EP0288818A2 - Bor-tris-(dialkyl-dithiocarbamates) and process for their preparation - Google Patents

Bor-tris-(dialkyl-dithiocarbamates) and process for their preparation Download PDF

Info

Publication number
EP0288818A2
EP0288818A2 EP88105850A EP88105850A EP0288818A2 EP 0288818 A2 EP0288818 A2 EP 0288818A2 EP 88105850 A EP88105850 A EP 88105850A EP 88105850 A EP88105850 A EP 88105850A EP 0288818 A2 EP0288818 A2 EP 0288818A2
Authority
EP
European Patent Office
Prior art keywords
boron
dithiocarbamate
tris
dialkyl
general formula
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.)
Granted
Application number
EP88105850A
Other languages
German (de)
French (fr)
Other versions
EP0288818A3 (en
EP0288818B1 (en
Inventor
Wolfram Dr. Spiess
Rolf Himmelreich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dr Spiess Chemische Fabrik & Co GmbH
Original Assignee
Cf Spiess & Sohn & Co Chemische Fabrik GmbH
CF Spiess and Sohn GmbH and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cf Spiess & Sohn & Co Chemische Fabrik GmbH, CF Spiess and Sohn GmbH and Co filed Critical Cf Spiess & Sohn & Co Chemische Fabrik GmbH
Priority to AT88105850T priority Critical patent/ATE100080T1/en
Publication of EP0288818A2 publication Critical patent/EP0288818A2/en
Publication of EP0288818A3 publication Critical patent/EP0288818A3/en
Application granted granted Critical
Publication of EP0288818B1 publication Critical patent/EP0288818B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to boron tris (dialkyldithiocarbamates of the general formula in which R and R ⁇ represent the same or different, branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 12 carbon atoms.
  • alkyl radicals can also be cycloalkyl radicals such as cyclohexyl.
  • the invention further relates to processes for the preparation of the bordithiocarbamates of the general formula I.
  • the preparation of these compounds is carried out according to the following equations: In it R and R ⁇ have the above meaning, X stands for bromide, chloride or fluoride and Me is an alkali or ammonium ion, preferably the sodium ion.
  • the production of the alkalidialalkydithiocarbamates is known in principle.
  • the procedure for the preparation of the sodium dialkyldithiocarbamates is generally as follows:
  • a 50% sodium hydroxide solution is introduced into methanol.
  • the secondary amine is added and carbon disulfide is added dropwise. All reaction components are used in stoichiometric amounts, carbon disulfide can also be used in excess.
  • the mixture is stirred mechanically for 1 to 3 hours. Then the formation of sodium dithiocarbamate is complete.
  • This solution can be used directly as a starting product for the subsequent preparation of boron tris (dialkyl dithiocarbamates) and the reaction can be continued in the same vessel if 1 mol of a solution of the complex of boron trifluoride with diethyl ether or Methanol added dropwise in diethyl ether.
  • methanol instead of methanol, other water-miscible solvents such as ethylene glycol monoalkyl ether, tetrahydrofuran, dioxane, ethanol, propanol or isopropanol can also be used.
  • ethylene glycol monoalkyl ether tetrahydrofuran
  • dioxane ethanol
  • propanol propanol or isopropanol
  • the boron trifluoride complex compounds are not as sensitive to hydrolysis as the free boron halides so that it is possible to work in aqueous-alcoholic solution, but the water content in the reaction medium should not exceed 15 percent by weight.
  • the reaction is weakly exothermic in both stages. Additional heating or external cooling is therefore generally not necessary.
  • the reaction is therefore carried out at 0 to 90, preferably 20 to 70 ° C.
  • Suitable inert solvents for the reaction in the anhydrous medium are aliphatic or aromatic hydrocarbons or lower dialkyl ethers. The same applies to the temperature profile and the temperatures to be observed as when working in a water-containing environment.
  • the so-called “one-pot process” can be used, i.e. the preparation of the boron tris (dialkyl dithiocabamate) can take place in the same reaction vessel in which the alkali metal or ammonium dialkyldithiocarbamate is prepared in the first stage from a corresponding secondary amine, carbon disulfide and alkali metal hydroxide or by another known process has been.
  • the new bordithiocarbamates of the general formula I are suitable as additives for hydraulic oils or gear oils.
  • Example 1 Boron tris (di-2-ethylhexyl dithiocarbam).
  • Example 2 Boron tris (di-2-ethylhexyl dithiocarbamate).
  • Example 3 Boron tris (di-2-ethylhexyl dithiocarbamate).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Boron tris-(dialkyl-dithiocarbamate) of the general formula <IMAGE> (I) wherein R and R' represent the same or different branched- or straight-chain saturated or unsaturated alkyl radicals having from 1 to 16 carbon atoms and a process for preparing the same, comprising reacting 3 moles of an alkali dialkyl-dithiocarbamate of the general formula <IMAGE> wherein R and R' are as defined in claim 1 and Me+ represents Na+, K+ or NH4+ with one mole boron tribromide, boron trichloride or boron trifluoride in an inert medium, separating the so-formed alkali metal or ammonium halide and isolating the boron dithiocarbamates are suitable as additives for hydraulic oils or permanent gear lubricant oils.

