BE606300A - - Google Patents

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Publication number
BE606300A
BE606300A BE606300DA BE606300A BE 606300 A BE606300 A BE 606300A BE 606300D A BE606300D A BE 606300DA BE 606300 A BE606300 A BE 606300A
Authority
BE
Belgium
Prior art keywords
emi
mixture
immediate
amines
hydrochlorides
Prior art date
Application number
Other languages
French (fr)
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.)
Publication of BE606300A publication Critical patent/BE606300A/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14Dithiocarbamic acids; Derivatives thereof
    • C07C333/16Salts of dithiocarbamic acids
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14Di-thio analogues thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

       

   <EMI ID=1.1> 

  
 <EMI ID=2.1>  La présente invention a pour objet des oomposés fongicides contenant comme substance active un mélange de sels insolubles formés par un métal, de préférence le zinc, avec des acides al-

  
 <EMI ID=3.1> 

  
Cette invention a aussi pour objet un procédé pour la préparation des composés ci-dessus.

  
 <EMI ID=4.1> 

  
des alcoylènedithiocarbamates sont connues depuis longtemps.

  
Parmi les composés de ce dernier type, l'éthylène-bis-

  
 <EMI ID=5.1> 

  
importance pratique remarquable comme fongicide servant, dans l'agriculture, à lutter contre le mildiou de la vigne, de la pomme de terre et de la tomate et d'autres maladies cryptogamiquas de moindre importance touchant d'autres végétaux, et à protéger le pommier et le poirier contre la tavelure et dtautres maladies oryptogamiques.

  
Comme on le sait, le procédé industriel de préparation de l'éthylène diamine consiste à faire réagir le dichloréthane et l'ammoniac.

  
 <EMI ID=6.1> 

  
 <EMI ID=7.1> 

  
amine et des composés azotés cycliques qui constituent, dans leur ensemble, le sous-produit de ce procédé.

  
On sépare les amines de leurs chlorhydrates en traitant

  
 <EMI ID=8.1> 

  
 <EMI ID=9.1> 

  
on obtient une solution aqueuse contenant le mélange qui est formé d'éthylènediamine et de polyalcoylènepolyamines,

  
 <EMI ID=10.1> 

  
calcium provenant de la décomposition des chlorhydrates.

  
 <EMI ID=11.1> 

  
 <EMI ID=12.1>  

  
plus de petites quantités de composés azotés cycliques qui sont formés en majeure partie de pipérazine.

  
De façon surprenante, la demanderesse a trouvé mainte-

  
 <EMI ID=13.1> 

  
 <EMI ID=14.1> 

  
 <EMI ID=15.1> 

  
 <EMI ID=16.1>  

  
 <EMI ID=17.1> 

  
 <EMI ID=18.1> 

  
présente invention peut varier entre certaines limites (ces limites dépendait des conditions dans lesquelles on a fait

  
 <EMI ID=19.1> 

  
 <EMI ID=20.1> 

  
 <EMI ID=21.1> 

  
 <EMI ID=22.1> 

  
 <EMI ID=23.1> 

  
 <EMI ID=24.1> 

  
 <EMI ID=25.1> 

  
 <EMI ID=26.1> 

  
procédé ci-dessus présente une activité fongicide non seule-

  
 <EMI ID=27.1>  <EMI ID=28.1>  <EMI ID=29.1> 

  
 <EMI ID=30.1> 

  
 <EMI ID=31.1>   <EMI ID=32.1> 

  
 <EMI ID=33.1> 

  
thermomètre, d'un réfrigérant à reflux et d'un entonnoir

  
 <EMI ID=34.1> 

  
 <EMI ID=35.1> 

  
t< _.,, 

  
 <EMI ID=36.1> 

  
Après avoir agité la mélange pendant 15 minutes, on

  
 <EMI ID=37.1> 

  
 <EMI ID=38.1> 

  
 <EMI ID=39.1> 

  
 <EMI ID=40.1> 

  
 <EMI ID=41.1>  

  
Tableau 1.

