DE2032426A1 - Trialkyl lead acetate - by oxidation of hexaalkyldiplumbane - Google Patents
Trialkyl lead acetate - by oxidation of hexaalkyldiplumbaneInfo
- Publication number
- DE2032426A1 DE2032426A1 DE19702032426 DE2032426A DE2032426A1 DE 2032426 A1 DE2032426 A1 DE 2032426A1 DE 19702032426 DE19702032426 DE 19702032426 DE 2032426 A DE2032426 A DE 2032426A DE 2032426 A1 DE2032426 A1 DE 2032426A1
- Authority
- DE
- Germany
- Prior art keywords
- lead
- acetate
- trialkyl
- oxidation
- hexaalkyldiplumbane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229940046892 lead acetate Drugs 0.000 title abstract description 5
- 230000003647 oxidation Effects 0.000 title abstract description 5
- 238000007254 oxidation reaction Methods 0.000 title abstract description 5
- 239000011133 lead Substances 0.000 claims abstract description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 150000001242 acetic acid derivatives Chemical class 0.000 claims abstract description 4
- ACKFDYCQCBEDNU-UHFFFAOYSA-J lead(2+);tetraacetate Chemical compound [Pb+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ACKFDYCQCBEDNU-UHFFFAOYSA-J 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000003139 biocide Substances 0.000 abstract 1
- 239000002966 varnish Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl radical Chemical class 0.000 description 3
- RLMYUACRBQPRSH-UHFFFAOYSA-N tributyllead Chemical compound CCCC[Pb](CCCC)CCCC.CCCC[Pb](CCCC)CCCC RLMYUACRBQPRSH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007248 oxidative elimination reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KTOQRRDVVIDEAA-UHFFFAOYSA-N 2-methylpropane Chemical compound [CH2]C(C)C KTOQRRDVVIDEAA-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- LMDKALUFKHCRFQ-UHFFFAOYSA-M tributylplumbyl acetate Chemical compound CCCC[Pb](CCCC)(CCCC)OC(C)=O LMDKALUFKHCRFQ-UHFFFAOYSA-M 0.000 description 1
- DTTVFKVGEOETRX-UHFFFAOYSA-N triethyllead Chemical compound CC[Pb](CC)CC.CC[Pb](CC)CC DTTVFKVGEOETRX-UHFFFAOYSA-N 0.000 description 1
- ZFNWDVUSZNZYLD-UHFFFAOYSA-M triethylplumbyl acetate Chemical compound CC[Pb](CC)(CC)OC(C)=O ZFNWDVUSZNZYLD-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C07F7/24—Lead compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verfahren zur Herstellung von Trialkylbleiacetaten Die Trialkylbleiacylate besitzen wertvolle biocide Eigenschaften und finden als Zusatz in Antifoulinglacken Verwendung (vergl. H. Shapiro; F. W. Frey: "The Organic Compounds of Leadil, John Wiley s Sons, Inc., 1968).Process for the Preparation of Trialkyl Lead Acetates The trialkyl lead acylates have valuable biocidal properties and are used as an additive in antifouling paints Use (see H. Shapiro; F. W. Frey: "The Organic Compounds of Leadil, John Wiley s Sons, Inc., 1968).
Zur Herstellung der Trialkylbleiacylate sind verschiedene Methoden bekannt. Als Ausgangsmaterial können sowohl die Tetraalkylplumbane als auch die Hexaalkyldiplumbane dienen. Die Umwandlung der Tetraalkylplumbane in die Trialkylbleiacylate erscheint als ein wenig sinnvoller Weg. Die Abspaltung eines Alkylrestes, der in Form eines Kohlenwasserstoffes verloren geht, stellt einmal den wirtschaftlichen Nut- -zen dieser Methode in Zweifel, zum anderen verlaufen solche Reaktionen nicht einheitlich, so daß die nicht gewünschten Dialkyldicylate als Nebenprodukte entstehen, deren Abtrennung vom gewünschten Produkt schwer möglich isti Als besser geeignet zur Herstellung der Trialkylbleiacylate erweisen sich die Hexaalkyidiplumbane. Durch oxydative Spaltung der Pb-Pb-Bindung entstehen hieraus die gewünschten Produkte in reiner Form.Various methods are used to prepare the trialkyl lead acylates known. Both the tetraalkylplumbane and the Hexaalkyldiplumbanes are used. The conversion of the tetraalkylplumbanes into the trialkyl lead acylates seems like a little sensible way to go. The elimination of an alkyl radical, which is in The form of a hydrocarbon is lost, once the economic one Use this method in case of doubt, on the other hand such reactions do not take place uniform, so that the undesired dialkyl dicylates arise as by-products, which are difficult to separate from the desired product. As better suited the hexaalkyidiplumbanes prove to be used for the preparation of the trialkyl lead acylates. By oxidative cleavage of the Pb-Pb bond results in the desired products in pure form.
