DE1042569B - Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acid - Google Patents
Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acidInfo
- Publication number
- DE1042569B DE1042569B DEB38651A DEB0038651A DE1042569B DE 1042569 B DE1042569 B DE 1042569B DE B38651 A DEB38651 A DE B38651A DE B0038651 A DEB0038651 A DE B0038651A DE 1042569 B DE1042569 B DE 1042569B
- Authority
- DE
- Germany
- Prior art keywords
- amine
- complex compounds
- acid
- zinc
- production
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 8
- 239000011701 zinc Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052725 zinc Inorganic materials 0.000 title claims description 5
- 239000002253 acid Substances 0.000 title description 3
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- AWYFNIZYMPNGAI-UHFFFAOYSA-N ethylenebis(dithiocarbamic acid) Chemical compound SC(=S)NCCNC(S)=S AWYFNIZYMPNGAI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- JMZRZEXRYJUHEB-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate;zinc Chemical compound [Zn].NC(=S)SCCSC(N)=S JMZRZEXRYJUHEB-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- FROZIYRKKUFAOC-UHFFFAOYSA-N amobam Chemical compound N.N.SC(=S)NCCNC(S)=S FROZIYRKKUFAOC-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YRGVKPIUZUOJSJ-UHFFFAOYSA-N n,n'-dibutylethane-1,2-diamine Chemical compound CCCCNCCNCCCC YRGVKPIUZUOJSJ-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000004992 toluidines Chemical class 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
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Amin-Zink-Komplexverbindungen der Äthylenbisdithiocarbaminsäure Es ist bekannt, daß Salze der allgemeinen Formel in der R eine zweiwertige Kohlenwasserstoffgruppe oder eine zweiwertige aliphatische Gruppe mit mehr als 3 Kohlenstoffatomen darstellt, die durch mindestens 1 Stickstoffatom zwecks Bildung von Äthylengruppen mit mindestens je 2 Kohlenstoffatomen voneinander getrennt sind, R' und R" jedes für sich Wasserstoff oder in Verbindung miteinander eine zweiwertige Kohlenwasserstoffgruppe darstellen, fungizid wirksam sind. Ein Nachteil dieser Verbindungen, z. B. von Zinkäthylenbisdithiocarbamat, ist, daß sie unbeständig sind und zum Zerfall neigen, so daß sie nach längerem Lagern besonders bei Wärme sich zersetzen und an fungizider M'firksamkeit verlieren. Auch nach dem Aufbringen auf die Pflanzen beginnen sie besonders in tropischen und subtropischen Gebieten unter dem Einfluß des Sonnenlichtes zu zerfallen und ihre fungizide Wirksamkeit zu vermindern, weshalb eine mehrmalige Behandlung mit diesen Mitteln oft notwendig wird.Process for the preparation of amine-zinc complex compounds of ethylene bisdithiocarbamic acid It is known that salts of the general formula in which R represents a divalent hydrocarbon group or a divalent aliphatic group with more than 3 carbon atoms, which are separated from one another by at least 1 nitrogen atom for the purpose of forming ethylene groups with at least 2 carbon atoms each, R 'and R "are each hydrogen or in combination with one another A disadvantage of these compounds, for example zinc ethylene bisdithiocarbamate, is that they are unstable and tend to disintegrate, so that after prolonged storage, especially when heated, they decompose and lose their fungicidal effectiveness. Even after they have been applied to the plants, they begin to disintegrate under the influence of sunlight, especially in tropical and subtropical areas, and reduce their fungicidal effectiveness, which is why repeated treatment with these agents is often necessary.
Es wurde nun gefunden, daß Amin-Zink-Komplexverbindungen der Äthylenbisdithiocarbaminsäure nicht nur ausgezeichnete Fungizide sind, sondern auch eine vorzügliche Stabilität aufweisen, die schon bei der Produktion schärfere Herstellungsbedingungen zuläßt und bei dem Verbrauch im Freiland bei Sonnenbestrahlung eine Zersetzung des fein verteilten Materials bedeutend vermindert.It has now been found that amine-zinc complex compounds of Äthylenbisdithiocarbamic acid are not only excellent fungicides but also excellent stability have, which allows more stringent manufacturing conditions during production and when consumed outdoors in sunlight, a decomposition of the fine distributed material is significantly reduced.
