DE1202792B - Process for the preparation of bisquaternaeren compounds by addition of tertiary amines to di- (chloromethyl) ethers of dihydric alcohols - Google Patents
Process for the preparation of bisquaternaeren compounds by addition of tertiary amines to di- (chloromethyl) ethers of dihydric alcoholsInfo
- Publication number
- DE1202792B DE1202792B DEC21955A DEC0021955A DE1202792B DE 1202792 B DE1202792 B DE 1202792B DE C21955 A DEC21955 A DE C21955A DE C0021955 A DEC0021955 A DE C0021955A DE 1202792 B DE1202792 B DE 1202792B
- Authority
- DE
- Germany
- Prior art keywords
- chloromethyl
- ether
- parts
- ethers
- compounds
- 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
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical class ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 title claims description 20
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 8
- 150000001298 alcohols Chemical class 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000003512 tertiary amines Chemical class 0.000 title claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von bisquatemären Verbindungen durch Anlagerung tertiärer Amine an Di-(chlonnethyl)-äther von zweiwertigen Alkoholen Bekanntlich sind die Di-(chlormethyl)-äther von Diolen fähig, sich an 2 Mol Pyridin zu den entsprechenden bisquaternären Verbindungen anzulagern. Beispielsweise liefert der Di-(chlormethyl)-äther von Äthylenglykol, d. h. Äthandiol-(1,2), eine Verbindung der nachstehenden Formel: Die für die Herstellung von Verbindungen dieser Art bekannten Verfahren lassen sich schwer in den Maßstab technisch brauchbarer Verfahren übertragen. Die Reaktion verläuft nämlich sehr stark exotherm; wenn man Pyridin in dünnem Strahl in den Di-(chlormethyl)-äther des betreffenden zweiwertigen Alkohols gießt, zeigt sich das Reaktionsprodukt zunächst in kautschukartiger Form und bleibt an der Wandung des Reaktionsgefäßes haften, wodurch das Abführen der überschüssigen Wärme zu einer schwierigen Aufgabe wird. Dies gilt auch für den Fall, daß man den Di-(chlormethyl)-äther des Diols in Pyridin gießt. Verwendet man Benzol als Reaktionsmedium, so kann zwar die Reaktionswärme leicht abgeführt werden, doch wird das Reaktionsprodukt in harzartigem Zustand ausgefällt, wodurch das Abfiltrieren sehr erschwert wird. Außerdem bleibt das Produkt nach dem Filtrieren stark mit Benzol durchtränkt, das sich ohne Erwärmung, selbst im Vakuum, nur schwer beseitigen läßt. Dies ist natürlich wegen der Wärmeempfindlichkeit des Reaktionsproduktes ein großer Nachteil. Man hat als Reaktionsmedium auch Äther vorgeschlagen, doch ist die Verwendung dieses Lösungsmittels in gewerblichen Betrieben gefährlich.Process for the preparation of bisquaternary compounds by adding tertiary amines to di (chloromethyl) ethers of dihydric alcohols It is known that the di (chloromethyl) ethers of diols are capable of adding to 2 moles of pyridine to form the corresponding bisquaternary compounds. For example, provides the di- (chloromethyl) ether of ethylene glycol, d. H. Ethanediol- (1,2), a compound of the formula below: The processes known for the preparation of compounds of this type are difficult to transfer to the scale of industrially useful processes. The reaction is very exothermic; If a thin stream of pyridine is poured into the di (chloromethyl) ether of the dihydric alcohol in question, the reaction product initially appears in rubber-like form and adheres to the wall of the reaction vessel, making it a difficult task to dissipate the excess heat. This also applies in the event that the di (chloromethyl) ether of the diol is poured into pyridine. If benzene is used as the reaction medium, the heat of reaction can easily be dissipated, but the reaction product is precipitated in a resinous state, which makes filtering off very difficult. In addition, after filtering the product remains heavily saturated with benzene, which can only be removed with difficulty without heating, even in a vacuum. This is of course a major disadvantage because of the heat sensitivity of the reaction product. Ether has also been proposed as a reaction medium, but the use of this solvent in commercial operations is dangerous.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung bisquaternärer Verbindungen durch Anlagerung tertiärer Amine an Di-(chlormethyl)-äther von zweiwertigen Alkoholen, das dadurch gekennzeichnet ist, daß man den Di-(chlormethyl)-äther eines zweiwertigen Alkohols mit einer tertiären Base bei 0 bis 78'C in Gegenwart von Aceton oder Methyläthylketon umsetzt.The invention relates to a process for the preparation of bisquaternary compounds by addition of tertiary amines to di (chloromethyl) ethers of dihydric alcohols, which is characterized in that the di (chloromethyl) ether of a dihydric alcohol with a tertiary base at 0 to 78'C in the presence of acetone or methyl ethyl ketone.