Hexaalkyidiplumbane entstehen bei geeigneter Reaktionsführung durch Alkylierung von Bleichlorid mittels Grignard-Verbindungen. jCndere anorganische Bleiverbindungen reagieren kaum oder gar nicht. Ebenso verläuft die Alkylierung der Blei-(ll)-acylate mittels Grignard-Verbindungen aus bekannten Gründen in unerwünschter Weise. Doch so gut dieses Grignard-Verfahren zur Herstellung der Hexaalkyldiplumbane für das Labor geeignet ist, umso schwieriger gestaltet sich seine Verwendung im technischen Maßstab.Hexaalkyidiplumbane are formed when the reaction is carried out appropriately Alkylation of lead chloride using Grignard compounds. jOther inorganic Lead compounds hardly react or not at all. The alkylation proceeds in the same way the lead (II) acylates by means of Grignard compounds are undesirable for known reasons Way. But so good is this Grignard process for the production of hexaalkyldiplumbanes is suitable for the laboratory, the more difficult it is to use it in the technical scale.
Hier sollten sich die leicht zugänglichen und für den Fachmann einfach zu handhabenden Alkylverbindungen von Metallen der III. Gruppe des Periodensystems, insbesondere die Aluminiumalkyle, als besonders vorteilhaft erweisen. Durch Alkylierung von Bleichlorid mittels Aluminiumalkylen werden jedoch stets Tetraalkylbleiverbindungen erhalten (L. C. Willemsens, 1. c., deutsche Patentschrift 1.216.301). Allenfalls entsteht wenig Hexaalkyldiplumban als unerwünschtes Nebenprodukt.These should be easily accessible and simple for the professional to be handled alkyl compounds of metals of III. Group of the periodic table, especially the aluminum alkyls, prove to be particularly advantageous. By alkylation lead chloride by means of aluminum alkyls, however, always becomes tetraalkyl lead compounds obtained (L. C. Willemsens, 1. c., German patent specification 1.216.301). At most Little hexaalkyldiplumbane is produced as an undesirable by-product.
Blei-(ll)-acylate als Ausgangsvarbindung für die Alkylierung mittels der Aluminiumalkyle zu verwenden, erschien eingedenk der Grignard-Reaktion als wenig aussichtsreich. Umso überraschender war das Ergebnis, daß sich nämlich die Blei-(ll)-acylate vom Typ Pb(OCORt)2, worin RI einen Arylrest oder einen gesättigten oder ungesättigten aliphatischen oder cycloaliphatischen Rest darstellt, insbesondere jedoch das Blei-(II)-acetat, in einfacher Weise mit den Aluminiumalkylen derÄllgemei nen Formel AlR3, worin R einen Alkylrest mit 1 bis 20 C-Atomen darstellt, zu den 'Hexaalkyldiplumbanen umsetzen. Die Reaktion dürfte nach folgendem Schema verlaufen Die oxydative Spaltung der Pb-Pb-Bindung in den Hexaalkyldiplumbanen zu den T&ialkylbleiacylaten gelingt, z. B. mittels Wasserstoffperoxid in Gegenwart einer Carbonsäure (siehe L. C. Willemsens; G. J. M. van der Kerk: 1lnvestigations in the Field of Organolead Chemistry"' Seite 67; Schotanus # Jens Utrecht N. V. - Utrecht 1965) oder direkt mittels organischer Persäuren (siehe H. O. Wirth, R, Maul, H. H. Friedrich: Tetrahedron Letters 1969, 2959 - 2962). In beiden Fällen kann es je doch leicht zur Bildung von Dialkylbleidiacylaten kommen" die sich schwer von dem gewünschten Produkt abtrennen lassen.Using lead (II) acylates as the starting compound for the alkylation by means of the aluminum alkyls, in view of the Grignard reaction, did not appear to be very promising. All the more surprising was the result that namely the lead (II) acylates of the Pb (OCORt) 2 type, in which RI is an aryl radical or a saturated or unsaturated aliphatic or cycloaliphatic radical, but in particular lead (II) acetate , in a simple manner with the aluminum alkyls of the general formula AlR3, in which R is an alkyl radical having 1 to 20 carbon atoms, to form the 'hexaalkyldiplumbanes. The reaction should proceed according to the following scheme The oxidative cleavage of the Pb-Pb bond in the Hexaalkyldiplumbanen to the T & ialkylbleiacylaten succeeds, z. B. by means of hydrogen peroxide in the presence of a carboxylic acid (see LC Willemsens; GJM van der Kerk: Investigations in the Field of Organolead Chemistry "'page 67; Schotanus # Jens Utrecht NV - Utrecht 1965) or directly by means of organic peracids (see HO Wirth, R , Maul, HH Friedrich: Tetrahedron Letters 1969, 2959-2962). In both cases, however, dialkyl lead diacylates can easily be formed, which are difficult to separate from the desired product.