Description

Dithiocarabamate von Metallen sind in großer Anzahl beschrieben, siehe Elsevier Monographs "The Dithio­carbamates and related Compounds" von Thorn and Ludwig (1962), Tabelle I, Seite 12 bis 34. Es sind aber keine Dithiocarbamate des Bors bekannt.Dithiocarabamates of metals are described in large numbers, see Elsevier Monographs "The Dithiocarbamates and related Compounds" by Thorn and Ludwig (1962), Table I, pages 12 to 34. However, no boron dithiocarbamates are known.

Gegenstand der Erfindung sind Bor-tris-(dialkyl­dithiocarbamate der allgemeinen Formel

Figure imgb0001
in der R und Rʹ gleiche oder verschiedene, ver­zweigte oder unverzweigte, gesättigte oder unge­sättigte Alkylreste mit 1 bis 12 Kohlenstoffatomen bedeuten. Diese Alkylreste können auch Cycloalkylreste wie z.B. Cyclohexyl sein.The invention relates to boron tris (dialkyldithiocarbamates of the general formula
Figure imgb0001
 in which R and Rʹ represent the same or different, branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 12 carbon atoms. These alkyl radicals can also be cycloalkyl radicals such as cyclohexyl.

Gegenstand der Erfindung sind ferner Verfahren zur Herstellung der Bordithiocarbamate der allgemeinen Formel I. Die Herstellung dieser Verbindungen er­folgt nach den folgenden Gleichungen:

Figure imgb0002
Darin haben R und Rʹ die obige Bedeutung, X steht für Bromid, Chlorid oder Fluorid und Me ist ein Alkali- oder Ammoniumion, vorzugsweise das Natriumion.The invention further relates to processes for the preparation of the bordithiocarbamates of the general formula I. The preparation of these compounds is carried out according to the following equations:
Figure imgb0002
 In it R and Rʹ have the above meaning, X stands for bromide, chloride or fluoride and Me is an alkali or ammonium ion, preferably the sodium ion.

Die Herstellung der Alkalidialalkydithiocarbamate ist im Prinzip bekannt. Zur Herstellung der Natrium­dialkyl-dithiocarbamate wird im allgemeinen folgender­maßen verfahren:The production of the alkalidialalkydithiocarbamates is known in principle. The procedure for the preparation of the sodium dialkyldithiocarbamates is generally as follows:

Eine 50%-ige Natronlauge wird in Methanol eingetragen. Dazu gibt man das sekundäre Amin und tropft Schwefel­kohlenstoff zu. Alle Reaktionskomponenten werden in stöchiometrischen Mengen eingesetzt, Schwefelkohlen­stoff kann auch mit einem Überschuss eingesetzt werden. Die Mischung wird 1 bis 3 Stunden mechanisch gerührt. Dann ist die Bildung des Natriumdithiocarbamats be­endet.
Diese Lösung kann direkt als Ausgangsprodukt für die nachfolgende Herstellung von Bor-tris-(dialkyl-dithio­carbamaten) eingesetzt und die Reaktion im gleichen Gefäß fortgesetzt werden, wenn man anschließend auf 3 Mol des Natriumdithiocarbamats 1 Mol einer Lösung des Komplexes von Bortrifluorid mit Diethylether- oder Methanol in Diethylether zutropft.A 50% sodium hydroxide solution is introduced into methanol. The secondary amine is added and carbon disulfide is added dropwise. All reaction components are used in stoichiometric amounts, carbon disulfide can also be used in excess. The mixture is stirred mechanically for 1 to 3 hours. Then the formation of sodium dithiocarbamate is complete.
This solution can be used directly as a starting product for the subsequent preparation of boron tris (dialkyl dithiocarbamates) and the reaction can be continued in the same vessel if 1 mol of a solution of the complex of boron trifluoride with diethyl ether or Methanol added dropwise in diethyl ether.