  
Evaluation de l'activité fongicide immédiate.

  

 <EMI ID=42.1> 


  
 <EMI ID=43.1> 

  
 <EMI ID=44.1> 

  
 <EMI ID=45.1> 

  
 <EMI ID=46.1> 

  
thermomètre, d'un réfrigérant 'reflux et d'un entonnoir

  
 <EMI ID=47.1> 

  
260 de, 

  
 <EMI ID=48.1> 

  
 <EMI ID=49.1> 

  
 <EMI ID=50.1>  

  
 <EMI ID=51.1> 

  
 <EMI ID=52.1> 

  
 <EMI ID=53.1> 

  
 <EMI ID=54.1> 

  
 <EMI ID=55.1> 

  
 <EMI ID=56.1>  <EMI ID=57.1> 

  
chauffant à 4000 pendant 1 heure. 

  
Après avoir agité pendant 30 minâtes, on filtre le mélange, on le lave et on le sèche ; on obtient 410 g d'an

  
 <EMI ID=58.1> 

  
 <EMI ID=59.1> 

Exemple 2.

  
 <EMI ID=60.1> 

  
 <EMI ID=61.1> 

  
 <EMI ID=62.1> 

  
 <EMI ID=63.1> 

  
dans la solution d'éthylènediamine et de polyéthylène-  diamine), puis, en l'espace d'une heure, au mélangé agit*

  
 <EMI ID=64.1> 

  
qui présente les caractéristiques suivantes : 

  

 <EMI ID=65.1> 
 

  
(La composition du mélange ci-dessus correspond à celle que l'on obtient industriellement en faisant réagir la diohloréthane et l'ammoniac, puis an décomposant les,, chlorhydrates d'aminé ainsi obtenues au moyen de soude caustique)*

  
 <EMI ID=66.1> 

  
 <EMI ID=67.1> 

  
 <EMI ID=68.1> 

  
 <EMI ID=69.1> 

  
 <EMI ID=70.1> 

  
 <EMI ID=71.1> 

  
 <EMI ID=72.1> 

  
 <EMI ID=73.1> 

  
 <EMI ID=74.1> 

  
 <EMI ID=75.1> 

  
 <EMI ID=76.1> 

  
 <EMI ID=77.1> 

  
la composition suivante 
 <EMI ID=78.1> 
  <EMI ID=79.1> 

  
 <EMI ID=80.1> 

  
 <EMI ID=81.1> 

  
 <EMI ID=82.1> 

  
 <EMI ID=83.1> 

  
 <EMI ID=84.1> 

  
Au bout de 30 minutes, on filtre le mélange, on lave

  
 <EMI ID=85.1> 

  
 <EMI ID=86.1> 

  
 <EMI ID=87.1>  <EMI ID=88.1> 

  
 <EMI ID=89.1> 

  
,tamisant méthodes différentes, résumées brièvement ci-dessous : 

  
1ère méthode

  
 <EMI ID=90.1> 

  
 <EMI ID=91.1> 

  
 <EMI ID=92.1> 

  
 <EMI ID=93.1> 

  
 <EMI ID=94.1> 

  
Essai d'activité contre le peronospora,

  
On rassemble des feuilles de vigne que l'on a cultivées

  
 <EMI ID=95.1> 

  
 <EMI ID=96.1> 

  
 <EMI ID=97.1> 

  
petit morceau d'épongé artificielle imbibée d'eau.

  
 <EMI ID=98.1> 

  
le haut, on les traite par des suspensions aqueuses des produits à examiner et, en séchant le dépôt, on les infecte avec des conidies de peronospora.

  
Au bout de 12 jours, on lit les résultats en dénombrant les taches d'infection de peronospora sur chaque feuille.

  
 <EMI ID=99.1> 

  
 <EMI ID=100.1> 

  
On traite les deux feuilles primaires 4* un jeune plant

  
 <EMI ID=101.1> 

  
 <EMI ID=102.1> 

  
spores de mildiou. 

