NO131934B - - Google Patents
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- NO131934B NO131934B NO4341/69A NO434169A NO131934B NO 131934 B NO131934 B NO 131934B NO 4341/69 A NO4341/69 A NO 4341/69A NO 434169 A NO434169 A NO 434169A NO 131934 B NO131934 B NO 131934B
- Authority
- NO
- Norway
- Prior art keywords
- halide
- mol
- reaction
- organotricyclohexyltin
- tricyclohexyltin
- Prior art date
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- -1 tricyclohexyl tin halide Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000007818 Grignard reagent Substances 0.000 description 8
- 150000004795 grignard reagents Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YICRPERKKBDRSP-UHFFFAOYSA-N methyl 3-amino-4-methylthiophene-2-carboxylate Chemical compound COC(=O)C=1SC=C(C)C=1N YICRPERKKBDRSP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- UBOGEXSQACVGEC-UHFFFAOYSA-K phenyltin(3+);trichloride Chemical compound Cl[Sn](Cl)(Cl)C1=CC=CC=C1 UBOGEXSQACVGEC-UHFFFAOYSA-K 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- LRLNMPJWOOOYNO-UHFFFAOYSA-N tricyclohexyl(phenyl)stannane Chemical compound C1CCCCC1[Sn](C=1C=CC=CC=1)(C1CCCCC1)C1CCCCC1 LRLNMPJWOOOYNO-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDFUNRTWHPWCKO-UHFFFAOYSA-N 4,5,9,10-tetrahydropyrene Chemical compound C1CC2=CC=CC3=C2C2=C1C=CC=C2CC3 XDFUNRTWHPWCKO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VKAAGRLEXPKJAI-UHFFFAOYSA-N cyclohexyltin Chemical class [Sn]C1CCCCC1 VKAAGRLEXPKJAI-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JUISPCSEIXBMNI-UHFFFAOYSA-N tetracyclohexylstannane Chemical compound C1CCCCC1[Sn](C1CCCCC1)(C1CCCCC1)C1CCCCC1 JUISPCSEIXBMNI-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical compound C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Fremgangsmåte til fremstilling av tricykloheksyltinnhalogenid.Process for the preparation of tricyclohexyl tin halide.
Description
Den foreliggende oppfinnelse går ut på en ny fremgangsmåte til fremstilling av tricykloheksyltinnhalogenid (CgH^) ^SnX, hvor X er klor eller brom, fortrinnsvis klor. The present invention concerns a new process for the production of tricyclohexyltin halide (CgH^)^SnX, where X is chlorine or bromine, preferably chlorine.
Fra US-PS 3 355 468 er det kjent å fremstille tricykloheksyltinnklorid eller -bromid ved omsetning av cykloheksylmagnesiumhalogenid og tinntetrahalogenid i et molforhold på 3:1. Denne kjente fremgangsmåte har imidlertid den ulempe at det er meget vanskelig å unngå samtidig dannelse av tetracykloheksyltinn i visse mengder. From US-PS 3 355 468 it is known to prepare tricyclohexyl tin chloride or bromide by reacting cyclohexyl magnesium halide and tin tetrahalide in a molar ratio of 3:1. However, this known method has the disadvantage that it is very difficult to avoid the simultaneous formation of tetracyclohexyltin in certain quantities.
En hensikt med oppfinnelsen er å skaffe en fremgangsmåte til fremstilling av forbedrede utbytter av tricykloheksyltinnhalogenid, spesielt et hovedsakelig rent tricykloheksyltinnhalogenidprodukt. One purpose of the invention is to provide a method for producing improved yields of tricyclohexyltin halide, in particular a substantially pure tricyclohexyltin halide product.