Gegenstand der Erfindung ist nun ein Verfahren zur Herstellung einer solchen Amin-Zink-Komplexv erbindung der Äthylenbisdithiocarbaminsäure. Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man ein wasserlösliches Salz der Äthvlenbisdithiocarbaminsäure der allgemeinen Formel Me-S-CS-NH-(CH2)2-NH-CS-SMe (Me =Na, K, NHq) mit 1 Mol eines wasserlöslichen Zinksalzes in Gegenwart von 1 Mol eines Amins in wäßriger Lösung bei 10 bis 60°C umsetzt.The invention now relates to a process for the production of such an amine-zinc complex compound of ethylene bisdithiocarbamic acid. The process according to the invention is characterized in that a water-soluble salt of Äthvlenbisdithiocarbamic acid of the general formula Me-S-CS-NH- (CH2) 2-NH-CS-SMe (Me = Na, K, NHq) with 1 mol of a water-soluble zinc salt in the presence of 1 mole of an amine in aqueous solution at 10 to 60 ° C.
Als Amine zur Bildung der Komplexverbindungen können verwendet werden: Methylamin, Äthylamin, Butylamin, Amylamin, Hexadecylamin, Octadecylamin, Dimethylamin, Diäthylamin, Dibutylamin, Diamylamin, Trimethylamin, Äthylendiamin, Cyclohexylamin, Piperidin, Diäthyläthylen-diamin, Dibutyläthylen-diamin, Diäthylen-triamin, Dimethyläthylen-diamin, Cyclohexylamin, Morpholin, Äthyl-cyclohexylamin, Benzylamin, Toluidin, N-Methyl-cyclohexylamin. Als wasserlösliche Zinksalze seien das Chlorid, Sulfat, Nitrat oder Acetat erwähnt.The following amines can be used to form the complex compounds: Methylamine, ethylamine, butylamine, amylamine, hexadecylamine, octadecylamine, dimethylamine, Diethylamine, dibutylamine, diamylamine, trimethylamine, ethylenediamine, cyclohexylamine, Piperidine, diethylethylene-diamine, dibutylethylene-diamine, diethylene-triamine, dimethylethylene-diamine, Cyclohexylamine, morpholine, ethyl-cyclohexylamine, benzylamine, toluidine, N-methyl-cyclohexylamine. Chloride, sulfate, nitrate or acetate may be mentioned as water-soluble zinc salts.
Zur Erläuterung des beanspruchten Verfahrens sollen die folgenden Beispiele dienen: Beispiel 1 Zu 500m1 einer wäßrigen Lösung, enthaltend 123g Ammoniumäthylenbisdithiocarbamat (0,5 Mol) und 30 g Äthylendiamin (0,5 Mol), werden bei 25°C und unter Rühren 150 ml einer Zinksulfatlösung, enthaltend 32,7 g Zn (0,5 g-Atom), rasch zugegeben. Anschließend wird bei dieser Temperatur noch 1 Stunde nachgerührt, danach der gebildete Niederschlag filtriert, mit Wasser gewaschen und getrocknet.The following examples are intended to illustrate the claimed process: Example 1 To 500m1 an aqueous solution containing 123g Ammoniumäthylenbisdithiocarbamat (0.5 mol) and 30 g of ethylenediamine (0.5 mole) are determined at 25 ° C and with stirring 150 ml of a zinc sulfate solution containing 32.7 g of Zn (0.5 g Atom), added quickly. The mixture is then stirred at this temperature for a further 1 hour, then the precipitate formed is filtered off, washed with water and dried.
Beispiel 2 Zu 500 ml einer wäßrigen Lösung, enthaltend 125 g Arnmoniumäthylen-bisdithiocarbamat (0,5 -11o1) und 22,5 g Dimethylamin (0,5 Mol), werden bei 25°C und unter Rühren 150 ml einer Zinksulfatlösung, enthaltend 32,7 g Zn (0,5 gAtom) rasch zugegeben. Anschließend wird bei dieser Temperatur noch 1 Stunde lang gerührt, danach der gebildete Niederschlag filtriert, mit Wasser gewaschen und getrocknet.Example 2 To 500 ml of an aqueous solution containing 125 g of ammonium ethylene bisdithiocarbamate (0.5 -11o1) and 22.5 g of dimethylamine (0.5 mol), 150 ml of a zinc sulfate solution containing 32.7 are added at 25 ° C. with stirring g Zn (0.5 gAtom) added quickly. The mixture is then stirred at this temperature for a further 1 hour, then the precipitate formed is filtered off, washed with water and dried.