Als geeignete zweiwertige Alkohole seien genannt: Äthylenglykol; Propandiol-(1,2); Propandiol-(1,3); Butandiol-(1,2); Butandiol-(1,3); Butandiol-(1,4); Butandiol-(2,3); 2,2-Dimethylolpropan bzw. Neopentylglykol und Diäthylenglykol. Die Isolierung der Di-(chlormethyl)-äther vor der Quaternierung der tertiären Amine ist nicht nötig. Man kann vielmehr einen zweiwertigen Alkohol mit Paraformaldehyd und Chlorwasserstoffgas bei 0 bis 50'C umsetzen, dem den Di-(chlormethyl)-äther enthaltenden Reaktionsgemisch kristallwasserfreies Calciumchlorid zusetzen, die untere wäßrige Schicht dekantieren und die obere Schicht bei 0 bis 78'C mit einer tertiären Base in Gegenwart von Aceton oder Methyläthylketon ohne Isolierung des Di-(chlormethyl)-äthers umsetzen.Suitable dihydric alcohols are: ethylene glycol; Propanediol- (1,2); Propanediol- (1,3); Butanediol- (1,2); Butanediol- (1,3); Butanediol- (1,4); Butanediol- (2,3); 2,2-dimethylolpropane or neopentyl glycol and diethylene glycol. It is not necessary to isolate the di (chloromethyl) ethers before the quaternization of the tertiary amines. Rather, a dihydric alcohol can be reacted with paraformaldehyde and hydrogen chloride gas at 0 to 50 ° C , calcium chloride free of anhydrous calcium can be added to the reaction mixture containing the dichloromethyl ether, the lower aqueous layer decanted and the upper layer at 0 to 78 ° C with a implement tertiary base in the presence of acetone or methyl ethyl ketone without isolating the di (chloromethyl) ether.
Man kann beispielsweise den Di-(chlormethyl)-äther in die Lösung der tertiären Base in Aceton allmählich einführen, wobei die Temperatur bei 0 bis 78'C gehalten werden kann; die letzterwähnte Temperatur ist der Siedepunkt des Methyläthylketo-ns. Oft ist es vorteilhaft, die Temperatur zwischen 20 und 60'C zu halten. Die bisquaternäre Verbindung wird in der Form weißer, leicht filtrierbarer Kristalle ausgefällt, welche so wie sie anfallen oder nach dem Trocknen verwendet werden. Das Trocknen erfolgt z. B. in der Weise, daß man über das Filter einen Strom heißen Stickstoffs streichen läßt.For example, the di (chloromethyl) ether can be gradually introduced into the solution of the tertiary base in acetone, it being possible for the temperature to be kept at 0 to 78 ° C .; the last-mentioned temperature is the boiling point of methyl ethyl ketone. It is often advantageous to keep the temperature between 20 and 60 ° C. The bisquaternary compound is precipitated in the form of white, easily filterable crystals, which are obtained as they are or used after drying. Drying takes place e.g. B. in such a way that you can sweep a stream of hot nitrogen over the filter.
Der Grund dafür, daß die gemäß dem Verfahren der Erfindung erhältlichen bisquaternären Verbindungen leicht filtrierbar sind, ist der, daß diese sowohl in Aceton als auch in Methyläthylketon völlig unlöslich sind und in diesen auch nicht quellen, was den zusätzlichen Vorteil erhöhter Ausbeuten mit sich bringt.The reason that those obtainable according to the method of the invention bisquaternary compounds are easily filterable, is that they are both in Acetone and methyl ethyl ketone are completely insoluble and not in these either swell what the additional advantage of increased yields brings.
Als tertiäre Basen kann man beispielsweise Pyridin, die Picoline, Trimethylamin und Triäthylamin verwenden.As tertiary bases, for example, pyridine, the picolines, Use trimethylamine and triethylamine.
Beispiel 1 In einen emaillierten Apparat werden 62Teile Äthandiol-(1,2) und 60Teile Paraformaldehyd eingebracht. Dann fügt man langsam unter so starkem Rühren sowie Kühlen, daß die Temperatur von 25'C nicht überschreitet, 75 Teile Chlorwasserstoffgas hinzu. Allmählich verschwindet das Trioxymethylen, und das Gemisch wird dünnflüssig. Dann führt man 40 Teile kristallwasserfreies Calciumchlorid ein, setzt das Rühren bis zur völligen Auflösung fort und dekantiert das Produkt. Die von dem Di-(chlormethyl)-äther von Äthanol-(1,2) gebildete obere Schicht beträgt 130 Teile.Example 1 62 parts of ethanediol (1,2) and 60 parts of paraformaldehyde are introduced into an enamelled apparatus. Then, while stirring and cooling so vigorously that the temperature does not exceed 25 ° C., 75 parts of hydrogen chloride are slowly added. Gradually the trioxymethylene disappears and the mixture becomes thin. 40 parts of calcium chloride free from water of crystallization are then introduced, stirring is continued until it is completely dissolved and the product is decanted. The upper layer formed by the di (chloromethyl) ether of ethanol (1,2) is 130 parts.