Auch der Umweg über die Trialkylbleihalogenide, die aus den Hexaalkyldiplumbanen durch Oxydation mittels Halogenen erhältlich sind und aus denen zunächst die Trialkylbleihydroxide hergestellt werden müssen, bevor deren Neutralisierung mit einer beliebigen Carbonsäure das gewünschte Produkt liefert, stellt eine für den technischen Maßstab ungeeignete Methode dar.Also the detour via the trialkyl lead halides from the hexaalkyldiplumbanes are obtainable by oxidation by means of halogens and from which first the trialkyl lead hydroxides must be prepared before neutralizing them with any carboxylic acid delivers the desired product, is unsuitable for the industrial scale Method.
Die Oxydation der Hexaalkyldiplumbane mittels Blei-(lV)-acylaten ist bisher lediglich an einem Beispiel gezeigt worden: Aus Hexaäthyldiplumban und Blei-(lV)-acetat entsteht in mäßiger Ausbeute (49 §o) Triäthylbleiacetat (siehe G. A. Razuvaev et al.: Zhur. Obshchei Khim. 30 (1960) 2498; C. A. 55 (1961)14290). Wenn aber schon die Anfangsglieder einer homologen Reihe relativ schlecht reagieren, so sollte dies bei den höheren Homologen um so eher zutreffen. Es war daher nicht zu erwa rten, daß sich die Hexaalkyldiplumbane (CnH2n + 1>6 Pb2 (für n > 2) mit Blei-(lV)-acetat in glatt verlaufender Reaktion mit sehr guten Ausbeuten zu den Trialkylbleiacetaten (CnH2n + 1)3 PbOCOCH3 (für n > 2) umsetzen lassen.The oxidation of hexaalkyldiplumbanes by means of lead (IV) acylates is so far only one example has been shown: From hexaethyldiplumbane and lead (IV) acetate formed in moderate yield (49 §o) triethyl lead acetate (see G. A. Razuvaev et al .: Zhur. Obshchei Khim. 30 (1960) 2498; C.A. 55 (1961) 14290). But if it does the initial members of a homologous series react relatively poorly, so it should apply all the more to the higher homologues. It was therefore not to be expected that the hexaalkyldiplumbanes (CnH2n + 1> 6 Pb2 (for n> 2) with lead (IV) acetate in a smooth reaction with very good yields to the trialkyl lead acetate Let (CnH2n + 1) 3 PbOCOCH3 (for n> 2) convert.
Die Reaktion dürfte nach folgendem Schema verlaufen: Die Herstellung des Oxydationmittels Blei-(lV)-acetat geschieht in an sich bekannter Weise, indem man Mennige mit Essigsäure in Gegenwart von Essigsäurehydrid umsetzt: Bei dieser Reaktion entsteht nicht nur das zur Herstellung der Trialkyl bleiacetate aus den Hexaalkyldiplumbanen notwendige Oxydationsmittel, nämlich Blei-(lV)-acetat, sondern auch das zur Herstellung der Hexaalkyldiplumbane mittels der Aluminiumalkyle nötige Ausgangsmaterial, nämlich Blei-(ll)-acetat.The reaction should proceed according to the following scheme: The oxidizing agent lead (IV) acetate is produced in a manner known per se by reacting red lead with acetic acid in the presence of acetic acid hydride: This reaction not only produces the oxidizing agent necessary to produce the trialkyl lead acetate from the hexaalkyldiplumbanes, namely lead (IV) acetate, but also the starting material necessary to produce the hexaalkyldiplumbanes using the aluminum alkyls, namely lead (II) acetate.