Fremgangsmåten ifølge oppfinnelsen til fremstilling av tricyklo-heksyltinnhalogeni<d> (<Cg>H^^)^<S>nX, hvor X er klor eller brom, er karakterisert ved at et organotinntrihalogenid RSnX^ hvor R er alkyl eller alkenyl med høyst 8 karbonatomer eller aryl, og cykloheksylmagnesiumhalogenid (CgH^)MgX i et forhold på minst 3 mol cykloheksylmagnesiumhalogenid per mol organotinntrihalogenid omsettes i et første trinn for å danne -et organotricykloheksyltinn (CgH^)^SnR, og at dette organotricykloheksyltinn og tinntetrahalogenid omsettes i et annet trinn for å gi tricykloheksyltinnhalogenid. The process according to the invention for the production of tricyclohexyltin halide<d> (<Cg>H^^)^<S>nX, where X is chlorine or bromine, is characterized by an organotin trihalide RSnX^ where R is alkyl or alkenyl with at most 8 carbon atoms or aryl, and cyclohexylmagnesium halide (CgH^)MgX in a ratio of at least 3 mol of cyclohexylmagnesium halide per mol of organotin trihalide is reacted in a first step to form -an organotricyclohexyltin (CgH^)^SnR, and that this organotricyclohexyltin and tin tetrahalide are reacted in another step to give tricyclohexyltin halide.
Tricykloheksyltinnproduktet (CgH^)^<S>nX som dannes med høyt utbytte ved utførelse av oppfinnelsen, kan innbefatte produkter hvor cykloheksylgruppen, som er betegnet som CgH^l5 er inert substituert. Typiske produkter som kan fremstilles ved fremgangsmåten ifølge opp- - finnelsen, kan i tillegg til tricykloheksyltinnbromid og tricykloheksyltinnklorid omfatte: Tri-3-metylcykloheksyltinnklorid, tri(4-butylcykloheksyl)tinnklorid, tri(3-fenylcykloheksyl)tinnklorid, tri(3,3>5-trimetylcykloheksyl)tinnklorid, tri(3>3,5-cykloheksyl)tinn-klorid, tri(3,5-dimetylcykloheksyl)tinnklorid, tri(4-t-butylcyklo-heksyl)tinnklorid, tri(4-isopropyl-5-metylcykloheksyl)tinnklorid, tri(3,5-dimetylcykloheksyl)tinnklorid, tri(3,4-dimetylcykloheksyl)tinn-klorid og de tilsvarende bromider. The tricyclohexyltin product (CgH^)^<S>nX, which is formed with high yield when carrying out the invention, may include products where the cyclohexyl group, which is designated as CgH^l5, is inertly substituted. Typical products which can be produced by the method according to the invention, in addition to tricyclohexyl tin bromide and tricyclohexyl tin chloride, may include: Tri-3-methylcyclohexyl tin chloride, tri(4-butylcyclohexyl) tin chloride, tri(3-phenylcyclohexyl) tin chloride, tri(3,3> 5-trimethylcyclohexyl)tin chloride, tri(3>3,5-cyclohexyl)tin chloride, tri(3,5-dimethylcyclohexyl)tin chloride, tri(4-t-butylcyclohexyl)tin chloride, tri(4-isopropyl-5- methylcyclohexyl)tin chloride, tri(3,5-dimethylcyclohexyl)tin chloride, tri(3,4-dimethylcyclohexyl)tin chloride and the corresponding bromides.
Det tinntetrahalogenid som kan anvendes ved utførelse av oppfinnelsen, er SnX^, hvor X er klor eller brom. The tin tetrahalide that can be used in carrying out the invention is SnX^, where X is chlorine or bromine.
Ved utførelse av oppfinnelsen blir der fremstilt organotricykloheksyltinn ved omsetning av organotinntrihalogenid med cykloheksylmagnesiumhalogenid i en mengde på minst 3 mol per mol organotinntrihalogenid. Det nøyaktige forhold mellom Grignard-reagensen og organo-tinntrihalogenidet er ikke av kritisk betydning. Por å redusere den samtidige dannelse av uønskede cykloheksyltinnforbindelser er et overskudd av Grignard-reagens ønskelig. When carrying out the invention, organotricyclohexyltin is produced by reacting organotin trihalide with cyclohexylmagnesium halide in an amount of at least 3 mol per mol of organotin trihalide. The exact ratio of the Grignard reagent to the organotin trihalide is not critical. In order to reduce the simultaneous formation of undesirable cyclohexyltin compounds, an excess of Grignard reagent is desirable.
