DE954878C - Process for the production of alkyl mercury chlorides, bromides or iodides - Google Patents
Process for the production of alkyl mercury chlorides, bromides or iodidesInfo
- Publication number
- DE954878C DE954878C DEF17351A DEF0017351A DE954878C DE 954878 C DE954878 C DE 954878C DE F17351 A DEF17351 A DE F17351A DE F0017351 A DEF0017351 A DE F0017351A DE 954878 C DE954878 C DE 954878C
- Authority
- DE
- Germany
- Prior art keywords
- methylene chloride
- iodides
- bromides
- production
- mercury
- 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.)
- Expired
Links
- -1 alkyl mercury chlorides Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000004694 iodide salts Chemical class 0.000 title claims 2
- 150000003842 bromide salts Chemical class 0.000 title 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000001649 bromium compounds Chemical class 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UMOVEROQRKQOQB-UHFFFAOYSA-N chloroethane;mercury Chemical compound [Hg].CCCl UMOVEROQRKQOQB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/10—Mercury compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Alkylquecksilberchloriden, -bromiden bzw. -jodiden Es. ist bekannt, daß man Alkylquecksilberhalogenide aus Quecksilberhalogeniden Hg X2 durch Umsetzung mit aluminiumorganischen Verbindungen., wie Alkyl-aluminium-sesquihalogeniden, A1 R2 Cl, AIR C12 oder Aluminiumtrialkylen, in einem in.erten Lösungsmittel, z. B. in gesättigten, alicyclischen oder aromatischen Kohlenwasserstoffen oder Äthern bei Temperaturen, bis i5o" erhalten. kann. Im allgemeinen wird die Reaktion in Cyclohexan ausgeführt, zunächst bei tiefen Temperaturen eingeleitet und dann bei hohen Temperaturen, gewöhnlich bei 8o bis 85°', zu Ende geführt. Hierbei werden Ausbeuten zwischen 45 und 70 % der Theorie erhalten. Es wurde nun gefunden, daß man praktisch quantitative Ausbeuten erhält, wenn man Methylenchlorid (Kp. q2'°) als Lösungsmittel verwendet. Methylenchlorid ist auch deshalb besonders günstig, weil infolge seines hohen Dampfdruckes bei Zimmertemperatur die sonst beim Arbeiten mit aluminiumorganischen Verbindungen erforderlichen Vorsichtsmaßnahmen, z. B. eine Überlagerung mit Stickstoff, unnötig sind.Process for the production of alkyl mercury chlorides, bromides or -iodides Es. it is known that alkyl mercury halides can be obtained from mercury halides Hg X2 by reaction with organoaluminum compounds, such as alkyl aluminum sesquihalides, A1 R2 Cl, AIR C12 or aluminum trialkylene, in an inert solvent, e.g. B. in saturated, alicyclic or aromatic hydrocarbons or ethers at temperatures up to 150 ". In general, the reaction is carried out in cyclohexane executed, initiated first at low temperatures and then at high temperatures, usually at 80 to 85 degrees. Yields between 45 and received 70% of theory. It has now been found that practically quantitative Yields obtained when methylene chloride (boiling point q2 °) is used as the solvent. Methylene chloride is also particularly beneficial because of its high vapor pressure at room temperature that is usually the case when working with organoaluminum compounds necessary precautionary measures, e.g. B. an overlay with nitrogen, unnecessary are.
Es. ist ein weiterer Vorteil der Verwendung von Methylenchlorid -als Lösungsmittel, daß die Reaktionszeit, die bei dem bekannten Verfahren etwa i bis 5 Stunden, beträgt, wesentlich verkürzt wird und. nur einige Minuten .beträgt. Dieses ist um so überraschender, als die Reaktion nach dem vorliegenden Verfahren auch bei wesentlich niedrigeren. Temperaturen durchgeführt wird als bei dem bekannten,, längere Zeit erfordernden, Verfahren.It. is another benefit of using methylene chloride -as Solvent that the reaction time, which in the known process is about i to 5 hours, is significantly shortened and. just a few minutes .amounts to. This is all the more surprising as the reaction according to the present one Procedure even at much lower. Temperatures is carried out as at the well-known, long-term, process.
Ein weiterer Vorteil des vorliegenden, Verfahrens besteht darin, daß die beim Arbeiten, in anderen Lösungsmitteln vorübergehend auftretenden halb festen Substanzen, äie Quecksilberhalogenid einschließen und somit der Reaktion entziehen, nicht gebildet werden.Another advantage of the present method is that the semi-solid ones that appear temporarily when working in other solvents Substances that include mercury halide and thus withdraw from the reaction, not be formed.