Anstelle des Methanols können auch andere mit Wasser mischbare Lösungsmittel wie Ethylenglykolmonoalkylether, Tetrahydrofuran, Dioxan, Ethanol, Propanol oder Isopropanol eingesetzt werden. Die Bortrifluorid-­Komplexverbindungen sind zwar nicht so hydrolyse­empfindlich wie die freien Borhalogenide, so daß in wässrig-alkoholischer Lösung gearbeitet werden kann, der Wassergehalt im Reaktionsmedium sollte aber 15 Ge­wichtsprozent nicht übersteigen.Instead of methanol, other water-miscible solvents such as ethylene glycol monoalkyl ether, tetrahydrofuran, dioxane, ethanol, propanol or isopropanol can also be used. The boron trifluoride complex compounds are not as sensitive to hydrolysis as the free boron halides so that it is possible to work in aqueous-alcoholic solution, but the water content in the reaction medium should not exceed 15 percent by weight.

Die Reaktion läuft in beiden Stufen schwach exotherm ab. Eine zusätzliche Erwärmung oder äußere Kühlung sind daher in der Regel nicht erforderlich. Die Umsetzung wird daher bei 0 bis 90, vorzugsweise 20 bis 70°C durchgeführt.The reaction is weakly exothermic in both stages. Additional heating or external cooling is therefore generally not necessary. The reaction is therefore carried out at 0 to 90, preferably 20 to 70 ° C.

Nach beendeter Umsetzung mit dem Bortrifluoridkomplex wird die Mischung noch einige Stunden nachgerührt. Dann wird vom auskristallisierten Alkalifluorid ab­gesaugt. Aus dem Filtrat wird das Gemisch von Wasser und Lösungsmittel abdestilliert. Auch hierbei sollte eine Temperatur von 70°C nicht überschritten werden. Restmengen an Lösungsmittel werden daher zweckmäßig im Vakuum abdestilliert. Man erhält schwach gelbliche bis bernsteinfarbene Öle, die vorzugsweise nochmals klar filtriert werden.After the reaction with the boron trifluoride complex has ended, the mixture is stirred for a few hours. The alkali metal fluoride which has crystallized out is then suctioned off. The mixture of water and solvent is distilled off from the filtrate. Here, too, a temperature of 70 ° C should not be exceeded. Residual amounts of solvent are therefore expediently distilled off in vacuo. Pale yellowish to amber-colored oils are obtained, which are preferably filtered again clearly.

Wenn man anstelle des Borfluorid-Diethylether- oder -Methanol-Komplexes Bortribromid, Bortrichlorid oder Bortrifluorid als Reaktionskomponente verwenden will, ist es erforderlich, das entsprechende Alkali-alkyl­dithiocarbamat in wasserfreier Form einzusetzen. Die zunächst erhaltene wässrige Lösung muß also zur Trockne eingeengt werden, ehe das Alkali-alkyl-dithio­carbamat in einem wasserfreien inerten Lösungsmittel mit dem Borhalogenid umgesetzt werden kann.If one wants to use boron tribromide, boron trichloride or boron trifluoride as the reaction component instead of the boron fluoride-diethyl ether or methanol complex, it is necessary to use the corresponding alkali alkyl dithiocarbamate in anhydrous form. The aqueous solution initially obtained must therefore be evaporated to dryness before the alkali alkyl dithiocarbamate can be reacted with the boron halide in an anhydrous inert solvent.

Geeignete inerte Lösungsmittel für die Umsetzung im wasserfreien Medium sind aliphatische oder aromatische Kohlenwasserstoffe oder niedere Dialkylether. Für den Temperaturverlauf und die einzuhaltenden Temperaturen gilt hier das gleiche wie beim Arbeiten in einem was­serhaltigen Milieu.Suitable inert solvents for the reaction in the anhydrous medium are aliphatic or aromatic hydrocarbons or lower dialkyl ethers. The same applies to the temperature profile and the temperatures to be observed as when working in a water-containing environment.

In beiden Fällen kann im sogenannten "Eintopfverfah­ren" gearbeitet werden, d.h. die Herstellung des Bor-tris-(dialkyl-dithiocabamats) kann in dem gleichen Reaktionsgefäß erfolgen, in dem auch schon in der ersten Stufe aus einem entsprechenden sekundären Amin, Schwefelkohlenstoff und Alkalihydroxid oder nach einem anderen bekannten Verfahren das Alkali- ­oder Ammonium-dialkyldithiocarbamat hergestellt wurde.In both cases, the so-called "one-pot process" can be used, i.e. the preparation of the boron tris (dialkyl dithiocabamate) can take place in the same reaction vessel in which the alkali metal or ammonium dialkyldithiocarbamate is prepared in the first stage from a corresponding secondary amine, carbon disulfide and alkali metal hydroxide or by another known process has been.

