CH367162A - Process for the preparation of a new cuprous derivative of ethylene-bis-dithiocarbamic acid and use of this derivative - Google Patents
Process for the preparation of a new cuprous derivative of ethylene-bis-dithiocarbamic acid and use of this derivativeInfo
- Publication number
- CH367162A CH367162A CH5240157A CH5240157A CH367162A CH 367162 A CH367162 A CH 367162A CH 5240157 A CH5240157 A CH 5240157A CH 5240157 A CH5240157 A CH 5240157A CH 367162 A CH367162 A CH 367162A
- Authority
- CH
- Switzerland
- Prior art keywords
- ethylene
- derivative
- bis
- cuprous
- chloride
- Prior art date
Links
- AWYFNIZYMPNGAI-UHFFFAOYSA-N ethylenebis(dithiocarbamic acid) Chemical class SC(=S)NCCNC(S)=S AWYFNIZYMPNGAI-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000000243 solution Substances 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- UQJQVUOTMVCFHX-UHFFFAOYSA-L nabam Chemical compound [Na+].[Na+].[S-]C(=S)NCCNC([S-])=S UQJQVUOTMVCFHX-UHFFFAOYSA-L 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Procédé de préparation d'un nouveau dérivé cuivreux de l'acide éthylène-bis-dithiocarbamique et utilisation de ce dérivé
La présente invention concerne un dérivé cuivreux de l'acide éthylène-bis-dithiocarbamique à environ 48 % de cuivre non décrit jusqu'ici dans la littérature et remarquable notamment par son pouvoir fongicide élevé permettant son application en agriculture pour le traitement du mildiou et autres maladies des plantes causées par des fongi. Le nouveau composé est vraisemblablement un chelate, le produit étant essentiellement défini par son mode de préparation décrit plus loin et par sa teneur en cuivre qui est de 47 à 49 %.
Pour préparer le nouveau dérivé cuivreux de l'acide éthylène-bis-dithiocarbamique contenant de 47 à 49 % de cuivre on fait réagir, sous atmosphère de gaz inerte et à la température ordinaire, une solution aqueuse d'éthylène-bis-dithiocarbamate d'un métal alcalin ou alcalino-terreux avec une solution de chlorure cuivreux en présence d'un chlorure d'un métal alcalin et en maintenant le pH du mélange réactionnel à une valeur comprise entre 3 et 4, essore le précipité et le lave jusqu'à ce qu'il soit exempt de chlorures et sèche le produit ainsi obtenu renfermant moins de 0,25 % de sels hydrosolubles.
La solution aqueuse d'éthylène-bis-dithiocarbamate de sodium peut être préparée extemporanément par action du sulfure de carbone sur l'éthylène diamine suivie d'une neutralisation par la soude.
On peut effectuer la double décomposition avec le chlorure cuivreux en utilisant un éthylène-bisdithiocarbamate d'un autre métal alcalin que le sodium ou encore employer les éthylène-bis-dithiocarbamates des métaux alcalino-terreux. La réaction est effectuée à la température ordinaire et sous gaz inerte, de façon à éviter le passage du sel cuivreux en sel cuivrique. Après la double décomposition, on essore le précipité du produit formé, vraisemblablement de chelate, qu'on lave jusqu'à ce que les eaux de lavage ne renferment plus de chlorure. Le produit séché titre généralement 48,2-48,8 % de cuivre métal.
L'exemple suivant illustre l'invention.
On dissout 60 g de chlorure cuivreux dans 500 cm3 de solution aqueuse saturée de chlorure de sodium et ajoute de l'acide chlorhydrique concentré de façon à amener le pH de cette solution à une valeur comprise entre 3 et 4.
A 205 cm3 de cette solution on ajoute, sous agitation et sous atmosphère d'azote, 200 cm8 de solution saturée de chlorure de sodium, vérifie encore une fois que le pH est bien compris entre 3 et 4 sans interrompre l'agitation ni le courant gazeux, on introduit assez rapidement (en cinq minutes environ) 83 cm3 de la solution d'éthylène-bis-dithiocar- bamate de sodium dont on décrit la préparation ci-après, mélangée au préalable à 56 cm3 d'eau et 66 cm3 de solution saturée de chlorure de sodium, tout en maintenant le pH du mélange entre 3 et 4. On agite encore quelques minutes et filtre. Le précipité essoré constitué par le nouveau dérivé cuivreux est lavé d'abord avec 100cm3 de solution saturée de chlorure de sodium, puis avec 100 cm3 d'ammoniaque à 10 % et enfin à l'eau jusqu'à ce que les eaux de lavage soient exemptes de chlorures.
On essore à fond et sèche sous vide.
Rendement: 30,4 g. Le produit se présente sous forme d'une poudre brun foncé contenant de 47 à 49 % de cuivre, insoluble dans l'eau, les acides et alcalis dilués ainsi que dans la plupart des solvants usuels. I1 renferme moins de 0,25 % de sels hydrosolubles.