Ved utførelse av oppfinnelsen kan reaksjonen mellom organotinn-trihalogenidet og cykloheksylmagnesiumhalogenidet være som følger: When carrying out the invention, the reaction between the organotin trihalide and the cyclohexylmagnesium halide can be as follows:
Som nevnt ovenfor er molforholdet mellom cykloheksylmagnesiumhalogenid og organotinntrihalogenid ikke av avgjørende betydning, bortsett fra at der for oppnåelse av de høye utbytter ifølge oppfinnelsen bør anvendes minst 3 mol cykloheksylmagnesiumhalogenid per mol organotinntrihalogenid. Den endoterme reaksjonsblanding fra det første- trinn bør fortrinnsvis. holdes på en temperatur av 25-95°C, fortrinnsvis lavere enn 80°C. Reaksjonstiden kan ligge på mellom 60 og 150 minutter. Organotri-cykloheksyltinnproduktet kan utvinnes på vanlige måter, f.eks. ved ekstraksjon eller destillasjon. As mentioned above, the molar ratio between cyclohexylmagnesium halide and organotin trihalide is not of decisive importance, except that in order to achieve the high yields according to the invention, at least 3 mol of cyclohexylmagnesium halide per mol of organotin trihalide should be used. The endothermic reaction mixture from the first step should preferably. is kept at a temperature of 25-95°C, preferably lower than 80°C. The reaction time can be between 60 and 150 minutes. The organotricyclohexyltin product can be recovered by conventional means, e.g. by extraction or distillation.
Et høytkokende inert hydrokarbonoppløsningsmiddel, f.eks. xylen eller toluen, kan tilsettes og eteren fjernes før organotinntri-halogenidet tilsettes. På denne måte fås der en blanding som er relativt enkel å håndtere. Hvis fremgangsmåten utføres ved tilsetning av høytkokende inert hydrokarbon og organotinntrihalogenid til eter-oppløsningen og eteren senere destilleres fra for å tillate reaksjonen å utføres ved høy temperatur, fås der en seigtflytende blanding som er vanskelig å håndtere. A high-boiling inert hydrocarbon solvent, e.g. xylene or toluene, may be added and the ether removed before the organotin trihalide is added. In this way, a mixture is obtained that is relatively easy to handle. If the process is carried out by adding high-boiling inert hydrocarbon and organotin trihalide to the ether solution and the ether is later distilled off to allow the reaction to be carried out at high temperature, a viscous mixture is obtained which is difficult to handle.
I reaksjonsbestanddelen RSnX^ er R som nevnt alkyl eller alkenyl med høyst 8 karbonatomer eller aryl, herunder disse radikaler når de er inert substituert. Når R er alkyl, kan det som et typisk eksempel være alkyl med rett eller forgrenet kjede, herunder metyl, etyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, neopentyl, isoamyl, n-heksyl, isoheksyl, heptyler eller oktyler. Når R er alkenyl, kan det typisk være vinyl, allyl, 1-propenyl, metallyl, buten-l-yl, buten-2-yl, buten-3-yl, penten-1-yl, heksenyl, heptenyl eller oktenyl. Når R er aryl, kan det typisk være fenyl, naftyl etc. R kan være inert substituert, dvs. bære ikke-reaktive substituenter som alkyl, aryl, cykloalkyl, aralkyl, alkaryl, alkenyl, eter etc. Typiske substituerte alkyler omfatter 2-etoksyetyl etc. Substituerte alkenyler omfatter -fenylpropenyl etc. Inert substituert aryl omfatter klorfenyl, anisyl, bifenyl etc. In the reaction component RSnX^, as mentioned, R is alkyl or alkenyl with no more than 8 carbon atoms or aryl, including these radicals when they are inertly substituted. When R is alkyl, as a typical example it can be straight or branched chain alkyl, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl, heptyl or octyl. When R is alkenyl, it can typically be vinyl, allyl, 1-propenyl, metallyl, buten-1-yl, buten-2-yl, buten-3-yl, penten-1-yl, hexenyl, heptenyl or octenyl. When R is aryl, it can typically be phenyl, naphthyl etc. R can be inertly substituted, i.e. carry non-reactive substituents such as alkyl, aryl, cycloalkyl, aralkyl, alkaryl, alkenyl, ether etc. Typical substituted alkyls include 2-ethoxyethyl etc. Substituted alkenyls include -phenylpropenyl etc. Inert substituted aryl include chlorophenyl, anisyl, biphenyl etc.