Die neuen Bordithiocarbamate der allgemeinen For­mel I eignen sich als Additive für Hydrauliköle oder Getriebedaueröle.The new bordithiocarbamates of the general formula I are suitable as additives for hydraulic oils or gear oils.

Die Herstellung von erfindungsgemäßen Verbindungen wird an einigen Beispielen erläutert:The preparation of compounds according to the invention is illustrated using a few examples:

Beispiel 1: Bor-tris-(di-2-ethylhexyl-dithiocarbamt). Example 1 : Boron tris (di-2-ethylhexyl dithiocarbam).

15 kg einer 50%-igen Natronlauge werden in einer 200 Liter Glasapparatur unter mechanischem Rühren zu 94 Liter Methanol gegeben. Dann gibt man 45 kg Di-2-ethylhexyl-amin zu. Im Verlauf von 30 Minuten werden 15 kg Schwefelkohlenstoff zugetropft. Die Mischung wird anschließend noch 2 Stunden lang weiter gerührt. Dann wird im Verlauf von 90 Minuten die Lö­sung von 7,5 kg Bortrifluorid-Diethylether-Komplex (50%-ig) in 19 Liter Ether zugetropft. Die Mischung wird noch 3 Stunden lang weiter gerührt und bleibt dann über Nacht verschlossen stehen. Am anderen Mor­gen wird vom ausgefallenen Natriumfluorid durch eine Steingutnutsche abgesaugt. Aus dem Filtrat wird das Gemisch aus Methanol, Wasser und Ether abdestilliert, zum Schluß im Vakuum, wobei nicht über 70°C erwärmt wird. Nach dem Abkühlen wird das Öl noch einmal abge­saugt. Es wurden 46,6 kg eines klaren, bernsteinfar­benen Öls erhalten, das einen Gehalt von 100,1 % hat, bezogen auf Gesamt-Stickstoff. Die Ausbeute betrug 77,62 % der Theorie, bezogen auf BF₃.15 kg of a 50% sodium hydroxide solution are added to 94 liters of methanol in a 200 liter glass apparatus with mechanical stirring. Then 45 kg of di-2-ethylhexylamine are added. 15 kg of carbon disulfide are added dropwise in the course of 30 minutes. The mixture is then stirred for a further 2 hours. The solution of 7.5 kg of boron trifluoride-diethyl ether complex (50% strength) in 19 liters of ether is then added dropwise over the course of 90 minutes. The mixture is stirred for a further 3 hours and then remains closed overnight. The next morning, the precipitated sodium fluoride is sucked off through an earthenware filter. The mixture of methanol, water and ether is distilled off from the filtrate, at the end in a vacuum, heating not above 70 ° C. After cooling, the oil is sucked off again. 46.6 kg of a clear, amber-colored oil were obtained, which has a content of 100.1%, based on total nitrogen. The yield was 77.62% of theory, based on BF₃.

Beispiel 2: Bor-tris-(di-2-ethylhexyl-dithiocarbamat). Example 2 : Boron tris (di-2-ethylhexyl dithiocarbamate).

24 g einer 50%-igen Natronlauge werden zu 250 ml Wasser gegeben. Dazu gibt man 72,3 g Di-2-ethylhexyl­amin. Unter mechanischem Rühren werden im Verlauf von 20 Minuten 20 ml Schwefelkohlenstoff zugetropft. Die Mischung wird noch 30 Minuten lang weiter gerührt. Dann wird im Vakuum im Rotationsverdampfer bei einer Badtemperatur von 50°C zur Trockne eingeengt. Das staubtrockene Pulver wird mit 200 ml über Molekular­sieb getrockneten Di-isopropylether versetzt. Unter mechanischem Rühren tropft man dazu im Verlauf von einer Stunde die Lösung von 25 g Bortribromid in 100 ml gleichfalls über Molekularsieb getrockneten Di-isopropylether. Die Mischung wird noch 3 Stunden lang weiter gerührt und bleibt dann über Nacht ste­hen. Vom Natriumbromid wird mit schwachem Unterdruck abgesaugt. Der Di-isopropylether wird abdestilliert. Der Rückstand wird im Vakuum bei 70°C getrocknet. Man erhält 44 g eines gelblichen Öles, das einen Gehalt von 96,9 %, bezogen auf Stickstoff, hat.24 g of a 50% sodium hydroxide solution are added to 250 ml of water. 72.3 g of di-2-ethylhexylamine are added. With mechanical stirring, 20 ml of carbon disulfide are added dropwise in the course of 20 minutes. The mixture is stirred for a further 30 minutes. The mixture is then evaporated to dryness in vacuo in a rotary evaporator at a bath temperature of 50 ° C. The dust-dry powder is mixed with 200 ml of di-isopropyl ether dried over molecular sieves. With mechanical stirring, the solution of 25 g of boron tribromide in 100 ml of di-isopropyl ether, which is also dried over a molecular sieve, is added dropwise over the course of one hour. The mixture is stirred for a further 3 hours and then remains overnight. The sodium bromide is suctioned off with a weak negative pressure. The di-isopropyl ether is distilled off. The residue is dried in vacuo at 70 ° C. 44 g of a yellowish oil are obtained, which has a content of 96.9%, based on nitrogen.