  
Au bout de 15 Jours, on dénombre les sur chaque

  
 <EMI ID=103.1>  l'objet de la. présente intention. invention. 

  
 <EMI ID=104.1> 

  
 <EMI ID=105.1> 

  
 <EMI ID=106.1> 

  
 <EMI ID=107.1> 

  
 <EMI ID=108.1> 

  
tire las chiffres cités au tableau 5 lorsqu'on, appelle 

  
 <EMI ID=109.1> 

  
suivant des méthodes connues. 

  
 <EMI ID=110.1> 

  
à la concentration de 500 parties de substance active par

  
 <EMI ID=111.1> 

  
 <EMI ID=112.1>  

  
lecture exacte au microscope n'est plus possible et pour certains produits ces inconvénients apparaissent déjà à la concentration de 500 Parties par million.

  
Tableau 2.

  
Essais pour 1'évaluation de 1'activité fongicide immédiate sur

  
 <EMI ID=113.1> 

  
 <EMI ID=114.1> 

  
sur.4 répétitions pour chaque produit.

  

 <EMI ID=115.1> 
 

  
Tableau' .

  
Essais pour dévaluation de l'activité immédiate contre le

  
 <EMI ID=116.1> 

  
 <EMI ID=117.1> 

  

 <EMI ID=118.1> 
 

  
 <EMI ID=119.1> 

  
Basais pour l'évaluation de l'activité fongicide immédiate

  
 <EMI ID=120.1> 

  
chaque dose dans chaque essai ; moyenne de deux ou trois répétitions pour chaque dose de chaque produit.

  

 <EMI ID=121.1> 


  
 <EMI ID=122.1> 

  
 <EMI ID=123.1> 

  
données figurant aux tableaux précédents, si l'on appelle 1

  
 <EMI ID=124.1>  <EMI ID=125.1> 

  

 <EMI ID=126.1> 




   <EMI ID = 1.1>

  
 <EMI ID = 2.1> The present invention relates to fungicidal oomposées containing as active substance a mixture of insoluble salts formed by a metal, preferably zinc, with al-

  
 <EMI ID = 3.1>

  
This invention also relates to a process for the preparation of the above compounds.

  
 <EMI ID = 4.1>

  
alkylenedithiocarbamates have been known for a long time.

  
Among the compounds of the latter type, ethylene-bis-

  
 <EMI ID = 5.1>

  
remarkable practical importance as a fungicide used in agriculture to control downy mildew in grapes, potatoes and tomatoes and other fungal diseases of lesser importance affecting other plants, and to protect apple trees and pear against scab and other origins diseases.

  
As is known, the industrial process for preparing ethylene diamine consists in reacting dichloroethane and ammonia.

  
 <EMI ID = 6.1>

  
 <EMI ID = 7.1>

  
amine and cyclic nitrogen compounds which as a whole constitute the by-product of this process.

  
Amines are separated from their hydrochlorides by treating

  
 <EMI ID = 8.1>

  
 <EMI ID = 9.1>

  
an aqueous solution is obtained containing the mixture which is formed of ethylenediamine and polyalkylenepolyamines,

  
 <EMI ID = 10.1>

  
calcium from the decomposition of hydrochlorides.

  
 <EMI ID = 11.1>

  
 <EMI ID = 12.1>

  
plus small amounts of cyclic nitrogen compounds which are formed mostly from piperazine.

  
Surprisingly, the plaintiff has now found

  
 <EMI ID = 13.1>

  
 <EMI ID = 14.1>

  
 <EMI ID = 15.1>

  
 <EMI ID = 16.1>

  
 <EMI ID = 17.1>

  
 <EMI ID = 18.1>

  
present invention may vary between certain limits (these limits depended on the conditions under which we made

  
 <EMI ID = 19.1>

  
 <EMI ID = 20.1>

  
 <EMI ID = 21.1>

  
 <EMI ID = 22.1>

  
 <EMI ID = 23.1>

  
 <EMI ID = 24.1>

  
 <EMI ID = 25.1>

  
 <EMI ID = 26.1>

  
above process exhibits non-only fungicidal activity.

