounds). Stockholm 1962. Kungl. Bolitr. P. A. Norstedt & Saner. 620089