Ausbeute: 159,0 g entsprechend 99,2°/o der Theorie. Die nachfolgende
Tabelle gibt vergleichsweise die Stabilitäten von Zink- Amin-Komplexverbindungen
und von Zinl,:äthylenbisdithiocarbamat in Gegenwart von Wasser bei verschiedenen
Temperaturen wieder. Die Analyse erfolgte nach -der Methode aus »Analyst Chemistry:;,
Vol. 13, Nr. 12, Dezember 1951, S. 1842 bis 1844.
Bei Lagerung des Zinkäthylenbisdithiocarbamats ist nach 6 Monaten ohne Zusatz von Stabilisatoren der Gehalt an wirksamer Substanz bereits um 25 bis 30 0/0 vermindert. Auch ein Zusatz von Stabilisatoren gibt keine genügende Sicherheit, da auch stabilisiertes Zinkäthylenbisdithiocarbamat beim Lagern zersetzt wird und an fungizider Wirksamkeit einbüßt. Dagegen zeigen die Aminkomplexverbindungen auch bei normalen Bedingungen eine beachtliche Stabilität. Dieses bedeutet aber, daß sowohl ihre Lagerfähigkeit als auch die Beständigkeit des Spritzbelages auf den Pflanzen erheblich größer ist.When the zinc ethylene bisdithiocarbamate is stored it is after 6 months Without the addition of stabilizers, the content of active substance can already be increased by 25 to 30 0/0 decreased. Even the addition of stabilizers does not provide sufficient security, because stabilized zinc ethylene bisdithiocarbamate is also decomposed during storage and loses its fungicidal effectiveness. In contrast, the amine complex compounds also show Considerable stability under normal conditions. But this means that both their shelf life and the resistance of the spray coating on the Plants is considerably larger.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB38651A DE1042569B (en) | 1956-01-10 | 1956-01-10 | Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB38651A DE1042569B (en) | 1956-01-10 | 1956-01-10 | Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1042569B true DE1042569B (en) | 1958-11-06 |
Family
ID=6965569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB38651A Pending DE1042569B (en) | 1956-01-10 | 1956-01-10 | Process for the production of amine-zinc complex compounds of AEthylenbisdithiocarbamic acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1042569B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1202266B (en) * | 1961-10-06 | 1965-10-07 | Basf Ag | Process for the preparation of ammonia-containing complex compounds of the manganese salt of ethylene-bis-dithio-carbamic acid |
| US3536742A (en) * | 1968-08-26 | 1970-10-27 | Dow Chemical Co | Alkylenebisdithiocarbamate complex compounds |
| DE1542684B1 (en) * | 1965-01-29 | 1971-01-21 | Basf Ag | Fungicides |
| US3725445A (en) * | 1971-01-13 | 1973-04-03 | Nippon Kayaku Kk | A double salt of zinc ethylene-bis-dithiocarbamate and n-dodecylguanidine and preparation thereof |
-
1956
- 1956-01-10 DE DEB38651A patent/DE1042569B/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1202266B (en) * | 1961-10-06 | 1965-10-07 | Basf Ag | Process for the preparation of ammonia-containing complex compounds of the manganese salt of ethylene-bis-dithio-carbamic acid |
| DE1542684B1 (en) * | 1965-01-29 | 1971-01-21 | Basf Ag | Fungicides |
| US3536742A (en) * | 1968-08-26 | 1970-10-27 | Dow Chemical Co | Alkylenebisdithiocarbamate complex compounds |
| US3725445A (en) * | 1971-01-13 | 1973-04-03 | Nippon Kayaku Kk | A double salt of zinc ethylene-bis-dithiocarbamate and n-dodecylguanidine and preparation thereof |
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