DE1005964B - Process for the preparation of new alkoxy mercury compounds - Google Patents
Process for the preparation of new alkoxy mercury compoundsInfo
- Publication number
- DE1005964B DE1005964B DEB40038A DEB0040038A DE1005964B DE 1005964 B DE1005964 B DE 1005964B DE B40038 A DEB40038 A DE B40038A DE B0040038 A DEB0040038 A DE B0040038A DE 1005964 B DE1005964 B DE 1005964B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- mercury
- preparation
- compounds
- mercury 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
- -1 alkoxy mercury compounds Chemical class 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical class [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 229940100892 mercury compound Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren- zur Herstellung von neuen Alkoxymercuriverbindungen Es ist bekannt, ungesättigte Kohlenwasserstoffe, wie z. B. Styrol, Butadien, Isopren und Diallyl, mit Quecksilber(II)-acetat in alkoholischer Lösung in die entsprechenden Alkoxymercuriverbindungen überzuführen. Die Alkoxymercuriverbindung entsteht durch Anlagerung je eines Mercuriacetatrestes und eines Alkoxyrestes, der aus dem als Lösungsmittel angewendeten Alkohol kommt, an eine Doppelbindung. Die Reaktion verläuft quantitativ und kann zur quantitativen Bestimmung von Doppelbindungen durch Titration der bei der Reaktion frei werdenden Essigsäure verwendet werden.Process for the preparation of new alkoxymercuric compounds Es is known to use unsaturated hydrocarbons, such as. B. styrene, butadiene, isoprene and diallyl, with mercury (II) acetate in alcoholic solution in the corresponding Convert alkoxymercuric compounds. The alkoxy mercury compound is created by Addition of a Mercuriacetatrestes and an alkoxy radical, which from the as Solvent applied alcohol comes to a double bond. The reaction proceeds quantitative and can be used for the quantitative determination of double bonds by titration the acetic acid released during the reaction can be used.
Es wurde nun gefunden, daß man neue Alkoxymercuriverbindungen aus N-Vinylverbindungen, die bekanntlich in saurem Medium sehr instabil sind und in kürzester Zeit unter Acetataldehydentwicklung zersetzt werden, durch Anlagerung von Quecksilbersalzen erhält, wenn man die N-Vinylverbindungen in alkoholischer Lösung mit Quecksilber(II)-salzen organischer Säuren umsetzt. Man kann gegebenenfalls ein Absinken des pH-Wertes durch Neutralisation der bei der Reaktion entstehenden Säure verhindern. Die Reaktion wird zweckmäßig in Lösungsmitteln ausgeführt, in denen die entstehenden Alkoxymercuriverbindungen unlöslich sind, z. B. Methanol, Äthanol, Propanol, Iso- und n-Butanol. Aber auch in anderen Lösungsmitteln kann gearbeitet werden, wenn die alkoholische Komponente zugesetzt wird. In diesem Fall ist es nur nötig, die Reaktionsmischung nach Umsetzung einzudampfen. Auch in Gegenwart von Wasser ist die Reaktion ausführbar. Als Quecksilberverbindungen können alle Salze des Quecksilbers mit organischen Säuren Verwendung finden, z. B. die Acetate und Önanthate.It has now been found that new alkoxymercuric compounds can be produced N-vinyl compounds, which are known to be very unstable in an acidic medium and in be decomposed in a very short time with evolution of acetate aldehyde, by addition obtained from mercury salts when one converts the N-vinyl compounds into alcoholic Reacts solution with mercury (II) salts of organic acids. One can optionally a decrease in the pH value due to the neutralization of the resulting from the reaction Prevent acid. The reaction is expediently carried out in solvents, in which the resulting alkoxymercuric compounds are insoluble, e.g. B. methanol, Ethanol, propanol, iso- and n-butanol. But it can also be used in other solvents be worked when the alcoholic component is added. In this case it is only necessary to evaporate the reaction mixture after reaction. Even in the present the reaction can be carried out with water. As mercury compounds can all Find mercury salts with organic acids, z. B. the acetates and enanthates.
Die nach dem Verfahren der Erfindung herstellbaren neuen Verbindungen zeigen sehr gute fungizide Wirkung.The novel compounds which can be prepared by the process of the invention show very good fungicidal effects.
Die in den nachfolgenden Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the following examples are parts by weight.