Den Grignard-reagens som anvendes ved utførelse av fremgangsmåten ifølge oppfinnelsen, nemlig cykloheksylmagnesiumhalogenid, herunder Grignard-reagenser som inneholder inert substituerte cykloheksylradi-kaler som nevnt ovenfor, kan fremstilles ved omsetning av et cykloheksylhalogenid med magnesium i henhold til følgende ligning: The Grignard reagent used in carrying out the method according to the invention, namely cyclohexylmagnesium halide, including Grignard reagents containing inert substituted cyclohexyl radicals as mentioned above, can be prepared by reacting a cyclohexyl halide with magnesium according to the following equation:
Denne reaksjon utføres fortrinnsvis i en inert atmosfære, f.eks. nitrogengass, i nærvær av en alifatisk eter som f.eks. dietyleter, di-n-butyleter etc. eller i nærvær av en cyklisk eter. Forskjellige startere kan være tilstede for å lette dannelsen av Grignard-reagensen. Grignard-reagensen kan ha form av en oppløsning av sitt kompleks med en eter. This reaction is preferably carried out in an inert atmosphere, e.g. nitrogen gas, in the presence of an aliphatic ether such as e.g. diethyl ether, di-n-butyl ether etc. or in the presence of a cyclic ether. Various initiators may be present to facilitate the formation of the Grignard reagent. The Grignard reagent may take the form of a solution of its complex with an ether.
Reaksjonsblandingen kan deretter hydrolyseres for isolasjon av mellomproduktet organotricykloheksyltinn. Dette kan utføres ved The reaction mixture can then be hydrolysed to isolate the intermediate organotricyclohexyltin. This can be done by
tilsetning av en vandig oppløsning av sitronsyre, noe som fører til et tofasesystem. Det organiske skikt i tofasesystemet kan fraskilles ved dekantering. Oppløsningsmiddel kan fjernes fra det organiske skikt ved destillering. Destilleringen kan utføres ved atmosfæretrykk. addition of an aqueous solution of citric acid, leading to a two-phase system. The organic layer in the two-phase system can be separated by decantation. Solvent can be removed from the organic layer by distillation. The distillation can be carried out at atmospheric pressure.
Ved utførelse av det annet trinn ifølge oppfinnelsen, nemlig fremstillingen av tricykloheksyltinnhalogenid, kan reaksjonen mellom organotricykloheksyltinn og tinntetrahalogenid i hovedsakelig samme molforhold være som følger: When carrying out the second step according to the invention, namely the production of tricyclohexyltin halide, the reaction between organotricyclohexyltin and tin tetrahalide in essentially the same molar ratio can be as follows:
Reaksjonstemperaturen for denne prosess ligger mellom 0 og 120°C. Reaksjonstiden ligger mellom 30 og 90 minutter. The reaction temperature for this process is between 0 and 120°C. The reaction time is between 30 and 90 minutes.
Organotricykloheksyltinnet kan tilsettes i form av en oppløsning. Typiske oppløsningsmidler innbefatter xylen, hepten, heksen etc. Reaksjonsmediet på et hvilket som helst tidspunkt kan anses å være dannet ved blanding av reaksjonsbestanddelene i ekvimolekylære forhold. The organotricyclohexyltin can be added in the form of a solution. Typical solvents include xylene, heptene, hexene, etc. The reaction medium at any time can be considered to be formed by mixing the reaction components in equimolecular conditions.
Etter tilbakeløpskjøling av reaksjonsblandingen består denne stort sett av to faser. Oppløsningsmiddelet kan fjernes fra den øvre fase ved destillering. Tricykloheksyltinnhalogenidproduktet kan fjernes fra destillatet ved filtrering. After reflux cooling of the reaction mixture, this largely consists of two phases. The solvent can be removed from the upper phase by distillation. The tricyclohexyl tin halide product can be removed from the distillate by filtration.