Beispiel 3: Bor-tris-(di-2-ethylhexyl-dithiocarbamat). Example 3 : Boron tris (di-2-ethylhexyl dithiocarbamate).

40 g Natriumhydroxid, granuliert, werden in 350 ml Methanol gelöst. Dazu gibt man 241 g Di-2-ethylhexyl­amin. Unter mechanischem Rühren werden dazu im Ver­ lauf von 20 Minuten 64 ml Schwefelkohlenstoff ge­tropft. Die Mischung wird noch 2 Stunden lang weiter gerührt. Dann tropft man im Verlauf von einer Stunde 171 g Bortrifluorid-Methanol-Komplex (14 % BF₃) zu. Die Mischung wird noch 2 bis 3 Stunden lang gerührt und bleibt über Nacht verschlossen stehen. Vom Na­triumfluorid wird abgesaugt. Das Lösungsmittel wird abdestilliert und der Rückstand im Vakuum getrocknet. Schließlich wird nochmals abgesaugt. Man erhält 223 g eines gelblichen Öls, das einen Gehalt von 97,3 %, be­zogen auf Stickstoff, hat. Die Ausbeute betrug 69,7 % der Theorie, bezogen auf BF₃.40 g of sodium hydroxide, granulated, are dissolved in 350 ml of methanol. 241 g of di-2-ethylhexylamine are added. With mechanical stirring, Ver 64 ml of carbon disulphide were dropped over a period of 20 minutes. The mixture is stirred for a further 2 hours. Then dropwise over a period of one hour 171 g of boron trifluoride-methanol complex (14% BF₃). The mixture is stirred for a further 2 to 3 hours and remains closed overnight. The sodium fluoride is suctioned off. The solvent is distilled off and the residue is dried in vacuo. Finally, it is suctioned off again. 223 g of a yellowish oil are obtained, which has a content of 97.3%, based on nitrogen. The yield was 69.7% of theory, based on BF₃.

Beispiel 4: Bor-tris-(diamyl-dithiocarbamat). Example 4 : Boron tris (diamyl dithiocarbamate).

150 g einer 50%-igen Natronlauge werden in 940 ml Methanol eingetragen. Dazu gibt man 293 g Diamylamin. Unter mechanischem Rühren tropft man dazu 120 ml Schwefelkohlenstoff im Verlauf von 30 Minuten. Die Mischung wird noch 2 Stunden lang weiter gerührt. 75 g Bortrifluorid-Diethylether-Komplex werden in 190 ml Ether eingetragen. Diese Lösung tropft man innerhalb von 90 Minuten zur Lösung des Natriumdi­thiocarbamats. Die Mischung wird noch 3 Stunden lang weiter gerührt. Vom Natriumfluorid wird abgesaugt. Aus dem Filtrat wird das Lösungsmittelgemisch ab­destilliert. Der Rückstand wird im Vakuum im Wasser­bad bei 70°C eine Stunde lang getrocknet. Danach wird nochmals abgesaugt. Man erhält 325 g eines gelblich gefärbten Öls, das einen Gehalt von 98,45 %, bezogen auf N, hat. Die Ausbeute beträgt 83 % der Theorie, bezogen auf Bortrifluorid.150 g of a 50% sodium hydroxide solution are introduced into 940 ml of methanol. Add 293 g of diamylamine. 120 ml of carbon disulfide are added dropwise with mechanical stirring over the course of 30 minutes. The mixture is stirred for a further 2 hours. 75 g of boron trifluoride-diethyl ether complex are introduced into 190 ml of ether. This solution is added dropwise to the solution of the sodium dithiocarbamate within 90 minutes. The mixture is stirred for a further 3 hours. The sodium fluoride is suctioned off. The solvent mixture is distilled off from the filtrate. The residue is dried in vacuo in a water bath at 70 ° C for one hour. Then it is suctioned off again. 325 g of a yellowish-colored oil are obtained, which has a content of 98.45%, based on N. The yield is 83% of theory, based on boron trifluoride.