Gegenstand der Erfindung ist demnach ein Verfahren zur Herstellung der Trialkylbleiacetate, daß dadurch gekennzeichnet ist, daß man 1. zunächst in an sich bekannter Weise aus Mennige, Essigsäure und Essigsäureanhydrid Blei-(lV)- und Blei-(l 1)-acetat herstellt, 2. das Blei-(ll)-acetat mit Aluminiumalkylen zu. .. Hexaalkyldiplumbanen umsetzt und 3. die Hexaalkyldiplumbane mit dem zuvor hergestellten Blei-(lV)-acetat zu Tria lkylbleiaceta ten oxydiert. The invention accordingly relates to a method of production the trialkyl lead acetate, characterized in that 1. first in known manner from red lead, acetic acid and acetic anhydride lead (IV) - and lead (l 1) acetate produces, 2. the lead (II) acetate with aluminum alkyls. .. Reacts hexaalkyldiplumbanes and 3. the hexaalkyldiplumbanes with the previously prepared Lead (IV) acetate oxidized to Tria lkylbleiaceta th.
Das erfindungsgemäße Verfahren läßt sich durch folgendes Reaktionsschema veranschaulichen: Beispiel 1 a) Ivlerstellung von Pb-(lV)-acetat Zu einer auf 400 C erwärmten Mischung aus 1, 5 1 Essigsäure und 378 ml t4 Mol) Acetanhydrid gibt man portionsweise insgesamt 686 g (1 Mol) Mennige. Die Temperatur soll 60°C nicht überschreiten. Nach beendeter Zugabe läßt man noch so lange bei erhöhter Temperatur rühren, bis sich alle Mennige gelöst hat. Nach Abkühlen auf Raumtemperatur wird das ausgefallene, leicht bräunlich gefärbte Blei-0 (lV)-acetat abgesaugt und das Filtrat bei 40 C mit Äthylenglykol versetzt, um in Lösung befindliches Blei-(lV)-acetat zu zerstören. Danach wird die Essigsäure unter vermindertem Druck abdestllliert und der ölige Rückstand in Toluol aufgenommen. Das ausgeschiedene Blei-(Il)-acetat wird abgesaugt, mit Toluol gewaschen und bei 500 C im Vakuumtrockenschrank getrocknet.The process according to the invention can be illustrated by the following reaction scheme: EXAMPLE 1 a) Preparation of Pb (IV) acetate A total of 686 g (1 mol) of red lead is added in portions to a mixture of 1.5 l of acetic acid and 378 ml (4 mol) of acetic anhydride, heated to 400.degree. The temperature should not exceed 60 ° C. When the addition is complete, the mixture is left to stir at elevated temperature until all of the red lead has dissolved. After cooling to room temperature, the precipitated, slightly brownish colored lead-0 (IV) acetate is suctioned off and the filtrate is treated with ethylene glycol at 40 ° C. in order to destroy lead (IV) acetate in solution. The acetic acid is then distilled off under reduced pressure and the oily residue is taken up in toluene. The precipitated lead (II) acetate is filtered off with suction, washed with toluene and dried at 500 ° C. in a vacuum drying cabinet.
Ausbeute: Pb(OCOCH3)4 423 g = 95 ß Pb(OCOCH3)2 571 g = 88 % b) Alkyl ierung des Blei-(ll)-acetats Zu einer Lösung von 198 g (1 Mol) Aiuminiumtributyl in 500 ml Toluol gibt man unter Rühren bei -5°C 163 g (0,'5 Mol) wasserfreies und fein gepulvertes Blei-(ll)-acetat. Nach beendeter Zugabe erhitzt man eine 0 Stunde lang auf 40 C und zersetzt dann das Reaktionsgemisch mit Eiswasser. Gegebenenfalls verwendet man Säure, Alkali oder komplexbil dende Reagentien, um das ausgefallene Aluminiumhydroxid zu lösen. Yield: Pb (OCOCH3) 4,423 g = 95 β Pb (OCOCH3) 2,571 g = 88% b) alkyl ation of the lead (II) acetate To a solution of 198 g (1 mol) of aluminum tributyl 163 g (0.5 mol) of anhydrous and are added to 500 ml of toluene with stirring at -5 ° C finely powdered lead (II) acetate. After the addition has ended, the mixture is heated for 0 hour long at 40 C and then decomposed the reaction mixture with ice water. Possibly acid, alkali or complexing reagents are used to dissolve the precipitated To dissolve aluminum hydroxide.