On peut obtenir une solution d'éthylène-bisdithiocarbamate de sodium de la manière suivante:
Dans 360 cm3 de solution aqueuse à 10 % d'éthylène diamine chauffée à 400 C, on introduit, sous agitation, 96 g de sulfure de carbone en une t12 heure environ et continue l'agitation à 400 C pendant une heure. Sans laisser refroidir, on ajoute lentement 154,5 cm8 de soude à 31 % et l'introduction terminée, ce qui demande environ une heure, on continue l'agitation encore deux heures et filtre la solution jaune orangé obtenue.
Process for the preparation of a new cuprous derivative of ethylene-bis-dithiocarbamic acid and use of this derivative
The present invention relates to a cuprous derivative of ethylene-bis-dithiocarbamic acid containing approximately 48% copper, not previously described in the literature and remarkable in particular for its high fungicidal power allowing its application in agriculture for the treatment of mildew and others. plant diseases caused by fungi. The new compound is probably a chelate, the product being essentially defined by its method of preparation described below and by its copper content which is 47 to 49%.
To prepare the new cuprous derivative of ethylene-bis-dithiocarbamic acid containing 47 to 49% copper, an aqueous solution of ethylene-bis-dithiocarbamate is reacted under an inert gas atmosphere and at room temperature. an alkali or alkaline earth metal with a solution of cuprous chloride in the presence of a chloride of an alkali metal and while maintaining the pH of the reaction mixture at a value between 3 and 4, the precipitate is filtered off and washed until that it is free of chlorides and dries the product thus obtained containing less than 0.25% of water-soluble salts.
The aqueous solution of sodium ethylene bis-dithiocarbamate can be prepared extemporaneously by the action of carbon disulfide on ethylene diamine followed by neutralization with sodium hydroxide.
The double decomposition can be carried out with cuprous chloride using an ethylene-bisdithiocarbamate of an alkali metal other than sodium or alternatively using ethylene-bis-dithiocarbamates of the alkaline earth metals. The reaction is carried out at room temperature and under inert gas, so as to prevent the passage of the cuprous salt into the cupric salt. After the double decomposition, the precipitate of the product formed, probably chelate, is filtered off with suction, which is washed until the washing water no longer contains chloride. The dried product generally has 48.2-48.8% copper metal.
The following example illustrates the invention.
60 g of cuprous chloride are dissolved in 500 cm3 of saturated aqueous sodium chloride solution and concentrated hydrochloric acid is added so as to bring the pH of this solution to a value between 3 and 4.
To 205 cm3 of this solution is added, with stirring and under a nitrogen atmosphere, 200 cm8 of saturated sodium chloride solution, check once again that the pH is between 3 and 4 without interrupting the stirring or the current gas, 83 cm3 of sodium ethylene bis-dithiocarbamate solution, the preparation of which is described below, mixed beforehand with 56 cm3 of water and 66 cm3 of water, are introduced fairly quickly (in about five minutes). saturated sodium chloride solution, while maintaining the pH of the mixture between 3 and 4. The mixture is stirred for a few more minutes and filtered. The drained precipitate formed by the new cuprous derivative is washed first with 100 cm3 of saturated sodium chloride solution, then with 100 cm3 of 10% ammonia and finally with water until the washing water is free from chlorides.
It is filtered off thoroughly and dried under vacuum.
Yield: 30.4 g. The product is in the form of a dark brown powder containing 47 to 49% copper, insoluble in water, dilute acids and alkalis as well as in most common solvents. It contains less than 0.25% water-soluble salts.
Sodium ethylene bisdithiocarbamate solution can be obtained as follows:
Into 360 cm3 of 10% aqueous ethylene diamine solution heated to 400 ° C., 96 g of carbon disulfide are introduced, with stirring, in approximately one t12 hour and stirring is continued at 400 ° C. for one hour. Without allowing to cool, 154.5 cm8 of 31% sodium hydroxide are slowly added and the introduction is complete, which requires approximately one hour, stirring is continued for two more hours and the orange-yellow solution obtained is filtered.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR725304 | 1956-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH367162A true CH367162A (en) | 1963-02-15 |
Family
ID=8703937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH5240157A CH367162A (en) | 1956-11-08 | 1957-11-07 | Process for the preparation of a new cuprous derivative of ethylene-bis-dithiocarbamic acid and use of this derivative |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE562210A (en) |
| CH (1) | CH367162A (en) |
| NL (1) | NL99969C (en) |
-
0
- NL NL99969D patent/NL99969C/xx active
- BE BE562210D patent/BE562210A/xx unknown
-
1957
- 1957-11-07 CH CH5240157A patent/CH367162A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL99969C (en) | |
| BE562210A (en) |
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