Beispiel 5: Bor-tris-(ditridecyl-dithiocarbamat) Example 5 : Boron tris (ditridecyl dithiocarbamate)

80 g einer 50%-igen Natronlauge werden zu 500 ml Methanol gegeben. Dazu gibt man 381 g Ditridecyl­amin. Unter mechanischem Rühren am Rückflußkühler werden 64 ml Schwefelkohlenstoff im Verlauf von 30 Minuten zugetropft. Die Mischung wird noch 2 Stunden lang weiter gerührt. Dann tropft man im Verlauf von 1 Stunde die Lösung von 45 ml Bortri­fluorid-Ethylether-Komplex in 100 ml Ether zu. Die Mischung wird noch 3 Stunden lang weiter gerührt. Sie bleibt dann über Nacht verschlossen stehen. Vom Natriumfluorid wird abgesaugt. Aus dem Filtrat wird das Lösungsmittelgemisch abdestilliert. Der Rückstand wird im Vakuum im Rotationsverdampfer bei einer Badtemperatur von 70°C getrocknet. Das erhaltene Öl wird nach dem Erkalten nochmals abge­saugt. Man erhält 393 g eines bernsteinfarbenen, viskosen Öles, das einen Gehalt von 98,7 % hat. Die Ausbeute beträgt 85,4 % der Theorie.80 g of a 50% sodium hydroxide solution are added to 500 ml of methanol. 381 g of ditridecylamine are added. With mechanical stirring on the reflux condenser, 64 ml of carbon disulfide are added dropwise over the course of 30 minutes. The mixture is stirred for a further 2 hours. The solution of 45 ml of boron trifluoride-ethyl ether complex in 100 ml of ether is then added dropwise over the course of 1 hour. The mixture is stirred for a further 3 hours. It then remains closed overnight. The sodium fluoride is suctioned off. The solvent mixture is distilled off from the filtrate. The residue is dried in vacuo in a rotary evaporator at a bath temperature of 70 ° C. The oil obtained is suctioned off again after cooling. 393 g of an amber-colored, viscous oil are obtained, which has a content of 98.7%. The yield is 85.4% of theory.

Claims (10)