Man trennt die gelbe Toluolphase ab und bestimmt den Gehalt an Hexabutyldiplumban jodometrisch. Die Ausbeute, bezogen auf eingesetztes Blei-(ll)-acetat, beträgt 80 - 85 5to. The yellow toluene phase is separated off and the hexabutyldiplumbane content is determined iodometric. The yield, based on the lead (II) acetate used, is 80 - 85 5to.
c) Oxydation des Hexaalkyldiplumbans mit Blei-(lV)-acetat Zu der unter b) hergestellten Lösung von Hexabutyldiplumban in Toluol gibt man unter Rühren pro Mol dieser Verbindung ein Mol Blei-(lV)-acetat portionsweise hinzu, woraufhin die Temperatur 0 allmählich auf 40 - 50 C ansteigt. Nach beendeter Zugabe läßt man noch 30 Min. bei einer Temperatur von 40° C rühren, kühlt danach auf 20° C, filtriert vom abgeschiedenen Blei-(ll)-acetat ab und engt das Filtrat im Vakuum ein. Zum Rückstand gibt man 100 - 200 ml Aceton und läßt in der Kälte auskristallisieren. Die Ausbeute an Tributylbleiacetat (Fp 860 C) beträgt 85 - 90 o, bezogen auf das eingesetzte Hexabutyldiplumban.c) Oxidation of the hexaalkyldiplumbane with lead (IV) acetate To the below b) prepared solution of hexabutyldiplumban in toluene is added with stirring pro Mol of this compound one mole of lead (IV) acetate added in portions, whereupon the Temperature 0 gradually rises to 40 - 50 C. After the addition has ended, the mixture is left Stir for 30 minutes at a temperature of 40 ° C, then cool to 20 ° C, filtered from the separated lead (II) acetate and the filtrate is concentrated in vacuo. To the arrears 100-200 ml of acetone are added and allowed to crystallize in the cold. The yield of tributyl lead acetate (melting point 860 ° C.) is 85-90 °, based on the amount used Hexabutyldiplumbane.
Wie in Beispiel 1b) und 1c) beschrieben, wird jeweils 1 Mol Aluminlumalkyl mit 163 g (0,5 Mol) wasserfreiem Blei-(ll)-acetat in 500 ml Toluol umgesetzt und anschließend mit der äquivalenten Menge an Blei-(lV)-acetat oxydiert.As described in Example 1b) and 1c), 1 mole of each aluminum alkyl is used reacted with 163 g (0.5 mol) of anhydrous lead (II) acetate in 500 ml of toluene and then oxidized with the equivalent amount of lead (IV) acetate.
Beispiel Nr. R in AlR3 No Ausbeute % Ausbeute R6Pb2 R3PbOCOCH3 2 C3H7 80 65 3 iso-C4H9 70 75 4 C6H13 80 90 5 C8H17 cr 80 80 6 C8H9 80 50 (ß-Phenyl-äthyl) 7 C10H19 50 84 (3,7-Dimethyl-octen-6-yl-1)Example No. R in AlR3 No Yield% Yield R6Pb2 R3PbOCOCH3 2 C3H7 80 65 3 iso-C4H9 70 75 4 C6H13 80 90 5 C8H17 cr 80 80 6 C8H9 80 50 (ß-phenyl-ethyl) 7 C10H19 50 84 (3,7-dimethyl-octen-6-yl-1)
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702032426 DE2032426A1 (en) | 1970-06-22 | 1970-06-22 | Trialkyl lead acetate - by oxidation of hexaalkyldiplumbane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702032426 DE2032426A1 (en) | 1970-06-22 | 1970-06-22 | Trialkyl lead acetate - by oxidation of hexaalkyldiplumbane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2032426A1 true DE2032426A1 (en) | 1971-12-30 |
Family
ID=5775413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19702032426 Pending DE2032426A1 (en) | 1970-06-22 | 1970-06-22 | Trialkyl lead acetate - by oxidation of hexaalkyldiplumbane |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2032426A1 (en) |
-
1970
- 1970-06-22 DE DE19702032426 patent/DE2032426A1/en active Pending
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