Das Reaktionsprodukt fällt nach Zersetzen eines zweckmäßig verwendeten geringen Überschusses der aluminsumorganischen Verbindung mit verdünnter Sa,lzsäure und Abdestillieren des Methylenchlorids sofort schmelzpunkts- und analysenrein an-Die Wahl von Methylenchlorid als Lösungsmittel bedeutet daher für die Reaktionsführung, insbesondere beim Arbeiten in. größerem Maßstab, eine entscheidende Verbesserung.The reaction product falls after decomposition of an expediently used one small excess of the organoaluminum compound with dilute hydrochloric acid and distilling off the methylene chloride immediately melting point and analytically pure on-die The choice of methylene chloride as the solvent therefore means for the conduct of the reaction a decisive improvement especially when working on a larger scale.
Die erfindungsgemäße Reaktion kann vorteilhaft bei Atmosphärendruck, jedoch erforderlichenfalls bei Unter- oder Überdruck ausgeführt werden. Nach der vorliegenden, Reaktion können Alkylqueck silberhalogenide hergestellt werden, die ein Halogen mit einem Atomgewicht von. mindestens 35, das ist Chlor, Brom oder Jod, enthalten. Beispiel 1 Zu einer Suspension von 4o6,5 g Merkurichlorid (1,5 Mol) in iioog Methylenchlorid lä.Bt man innerhalb von, 15 Minuten unter Rühren eine Lösung von, 135 g Aluminiumäthylsesquichlorid (o,55 Mol) in zoo g Methylenehlorid einfließen. Dabei steigt die Temperatur bis zum Siedepunkt des Methylenchlorids (q2°) an. Anschließend hält man. den Ansatz io Minuten- auf 4o'°', wobei die letzten Reste des Merkurichlorids reagieren und eine klare Lösung entsteht. Nach Zugabe von 6oo ccm io/oiger Salzsäure scheidet sich eine weiße Substanz aus, die mit der Methylenchloridphase einen. Brei bildet, während die obere wässerige Phase das Aluminiumchlorid gelöst enthält und abgetrennt wird. Nach Abdampfen des Methylenchlorids bleiben 375 g (95o/oderTheorie) des kristallisierten. Quecksilberäthylchlorids (Schmelzpunkt igo bis ig2°) zurück. Beispiel -- Zu einer Suspension von 4o6,5_g Merkurichlorid (1,5M01) in iioo g Methylenchlorid läßt man. innerhalb von ao Minuten unter Rühren eine Lösung von 113 g Aluminiummethylsesquichlorid in 4oo g Methylenchlorid einfließen. Dabei steigt die Temperatur auf 429. Der Ansatz wird io Minuten bei dieser Temperatur unter Rückfluß gehalten. Man, zersetzt mit 6oo ccm io%iger Salzsäure, trennt die wässerige Phase ab und dampft von der Methylencbloridphase unter Rühren, das Methylenchlorid ab. Es bleiben 355 g (94% der Theorie) des kristallisiertenQuecksiibermethylchlorids (Schmelzpunkt 165 bis 167) zurück.The reaction according to the invention can advantageously be carried out at atmospheric pressure, but if necessary under reduced or elevated pressure. According to the present reaction, alkyl mercury silver halides can be prepared which are a halogen having an atomic weight of. Contains at least 35, that is chlorine, bromine or iodine. EXAMPLE 1 A solution of 135 g of aluminum ethyl sesquichloride (0.55 mol) in zoo g of methylene chloride is allowed to flow into a suspension of 406.5 g of mercury chloride (1.5 mol) in iioog methylene chloride over a period of 15 minutes with stirring. The temperature rises to the boiling point of methylene chloride (q2 °). Then one stops. the approach 10 minutes to 40 '°', whereby the last remnants of the mercury chloride react and a clear solution is formed. After the addition of 600 cc of 10% hydrochloric acid, a white substance separates out, which is one with the methylene chloride phase. Slurry forms while the upper aqueous phase contains the aluminum chloride in solution and is separated off. After evaporation of the methylene chloride, 375 g (95o / or theory) of the crystallized remain. Mercury ethyl chloride (melting point igo to ig2 °). Example - To a suspension of 406.5 g of mercury chloride (1.5M01) in 100 g of methylene chloride is added. A solution of 113 g of aluminum methyl sesquichloride in 4oo g of methylene chloride is poured in over a period of ao minutes with stirring. The temperature rises to 429. The batch is refluxed for 10 minutes at this temperature. It is decomposed with 600 cc of 10% strength hydrochloric acid, the aqueous phase is separated off and the methylene chloride is evaporated from the methylene chloride phase with stirring. 355 g (94% of theory) of the crystallized mercury overmethyl chloride (melting point 165 to 167) remain.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17351A DE954878C (en) | 1955-04-17 | 1955-04-17 | Process for the production of alkyl mercury chlorides, bromides or iodides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17351A DE954878C (en) | 1955-04-17 | 1955-04-17 | Process for the production of alkyl mercury chlorides, bromides or iodides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE954878C true DE954878C (en) | 1956-12-27 |
Family
ID=7088555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF17351A Expired DE954878C (en) | 1955-04-17 | 1955-04-17 | Process for the production of alkyl mercury chlorides, bromides or iodides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE954878C (en) |
-
1955
- 1955-04-17 DE DEF17351A patent/DE954878C/en not_active Expired
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