1. Bor-tris-(dialkyl-dithiocarbamate) der allgemeinen Formel
Figure imgb0003
 in der R und Rʹ gleiche oder verschiedene, ver­zweigte oder unverzweigte, gesättigte oder unge­sättigte Alkylreste mit 1 bis 12 Kohlenstoffatomen bedeuten.1. Boron tris (dialkyl dithiocarbamate) of the general formula
Figure imgb0003
 in which R and Rʹ represent the same or different, branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 12 carbon atoms. 2. Bor-tris-(di-2-ethylhexyl-dithiocarbamat).2. Boron tris (di-2-ethylhexyl dithiocarbamate). 3. Bor-tris-(diamyl-dithiocarbamat).3. Boron tris (diamyl dithiocarbamate). 4. Bor-tris-(ditridecyl-dithiocarbamat).4. Boron tris (ditridecyl dithiocarbamate). 5. Verfahren zur Herstellung von Bor-tris-(dialkyl­dithiocarbamaten der allgemeinen Formel I,
dadurch gekennzeichnet,
daß man 3 Mol eines Alkali-dialkyl-dithiocarbamats der allgemeinen Formel
Figure imgb0004
 in der R und Rʹ die Bedeutung des Anspruchs 1 haben und Me⁺ für Na⁺, K⁺ oder NH₄⁺ steht, mit einem Mol Bortribromid, Bortrichlorid oder Bortrifluorid in einem inerten Medium umsetzt, das gebildete Al­kali- oder Ammoniumhalogenid abtrennt und das Bor-­tris-(dialkyl-dithiocarbamat) isoliert.5. Process for the preparation of boron tris (dialkyldithiocarbamates of the general formula I
characterized,
that 3 mol of an alkali dialkyl dithiocarbamate of the general formula
Figure imgb0004
 in which R and Rʹ have the meaning of claim 1 and Me⁺ is Na⁺, K⁺ or NH₄⁺, reacted with a mole of boron tribromide, boron trichloride or boron trifluoride in an inert medium, the alkali metal or ammonium halide formed is separated off and the boron tris (dialkyl dithiocarbamate) isolated. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß als inertes Medium aliphatische oder aroma­tische Kohlenwasserstoffe oder Ether eingesetzt werden.6. The method according to claim 5, characterized in that aliphatic or aromatic hydrocarbons or ethers are used as the inert medium. 7. Verfahren zur Herstellung von Bor-tris-(dialkyl-­dithiocarbamaten) der Formel I,
dadurch gekennzeichnet, daß man 3 Mol eines Alkali-­dialkyl-dithiocarbamats der allgemeinen Formel
Figure imgb0005
 in der R und Rʹ die Bedeutung des Anspruchs 1 haben und Me⁺ für Na⁺, K⁺ oder NH₄⁺ steht, mit einem Mol des Komplexes von Bortrifluorid mit Diethylether oder Methanol in einem wasserhaltigen Medium umsetzt, das gebildete Alkalihalogenid abtrennt und das Bor-tris-(dialkyldithiocarbamat) isoliert.7. Process for the preparation of boron tris (dialkyl dithiocarbamates) of the formula I,
characterized in that 3 moles of an alkali dialkyl dithiocarbamate of the general formula
Figure imgb0005
 in which R and Rʹ have the meaning of claim 1 and Me⁺ is Na⁺, K⁺ or NH₄⁺, reacted with one mole of the complex of boron trifluoride with diethyl ether or methanol in a water-containing medium, the alkali metal halide formed is separated off and the boron tris (dialkyldithiocarbamate) isolated. 8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Reaktion in Methanol, Ethanol, Propanol, Isopropanol, Ethylen-glykol-monoalkyl-ether, Te­trahydrofuran oder Dioxan durchgeführt wird.8. The method according to claim 7, characterized in that the reaction is carried out in methanol, ethanol, propanol, isopropanol, ethylene glycol monoalkyl ether, tetrahydrofuran or dioxane. 9. Verfahren nach Anspruch 7 oder 8, dadurch ge­kennzeichnet, daß der Wassergehalt des Reaktiongs­mediums nicht mehr als 15 % beträgt.9. The method according to claim 7 or 8, characterized in that the water content of the reaction medium is not more than 15%. 10. Verfahren nach einem der Ansprüche 5 bis 9, da­durch gekennzeichnet, daß die Reaktion bei Tempera­turen von 0 bis 90, vorzugsweise 20 bis 70°C durchgeführt wird.10. The method according to any one of claims 5 to 9, characterized in that the reaction is carried out at temperatures from 0 to 90, preferably 20 to 70 ° C.
EP88105850A 1987-04-29 1988-04-13 Bor-tris-(dialkyl-dithiocarbamates) and process for their preparation Expired - Lifetime EP0288818B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88105850T ATE100080T1 (en) 1987-04-29 1988-04-13 BORON-TRIS-(DIALKYL-DITHIOCARBAMATE) AND PROCESS FOR THEIR PRODUCTION.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3714260 1987-04-29
DE19873714260 DE3714260A1 (en) 1987-04-29 1987-04-29 BOR TRIS (DIALKYL DITHIOCARBAMATE) AND METHOD FOR THE PRODUCTION THEREOF

Publications (3)

Publication Number Publication Date
EP0288818A2 true EP0288818A2 (en) 1988-11-02
EP0288818A3 EP0288818A3 (en) 1990-07-11
EP0288818B1 EP0288818B1 (en) 1994-01-12

Family

ID=6326505

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88105850A Expired - Lifetime EP0288818B1 (en) 1987-04-29 1988-04-13 Bor-tris-(dialkyl-dithiocarbamates) and process for their preparation

Country Status (7)

Country Link
US (2) US4879071A (en)
EP (1) EP0288818B1 (en)
JP (1) JPH0788393B2 (en)
AT (1) ATE100080T1 (en)
CA (1) CA1306264C (en)
DE (2) DE3714260A1 (en)
ES (1) ES2061541T3 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2862952A (en) * 1957-08-26 1958-12-02 American Cyanamid Co Method of preparing b-hydrocarbonsubstituted boron compounds
US2941000A (en) * 1958-03-24 1960-06-14 American Potash & Chem Corp Preparation of mixed anhydrides of lower alkanoic acids and pyroboric acid
DE3712133A1 (en) * 1987-04-10 1988-10-20 Siwa Gmbh LUBRICANTS OR LUBRICANT CONCENTRATE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMISCHE BERICHTE, Band 102, Nr. 1, 1969, Seiten 161-166; H. N\RTH et al.: "Beitr{ge zur Chemie des Bors, XLIV: Dimethylthiocarbamoylmercapto-borane" *