Utførelsen av oppfinnelsen skal nå belyses av de etterfølgende ikkebegrensende eksempler. The performance of the invention will now be illustrated by the following non-limiting examples.
Eksempel 1 Example 1
For fremstilling av fenyltinntriklorid ble en 5 liters kolbe med tre halser utrustet med luftmotor, rører, vannkondensator, termometer, tørkerør og nitrogeninnløpsrør fylt med 2135,5 g (5,0 mol) tetrafenyl-tinn. 3907,5 g (15,0 mol) av tetrakloridet ble raskt tilsatt. Reak-sj onsblandingen ble oppvarmet til 200°C og holdt på denne .temperatur i to timer. Blandingen ble filtrert, hvoretter filtratet ble separert. En uoppløselig filterkake ble kastet. Filtratet ble destillert og ga et fenyltinntrikloridprodukt med en vekt på 5423 g, et kokepunktområde på 84-91°C (0,5-0,7 mm Hg) og en brytningsindeks på 1,5836-1,5868. For the production of phenyltin trichloride, a 5 liter flask with three necks equipped with air motor, stirrer, water condenser, thermometer, drying tube and nitrogen inlet tube was filled with 2135.5 g (5.0 mol) of tetraphenyltin. 3907.5 g (15.0 mol) of the tetrachloride was quickly added. The reaction mixture was heated to 200°C and held at this temperature for two hours. The mixture was filtered, after which the filtrate was separated. An insoluble filter cake was discarded. The filtrate was distilled to give a phenyltin trichloride product with a weight of 5423 g, a boiling point range of 84-91°C (0.5-0.7 mm Hg) and a refractive index of 1.5836-1.5868.
For utførelse av det første trinn, fremstillingen av tricykloheksylfenyltinn, ble Grignard-reagensen fremstilt ved tilsetning av 62,0 g (2,55 mol) magnesiumspon til et reaksjonskar som var renset med nitrogengass. 100 milliliter tetrahydrofuran ble tilsatt sammen med en startblanding som inneholdt 6,0 g (0,5 mol) cykloheksylklorid og 4,3 g (0,5 mol) cykloheksylbromid. Til reaksjonsblandingen ble der langsomt tilsatt en blanding som inneholdt 289,9 g (2,43 mol) cykloheksylklorid og 1350 milliliter tetrahydrofuran. Etterat tilsetningen var fullført, ble reaksjonen tillatt å- fortsette eksotermt i to timer, hvoretter den ble avkjølt til 40°C. En charge inneholdende 202,0 g (0,67. mol) fenyltinntriklorid fremstilt som angitt ovenfor oppløst i 600 milliliter benzen ble tilsatt reaksjonsblandingen i løpet av 30 minutter. Reaksjonsblandingen ble holdt under vanlig tilbakeløp i 150 minutter, hvoretter reaksjonsblandingen ble avkjølt til værelsetemperatur og hydrolysert med en vandig oppløsning med 120 g sitronsyre i 1200 milliliter vann. Reaksjonsblandingen ble deretter fraskilt i et tofasesystem som ble filtrert for å fjerne uoppløst magnesiummetall. Filtratet ble overført til en separeringstrakt, og det vandige skikt ble fraskilt og ekstrahert med 1350 milliliter benzen. Oppløsningsmiddelet ble fjernet ved destillering, og 195 g tricykloheksylfenyltinn - et utbytte på 66% - met et smeltepunktområde på 188,5-192°C ble oppnådd. To carry out the first step, the preparation of tricyclohexylphenyltin, the Grignard reagent was prepared by adding 62.0 g (2.55 mol) of magnesium shavings to a reaction vessel purged with nitrogen gas. 100 milliliters of tetrahydrofuran was added along with a starting mixture containing 6.0 g (0.5 mol) of cyclohexyl chloride and 4.3 g (0.5 mol) of cyclohexyl bromide. A mixture containing 289.9 g (2.43 mol) of cyclohexyl chloride and 1350 milliliters of tetrahydrofuran was slowly added to the reaction mixture. After the addition was complete, the reaction was allowed to proceed exothermically for two hours, after which it was cooled to 40°C. A charge containing 202.0 g (0.67 mol) of phenyltin trichloride prepared as indicated above dissolved in 600 milliliters of benzene was added to the reaction mixture over 30 minutes. The reaction mixture was kept under normal reflux for 150 minutes, after which the reaction mixture was cooled to room temperature and hydrolyzed with an aqueous solution of 120 g of citric acid in 1200 milliliters of water. The reaction mixture was then separated in a two-phase system which was filtered to remove undissolved magnesium metal. The filtrate was transferred to a separatory funnel, and the aqueous layer was separated and extracted with 1350 milliliters of benzene. The solvent was removed by distillation, and 195 g of tricyclohexylphenyltin - a yield of 66% - with a melting point range of 188.5-192°C was obtained.