  
 <EMI ID = 27.1> <EMI ID = 28.1> <EMI ID = 29.1>

  
 <EMI ID = 30.1>

  
 <EMI ID = 31.1> <EMI ID = 32.1>

  
 <EMI ID = 33.1>

  
thermometer, reflux condenser and funnel

  
 <EMI ID = 34.1>

  
 <EMI ID = 35.1>

  
t <_. ,,

  
 <EMI ID = 36.1>

  
After stirring the mixture for 15 minutes,

  
 <EMI ID = 37.1>

  
 <EMI ID = 38.1>

  
 <EMI ID = 39.1>

  
 <EMI ID = 40.1>

  
 <EMI ID = 41.1>

  
Table 1.

  
Evaluation of immediate fungicidal activity.

  

 <EMI ID = 42.1>


  
 <EMI ID = 43.1>

  
 <EMI ID = 44.1>

  
 <EMI ID = 45.1>

  
 <EMI ID = 46.1>

  
thermometer, reflux condenser and funnel

  
 <EMI ID = 47.1>

  
260 of,

  
 <EMI ID = 48.1>

  
 <EMI ID = 49.1>

  
 <EMI ID = 50.1>

  
 <EMI ID = 51.1>

  
 <EMI ID = 52.1>

  
 <EMI ID = 53.1>

  
 <EMI ID = 54.1>

  
 <EMI ID = 55.1>

  
 <EMI ID = 56.1> <EMI ID = 57.1>

  
heating at 4000 for 1 hour.

  
After stirring for 30 minutes, the mixture is filtered, washed and dried; we get 410 g of a year

  
 <EMI ID = 58.1>

  
 <EMI ID = 59.1>

Example 2.

  
 <EMI ID = 60.1>

  
 <EMI ID = 61.1>

  
 <EMI ID = 62.1>

  
 <EMI ID = 63.1>

  
in the solution of ethylenediamine and polyethylene diamine), then, within an hour, the mixture acts *

  
 <EMI ID = 64.1>

  
which has the following characteristics:

  

 <EMI ID = 65.1>
 

  
(The composition of the above mixture corresponds to that obtained industrially by reacting diohloroethane and ammonia, then by decomposing the ,, amine hydrochlorides thus obtained by means of caustic soda) *

  
 <EMI ID = 66.1>

  
 <EMI ID = 67.1>

  
 <EMI ID = 68.1>

  
 <EMI ID = 69.1>

  
 <EMI ID = 70.1>

  
 <EMI ID = 71.1>

  
 <EMI ID = 72.1>

  
 <EMI ID = 73.1>

  
 <EMI ID = 74.1>

  
 <EMI ID = 75.1>

  
 <EMI ID = 76.1>

  
 <EMI ID = 77.1>

  
the following composition
 <EMI ID = 78.1>
  <EMI ID = 79.1>

  
 <EMI ID = 80.1>

  
 <EMI ID = 81.1>

  
 <EMI ID = 82.1>

  
 <EMI ID = 83.1>

  
 <EMI ID = 84.1>

  
After 30 minutes, the mixture is filtered, washed

  
 <EMI ID = 85.1>

  
 <EMI ID = 86.1>

  
 <EMI ID = 87.1> <EMI ID = 88.1>

  
 <EMI ID = 89.1>

  
, sifting different methods, briefly summarized below:

  
1st method

  
 <EMI ID = 90.1>

  
 <EMI ID = 91.1>

  
 <EMI ID = 92.1>

  
 <EMI ID = 93.1>

  
 <EMI ID = 94.1>

  
Activity test against peronospora,

  
We collect vine leaves that we have cultivated

  
 <EMI ID = 95.1>

  
 <EMI ID = 96.1>

  
 <EMI ID = 97.1>

  
small piece of artificial sponge soaked in water.