Also Published As

Publication number Publication date
JPS63275589A (en) 1988-11-14
EP0288818A3 (en) 1990-07-11
ES2061541T3 (en) 1994-12-16
US4960933A (en) 1990-10-02
ATE100080T1 (en) 1994-01-15
US4879071A (en) 1989-11-07
DE3886984D1 (en) 1994-02-24
DE3714260A1 (en) 1988-11-10
JPH0788393B2 (en) 1995-09-27
CA1306264C (en) 1992-08-11
EP0288818B1 (en) 1994-01-12

Similar Documents

Publication Publication Date Title
DE69824886T2 (en) METHOD FOR THE PRODUCTION OF 3-DIFFERENT MOLYBDENUM SULFUR COMPOUNDS AND THEIR USE AS LUBRICATING ADDITIVES
DE60114687T2 (en) Process for the preparation of lubricant additives
DE2753124C2 (en)
DE1014989B (en) Process for the production of aromatic dithiophosphinic acids or their salts
EP0288819B1 (en) Process for the preparation of dialkyldithiocarbamates of polyvalent metals
DE2212604A1 (en) Process for the preparation of 2-haloethylphosphonic acids
EP0288818B1 (en) Bor-tris-(dialkyl-dithiocarbamates) and process for their preparation
DE1247312B (en) Process for the preparation of bis-dihalo-tetraorganodisiloxanyl-m- or -p-carborane compounds
CH507989A (en) Preparation of tricyclohexyltin hydroxide
DE3640383A1 (en) HYDROCARBON-SOLUBLE METAL-ORGANIC COMPLEXES OF MAGNESIUM AND ALKALI-METALS AND A METHOD FOR THE PRODUCTION THEREOF
EP0534356A1 (en) Vanadium(IV)oxide-bis (dialkyldithiocarbamates) and process for their preparation
DE847900C (en) Process for the preparation of tertiary and quaternary diamines containing at least one ether group
DE2007864A1 (en) Thiophosphoric acid esters, process for their preparation and their use
DE899433C (en) Process for the preparation of insecticidal mixtures containing essentially octaalkyltetrapyrophosphoric acid
DE2020455C3 (en) Zinc alkyl thiophosphate mixtures and processes for their preparation and their use
EP0534357B1 (en) New tungsten-hexa-(dialkyldithiocarbamates) and process for their preparation
DE3830351A1 (en) METHOD FOR PRODUCING (ALPHA) AMINO ALCANOLS
DE3779772T2 (en) METHOD FOR PRODUCING 0.0-DI-LOW-ALKYL CHLOROTHIOPHOSPHATES.
DE60202639T2 (en) 2-Halo-1-Cycloalkenkarboxamide and their preparation
EP0317912B1 (en) Process for the preparation of 1-thiocyanatomethyl ethers
DE960191C (en) Process for the production of nitrogen-containing vinyl ethers
EP0115011A1 (en) Process for the preparation of dichlorophosphanes
DE952084C (en) Process for the production of organic isothiocyanates
DE2952477C2 (en) Process for the preparation of water-insoluble alkylamine poly- and / or -metaphosphates
DE2429757C3 (en) Process for the preparation of 3-hexyn-1-ol

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19900822

17Q First examination report despatched

Effective date: 19920227

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DR. SPIESS CHEMISCHE FABRIK GMBH & CO.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 100080

Country of ref document: AT

Date of ref document: 19940115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3886984

Country of ref document: DE

Date of ref document: 19940224

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

ET Fr: translation filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3010438

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940408

EPTA Lu: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2061541

Country of ref document: ES

Kind code of ref document: T3

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 88105850.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960201

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960401

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960410

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960416

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19960419

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960422

Year of fee payment: 9

Ref country code: AT

Payment date: 19960422

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960426

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19960429

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960430

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960627

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970413

Ref country code: GB

Effective date: 19970413

Ref country code: AT

Effective date: 19970413

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970414

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

Ref country code: BE

Effective date: 19970430

BERE Be: lapsed

Owner name: SPIESS CHEMISCHE FABRIK G.M.B.H. & CO.

Effective date: 19970430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19971031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971101

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3010438

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970413

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971101

EUG Se: european patent has lapsed

Ref document number: 88105850.7

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050413