In einen zweiten emaillierten Apparat, der mit einem leistungsfähigen Rührwerk versehen ist, bringt man 260 Teile Aceton und 162 Teile x-Picolin ein. In dieses Gemisch wird die vorher erhaltene Schicht von Di-(chlormethyl)-äther von Äthanol-(1,2) eingegossen. Die in der Zeiteinheit zugegebene Menge und die Kühlung durch in dem Doppelmantel umlaufendes Wasser werden so eingestellt, daß die Temperatur nicht über 40 bis 45'C ansteigt. Die bisquaternäre Verbindung fällt sofort in Form feiner weißer Kristalle aus, die man abfiltriert. Ausbeute: 290 Teile der bisquaternären Verbindung aus o#-Picolin und Di-(chlormethyl)-äther von Äthanol-(1,2). 260 parts of acetone and 162 parts of x-picoline are introduced into a second enamelled apparatus equipped with a powerful stirrer. The previously obtained layer of dichloromethyl ether of ethanol (1,2) is poured into this mixture. The amount added in the unit of time and the cooling by circulating water in the double jacket are adjusted so that the temperature does not rise above 40 to 45.degree. The bisquaternary compound precipitates immediately in the form of fine white crystals, which are filtered off. Yield: 290 parts of the bisquaternary compound from o # picoline and di (chloromethyl) ether of ethanol (1,2).
Beispiel 2 130Teile des nach Beispiell erhältlichen Di-(chlormethyl)-äthers werden langsam bei 40 bis 45'C in 260 Teile Methyläthylketon und 130 Teile Pyridin eingeführt. Die bisquaternäre Verbindung der obigen Formel fällt sofort in Form feiner weißer Kristalle aus. Ausbeute-, 258 Teile. Example 2 130 parts of the di- (chloromethyl) ether obtainable according to the example are slowly introduced at 40 to 45 ° C. into 260 parts of methyl ethyl ketone and 130 parts of pyridine. The bisquaternary compound of the above formula precipitates immediately as fine white crystals. Yield, 258 parts.
Beispiel 3 130Teile des erwähnten Di-(chlorniethyl)-äthers werden langsam bei 40 bis 45'C in 260 Teile Aceton und 130 Teile Pyridin eingeführt. Die bisquaternäre Verbindung fällt sofort aus. Ausbeute: 258 Teile. Beispiel 4 130 Teile des nach Beispiel 1 erhaltenen Di-(chlormethyl)-äthers werden langsam bei 40 bis 45'C in 260 Teile Aceton und 100 Teile Trimethylamin gegossen. Die bisquaternäre Verbindung fällt sofort in Form feiner Kristalle aus. Ausbeute: 225 Teile der Verbindung Beispiel 5 130Teile des erwähnten Di-(chlormethyl)-äthers werden langsam bei 40 bis 45'C in 260 Teile Aceton und 167 Teile Triäthylamin gegossen. Die bisquaternäre Verbindung fällt sofort in Form feiner Kristalle aus. Ausbeute: 294 Teile der Verbindung Example 3 130 parts of the mentioned di (chloro diethyl) ether are slowly introduced at 40 to 45 ° C. into 260 parts of acetone and 130 parts of pyridine. The bisquaternary connection fails immediately. Yield: 258 parts. Example 4 130 parts of the di (chloromethyl) ether obtained in Example 1 are slowly poured at 40 to 45 ° C. into 260 parts of acetone and 100 parts of trimethylamine. The bisquaternary compound immediately precipitates in the form of fine crystals. Yield: 225 parts of the compound Example 5 130 parts of the di- (chloromethyl) ether mentioned are slowly poured into 260 parts of acetone and 167 parts of triethylamine at 40 to 45 ° C. The bisquaternary compound immediately precipitates in the form of fine crystals. Yield: 294 parts of the compound
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1202792X | 1959-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1202792B true DE1202792B (en) | 1965-10-14 |
Family
ID=9672086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC21955A Pending DE1202792B (en) | 1959-07-21 | 1960-07-20 | Process for the preparation of bisquaternaeren compounds by addition of tertiary amines to di- (chloromethyl) ethers of dihydric alcohols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1202792B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4143C (en) * | J. LATAPIE in Paris | Fitting for shoes and hooves |
-
1960
- 1960-07-20 DE DEC21955A patent/DE1202792B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4143C (en) * | J. LATAPIE in Paris | Fitting for shoes and hooves |
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