Ved det annet trinn, som var fremstillingen av tricykloheksyltinnklorid, ble 26,8 g (0,06 mol) tricykloheksylfenyltinn, fremstilt som angitt ovenfor, oppløst i 40 milliliter xylen og ført inn i et reaksjonskar. Oppløsningen ble avkjølt til -20°C ved at reaksjonskaret ble anbragt i et ismetanolbad. En oppløsning av 15,7 g (0,06 mol) tinntetraklorid i 10 milliliter xylen ble raskt tilsatt. Reaksjonsblandingen ble holdt under tilbakeløpskjøling i 30 minutter og deretter avkjølt til værelsetemperatur. Reaksjonsblandingen besto da av to faser, en halvfast.lavere fase og en øvre væskefase. Fasene ble separert og oppløsningsmiddelet fjernet fra den øvre fase ved destillering, hvorved der ble oppnådd hvite krystaller og en ravgul væske. De hvite krystaller ble separert fra væsken ved filtrering. De hvite krystaller, som var tricykloheksyltinnklorid, oppviste etter vasking med metanol en vekt på 20,0 g og et smeltepunkt på 124-125°C Damp-fasekromatografisk analyse viste at tricykloheksyltinnkloridet var 98% rent. In the second step, which was the preparation of tricyclohexyltin chloride, 26.8 g (0.06 mol) of tricyclohexylphenyltin, prepared as indicated above, was dissolved in 40 milliliters of xylene and introduced into a reaction vessel. The solution was cooled to -20°C by placing the reaction vessel in an ice methanol bath. A solution of 15.7 g (0.06 mol) stannous tetrachloride in 10 milliliters of xylene was quickly added. The reaction mixture was kept under reflux for 30 minutes and then cooled to room temperature. The reaction mixture then consisted of two phases, a semi-solid lower phase and an upper liquid phase. The phases were separated and the solvent removed from the upper phase by distillation, whereby white crystals and an amber liquid were obtained. The white crystals were separated from the liquid by filtration. The white crystals, which were tricyclohexyltin chloride, showed after washing with methanol a weight of 20.0 g and a melting point of 124-125°C Vapor phase chromatographic analysis showed that the tricyclohexyltin chloride was 98% pure.
Eksempel 2 Example 2
Fremgangsmåten ifølge eksempel 1 ble fulgt ved fremstilling av 1,93 mol (1330 milliliter) tricykloheksylmagnesiumklorid-Grignard-reagens. 200,4 g (0,71 mol) butyltinntriklorid ble tilsatt Grignard-reagensen i 250 milliliter pentan. Etter avslutning av tilsetningen ble reaksjonen tillatt å fortsette eksotermt i ytterligere to timer. The procedure of Example 1 was followed in the preparation of 1.93 moles (1330 milliliters) of tricyclohexylmagnesium chloride Grignard reagent. 200.4 g (0.71 mol) of butyltin trichloride was added to the Grignard reagent in 250 milliliters of pentane. After completion of the addition, the reaction was allowed to proceed exothermically for a further two hours.
Det resulterende rå tricykloheksylbutyltinn-mellomprodukt ble vasket med 25 milliliter av en 5 vektprosents oppløsning av saltsyre i vann og separert. Tricykloheksylbutyltinnet hadde etter vasking med etanol en vekt på 199,6 g. The resulting crude tricyclohexylbutyltin intermediate was washed with 25 milliliters of a 5% by weight solution of hydrochloric acid in water and separated. After washing with ethanol, the tricyclohexylbutyl tin had a weight of 199.6 g.