Beispiel 1 100 Teile N-Vinylcarbazol und 165 Teile Quecksilber(II)-acetat werden unter Rühren in 640 Teilen Methanol gelöst. In kurzer Zeit tritt vollständige Lösung ein, dann fällt unmittelbar danach ein weißer kristalliner Niederschlag aus. Er wird gut abgesaugt und getrocknet. Man erhält 230 Teile a-Methoxyß-mercuriacetato-9-äthylcarbazol vom Fp. 149 bis 150°, das sind 92%, der Theorie. Durch Eindampfen der Mutterlauge können weitere 5 °/a gewonnen werden. Der Stoff ist unlöslich in Wasser und Petroläther, sehr wenig löslich in Methanol, löslich in Chloroform, Benzol und Aceton. Beispiel 2 28 Teile N-Vinylpyrrolidon und 80 Teile Quecksilber(II)-acetat werden in 500 Teilen Methanol gelöst. Nach kurzem Stehen wird eine Lösung von 6 Teilen Natriumhydroxyd in 20 Teilen Wasser zugegeben. Die vollkommen klare und farblose Lösung wird im Vakuum schonend eingedampft. Der Rückstand wird mit 600 Teilen Benzol kalt extrahiert, der Niederschlag abfiltriert und das Filtrat im Vakuum eingedampft. Man erhält 107 Teile a-Methoxy-ß-mercuriacetato-l-äthylpyrrolidon als klaren farblosen Sirup, das sind 90°/o der Theorie. Der Stoff löst sich in verdünnter Natronlauge, Wasser und den gebräuchlichen organischen Lösungsmitteln außer Petroläther.Example 1 100 parts of N-vinylcarbazole and 165 parts of mercury (II) acetate are dissolved in 640 parts of methanol with stirring. Complete in a short time Solution, then a white crystalline precipitate falls out immediately afterwards. It is well vacuumed and dried. 230 parts of α-methoxyβ-mercuriacetato-9-ethylcarbazole are obtained from mp. 149 to 150 °, that is 92%, of theory. By evaporation of the mother liquor a further 5 ° / a can be gained. The substance is insoluble in water and petroleum ether, very slightly soluble in methanol, soluble in chloroform, benzene and acetone. example 2 28 parts of N-vinylpyrrolidone and 80 parts of mercury (II) acetate are in 500 parts Dissolved methanol. After standing for a short time, a solution of 6 parts of sodium hydroxide is obtained added in 20 parts of water. The completely clear and colorless solution is in the Gently evaporated in a vacuum. The residue is extracted cold with 600 parts of benzene, the precipitate is filtered off and the filtrate is evaporated in vacuo. One receives 107 Share a-methoxy-ß-mercuriacetato-l-ethylpyrrolidone as a clear colorless syrup that are 90% of theory. The substance dissolves in dilute caustic soda, water and the common organic solvents except petroleum ether.
Beispiel 3 28 Teile Vinylcaprolactam werden in 350 Teilen Methanol mit 64 Teilen Quecksilber(II)-acetat versetzt. Nach kurzem Stehen tritt vollständige Lösung ein. Die vollkommen farblose und klare Lösung wird eingedampft. Der entstehende farblose Sirup wird scharf über K O H getrocknet. Man erhält 72 Teile a-Methoxy-ß-mercuriacetato-N-äthylcaprolactam als Sirup, das sind 84% der Theorie. Die Substanz löst sich in Wasser und den gebräuchlichen organischen Lösungsmitteln außer Petroläther.Example 3 28 parts of vinyl caprolactam are dissolved in 350 parts of methanol 64 parts of mercury (II) acetate are added. After standing for a short time, full occurs Solution one. The completely colorless and clear solution is evaporated. The emerging colorless syrup is sharply dried over K O H. 72 parts of α-methoxy-β-mercuriacetato-N-ethylcaprolactam are obtained as a syrup, that's 84% of theory. The substance dissolves in water and the common ones organic solvents except petroleum ether.
Beispiel 4 193 Teile Vinylcarbazol werden in 1000 Teilen Butanol mit 318 Teilen Quecksilber(II)-acetat versetzt und 2 Stunden bei 60° gehalten. Es ist dann klare Lösung eingetreten. Das überschüssige Butanol wird im Vakuum abgedampft. Der weiße Rückstand wird aus wäßrigem Methanol umkristallisiert. Man erhält 425 Teile a-Butoxy-ß-mercuriacetato-9-äthrylcarbazol als weiße, kristalline Substanz vom Fp. 150 bis 153°, das sind 81,1/o der Theorie.Example 4 193 parts of vinyl carbazole are mixed with 1000 parts of butanol 318 parts of mercury (II) acetate are added and the mixture is kept at 60 ° for 2 hours. It is then clear solution occurred. The excess butanol is evaporated off in vacuo. The white residue is recrystallized from aqueous methanol. 425 parts of a-butoxy-β-mercuriacetato-9-äthrylcarbazol are obtained as white, crystalline Substance with a melting point of 150 to 153 °, that is 81.1 / o of theory.
Beispiel 5 193 Teile Vinylcarbazol in 1750 Teilen Methanol werden unter Rühren bei 50° mit 460 Teilen Quecksilber(II)-önanthat versetzt. Nach 2 Stunden ist vollständige Lösung eingetreten. Das Methanol wird abdestilliert. Der weiße, pastenförmige Rückstand kristallisiert im Verlauf einiger Tage. Man erhält 495 Teile a-Methoxy-ß-mercuriönantho-9-äthylcarbazol, das sind 89% der Theorie.Example 5 193 parts of vinyl carbazole in 1750 parts of methanol are used 460 parts of mercury (II) oenanthate are added with stirring at 50 °. After 2 hours complete solution has occurred. The methanol is distilled off. The White, Pasty residue crystallizes in the course of a few days. 495 parts are obtained α-Methoxy-ß-mercuriönantho-9-ethylcarbazole, that is 89% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB40038A DE1005964B (en) | 1956-04-28 | 1956-04-28 | Process for the preparation of new alkoxy mercury compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB40038A DE1005964B (en) | 1956-04-28 | 1956-04-28 | Process for the preparation of new alkoxy mercury compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1005964B true DE1005964B (en) | 1957-04-11 |
Family
ID=6965969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB40038A Pending DE1005964B (en) | 1956-04-28 | 1956-04-28 | Process for the preparation of new alkoxy mercury compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1005964B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1111450B (en) * | 1959-07-31 | 1961-07-20 | Union Rheinische Braunkohlen | Combating insects that cause damage to plants and their stages of development |
-
1956
- 1956-04-28 DE DEB40038A patent/DE1005964B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1111450B (en) * | 1959-07-31 | 1961-07-20 | Union Rheinische Braunkohlen | Combating insects that cause damage to plants and their stages of development |
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