  
 <EMI ID = 98.1>

  
at the top, they are treated with aqueous suspensions of the products to be examined and, drying the deposit, they are infected with conidia of peronospora.

  
After 12 days, the results are read by counting the spots of peronospora infection on each leaf.

  
 <EMI ID = 99.1>

  
 <EMI ID = 100.1>

  
We treat the two primary leaves 4 * a young plant

  
 <EMI ID = 101.1>

  
 <EMI ID = 102.1>

  
mildew spores.

  
After 15 days, we count them on each

  
 <EMI ID = 103.1> the subject of the. present intention. invention.

  
 <EMI ID = 104.1>

  
 <EMI ID = 105.1>

  
 <EMI ID = 106.1>

  
 <EMI ID = 107.1>

  
 <EMI ID = 108.1>

  
draws the figures given in table 5 when calling

  
 <EMI ID = 109.1>

  
according to known methods.

  
 <EMI ID = 110.1>

  
at a concentration of 500 parts of active substance per

  
 <EMI ID = 111.1>

  
 <EMI ID = 112.1>

  
exact reading under a microscope is no longer possible and for some products these disadvantages already appear at the concentration of 500 parts per million.

  
Table 2.

  
Tests for the evaluation of immediate fungicidal activity on

  
 <EMI ID = 113.1>

  
 <EMI ID = 114.1>

  
about 4 repetitions for each product.

  

 <EMI ID = 115.1>
 

  
Board' .

  
Tests for devaluation of immediate activity against

  
 <EMI ID = 116.1>

  
 <EMI ID = 117.1>

  

 <EMI ID = 118.1>
 

  
 <EMI ID = 119.1>

  
Basis for the evaluation of immediate fungicidal activity

  
 <EMI ID = 120.1>

  
each dose in each trial; average of two or three repetitions for each dose of each product.

  

 <EMI ID = 121.1>


  
 <EMI ID = 122.1>

  
 <EMI ID = 123.1>

  
data appearing in the preceding tables, if we call 1

  
 <EMI ID = 124.1> <EMI ID = 125.1>

  

 <EMI ID = 126.1>



    

Claims (1)

<EMI ID=127.1> <EMI ID = 127.1> L'invention a pour objet : <EMI ID=128.1> The subject of the invention is: <EMI ID = 128.1> <EMI ID=129.1> <EMI ID = 129.1> <EMI ID=130.1> <EMI ID = 130.1> amines en solution aqueuse obtenu en décomposant par des bases plus fortes que les amines elles-mêmes les chlorhydrates d'amine amines in aqueous solution obtained by decomposing with bases stronger than the amines themselves amine hydrochlorides <EMI ID=131.1> <EMI ID=132.1> <EMI ID = 131.1> <EMI ID = 132.1> <EMI ID=133.1> <EMI ID = 133.1> <EMI ID=134.1> <EMI ID = 134.1> <EMI ID=135.1> <EMI ID = 135.1> <EMI ID=136.1> <EMI ID = 136.1> <EMI ID=137.1> <EMI ID = 137.1> que le métal est le zinc. that the metal is zinc. <EMI ID=138.1> <EMI ID = 138.1> actives les produits ci-dessus. active the above products.
BE606300D 1961-07-19 BE606300A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR868324A FR80120E (en) 1961-07-19 1961-07-19 Process for the preparation of an anticryptogamic product based on ethylenedithiocarbamates

Publications (1)

Publication Number Publication Date
BE606300A true BE606300A (en)

Family

ID=8759581

Family Applications (1)

Application Number Title Priority Date Filing Date
BE606300D BE606300A (en) 1961-07-19

Country Status (3)

Country Link
BE (1) BE606300A (en)
FR (2) FR1148709A (en)
NL (2) NL267310A (en)

Also Published As

Publication number Publication date
FR1148709A (en) 1957-12-13
NL267310A (en)
FR80120E (en) 1963-03-15
NL205932A (en)

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