Fremstillingen av tricykloheksyltinnkloridet ble utført ved dannelse av en oppløsning av 42,4 g (0,1 mol) tricykloheksylbutyltinn i 50 milliliter benzen. En oppløsning av 26,0 g (0,1 mol) tinntetraklorid (SnCl^) i 50 milliliter benzen ble deretter tilsatt dråpevis i løpet av et tidsrom på 45 minutter. Reaksjonsblandingen ble deretter separert i to faser. Fasene ble separert og butyltinntrikloridet ekstrahert med en oppløsning av 1052 saltsyre i vann. Tricykloheksyl-tinnkloridproduktet hadde etter vasking og filtrering en vekt på 39,1 g og et smeltepunkt på 124,5-126°C. The preparation of the tricyclohexyltin chloride was carried out by forming a solution of 42.4 g (0.1 mol) of tricyclohexylbutyltin in 50 milliliters of benzene. A solution of 26.0 g (0.1 mole) stannous tetrachloride (SnCl₂) in 50 milliliters of benzene was then added dropwise over a period of 45 minutes. The reaction mixture was then separated into two phases. The phases were separated and the butyltin trichloride extracted with a solution of 1052 hydrochloric acid in water. After washing and filtering, the tricyclohexyl tin chloride product had a weight of 39.1 g and a melting point of 124.5-126°C.
Claims (3)
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US77333168A | 1968-11-04 | 1968-11-04 | |
US81678369A | 1969-04-16 | 1969-04-16 |
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BE (1) | BE741260A (en) |
BR (1) | BR6913863D0 (en) |
CH (1) | CH539655A (en) |
DE (1) | DE1955463C3 (en) |
DK (1) | DK130300B (en) |
ES (1) | ES373121A1 (en) |
FR (1) | FR2022521A1 (en) |
GB (1) | GB1262986A (en) |
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NL (1) | NL166946C (en) |
NO (1) | NO131934C (en) |
SE (2) | SE361481B (en) |
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1969
- 1969-11-03 NO NO4341/69A patent/NO131934C/no unknown
- 1969-11-03 ES ES373121A patent/ES373121A1/en not_active Expired
- 1969-11-03 FR FR6937720A patent/FR2022521A1/fr active Pending
- 1969-11-03 SE SE15018/69A patent/SE361481B/xx unknown
- 1969-11-03 IL IL33291A patent/IL33291A/en unknown
- 1969-11-03 SE SE7216419A patent/SE393382B/en unknown
- 1969-11-03 DK DK579769AA patent/DK130300B/en not_active IP Right Cessation
- 1969-11-03 BR BR213863/69A patent/BR6913863D0/en unknown
- 1969-11-04 AT AT1036469A patent/AT293437B/en not_active IP Right Cessation
- 1969-11-04 DE DE1955463A patent/DE1955463C3/en not_active Expired
- 1969-11-04 CH CH1644669A patent/CH539655A/en not_active IP Right Cessation
- 1969-11-04 GB GB54060/69A patent/GB1262986A/en not_active Expired
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FR2022521A1 (en) | 1970-07-31 |
NL6916581A (en) | 1970-05-08 |
CH539655A (en) | 1973-07-31 |
IL33291A0 (en) | 1970-01-29 |
BE741260A (en) | 1970-04-16 |
NL166946C (en) | 1981-10-15 |
BR6913863D0 (en) | 1973-04-05 |
SE393382B (en) | 1977-05-09 |
GB1262986A (en) | 1972-02-09 |
AT293437B (en) | 1971-10-11 |
DE1955463A1 (en) | 1970-05-06 |
DE1955463C3 (en) | 1979-07-12 |
DE1955463B2 (en) | 1978-11-16 |
DK130300B (en) | 1975-02-03 |
SE361481B (en) | 1973-11-05 |
NO131934C (en) | 1975-08-27 |
NL166946B (en) | 1981-05-15 |
DK130300C (en) | 1975-06-30 |
ES373121A1 (en) | 1971-12-16 |
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