BE563341A - - Google Patents
Info
- Publication number
- BE563341A BE563341A BE563341DA BE563341A BE 563341 A BE563341 A BE 563341A BE 563341D A BE563341D A BE 563341DA BE 563341 A BE563341 A BE 563341A
- Authority
- BE
- Belgium
- Prior art keywords
- emi
- solutions
- high vacuum
- water
- solvent
- Prior art date
Links
- 150000002148 esters Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 241001124076 Aphididae Species 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 241000238876 Acari Species 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- UCQRPBLOYKRHFQ-UHFFFAOYSA-N CCOP(O)([ClH]CC)=S Chemical compound CCOP(O)([ClH]CC)=S UCQRPBLOYKRHFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- -1 ethylmercapto compound Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000009885 systemic effect Effects 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
<EMI ID=1.1>
pylique de constitution suivante :
<EMI ID=2.1>
<EMI ID=3.1>
pyliques ainsi obtenus peuvent, également par des méthodes connues, être chlorés avec du chlorure de thionyle, obtenant à partir de l'alcool secondaire le chlorure secondaire correspondant. Dans le cas du composé éthylmercapto on obtient les composés suivants A et B
<EMI ID=4.1>
On peut obtenir aisément les produits de réaction des chlorures d'acides dialcoylthionophosphoriques avec les alcools A en présence d'un agent fixateur d'acide (par exemple de la pyridine). Les chlorures B réagissent aisément avec les acides dialcoylthiol- ou dialcoylthionothiolphosphoriques, ou leurs sels, obtenant en l'occurrence les esters isomères thiol- ou thiol-thionophosphoriques analogues.
Les produits du procédé, obtenables de manière simple conformément à l'invention, se caractérisent par une excellente activité insecticide de contact. En même temps ces nouveaux composés développent une ac-
<EMI ID=5.1>
actifs dans le cas des.espèces de mites fileuses qui présentent déjà une certaine résistance envers les esters phosphoriques. L'application des nouveaux composés se fait de la manière usuelle pour les esters phosphoriques de constitution analogue, à savoir le plus souvent en combinaison avec les agents d'épandage ou de dilution usuels solides ou liquides.
Les exemples suivants expliquent le procédé.
EXEMPLE 1.
<EMI ID=6.1>
<EMI ID=7.1> <EMI ID=8.1>
fois. On sépare-la solution chloroformique, on la sèche avec du sulfate de sodium et on élimine le solvant par distillation. On obtient ainsi 42 g du nouvel ester sous la forme d'une huile brun clair, insoluble dans l'eau. Même sous vide poussé le nouvel ester ne distille pas.
<EMI ID=9.1>
EXEMPLE 2.
<EMI ID=10.1>
<EMI ID=11.1>
60 [deg.]C) tout en agitant à 45[deg.]C à une solution de 35 g de diéthylthiolphosphate d'ammonium dans 150 cm3 d'alcool anhydre. On maintient le produit de réaction pendant 20 heures à 60[deg.]C tout en agitant. Après cette période on refroidit à la température ordinaire. Le sel d'ammonium précipité est séparé par filtration et on élimine ensuite le solvant par distillation. Le résidu obtenu est repris dans 100cm3 d'éther et lavé à deux reprises chaque fois avec 40 cm3 d'eau. On sèche la solution étherée avec du sulfate de sodium. Après avoir chassé l'éther par distillation on obtient 36 g du nouvel ester sous la forme d'une huile jaune insoluble dans l'eau, non distillable même sous un vide poussé.
<EMI ID=12.1>
Les mites fileuses sont encore tuées à 100% à des concentrations de 0,001%. Les pucerons de même sont tués à 100% à des concentrations de 0,001%. En outre le composé présente une activité systémique prononcée.
EXEMPLE 3.
<EMI ID=13.1>
On dissout 29 g d'acide diéthyldithiophosphorique dans une solution d'
<EMI ID=14.1>
température ordinaire, on sépare par filtration sous vide le chlorure de sodium obtenu et on chasse le solvant par distillation. Le produit brut obtenu est clarifié par filtration sur du charbon actif. On obtient 34 g du nouvel ester sous la forme d'huile brun clair insoluble dans l'eau. Le composé n'est pas distillable, même sous! vide poussé,
Rendement 72,5% de la théorie.
<EMI ID=15.1>
Les mites fileuses sont tuées à 100% avec des solutions aqueuses qui contiennent 0,01% du composé. En outre le composé exerce une action ovicide marquée sur les oeufs des mites fileuses. Les pucerons sont encore tués à
60% à des concentrations de 0,0001%.
EXEMPLE 4.
<EMI ID=16.1>
On mélange 38 g de monochlorure d'acide diéthylthionophosphorique 'avec
<EMI ID=17.1>
sout le prodiut de réaction dans 120 cm3 de chloroforme. La solution chloroformique est extraite par agitation avec 100 cm3 d'eau glacée et 15 cm3 d'acide chlorhydrique concentré. On'sépare alors la phase aqueuse et on
<EMI ID=18.1>
d'eau. Après séchage de la solution chloroformique sur du sulfate de sodium on chasse par distillation le solvant. On maintient encore le résidu pendant 2 heures à une température de bain de 110[deg.]C sous une pression de 2,5 mm. On obtient ainsi 65 g du nouvel ester sous la forme d'une huile brune insoluble dans l'eau que l'on n'arrive pas à distiller, même
<EMI ID=19.1>
DL 0 chez le rat per os : 100 mg/kg.
Les mites fileuses et les pucerons sont tués à 100% avec des solutions à 0,01%. Les solutions à 0,1% tuent de même à 100% les chenilles.
EXEMPLE 5.
<EMI ID=20.1>
On mélange 32 g de monochlorure d'acide diéthylthionophosphorique et 27
<EMI ID=21.1>
alcool 3-chloro-l-cyano-isopropylique et du sel sodique de l'isopropylmercaptan en solution alcoolique ;
P.E. 0,01 mm/87-88[deg.]C). Tout en agitant on ajoute goutte à goutte à ce mélange 15 g de pyridine anhydre. Puis on agite le produit de réaction pendant 5 heures à 55[deg.]C. Après déclin de la réaction on ajoute le mélange
de réaction à 120 g de glace à laquelle on a ajouté 10 g d'acide chlorhydrique concentré. L'huile qui s'est séparée est reprise dans du chlorure de méthylène et lavée plusieurs fois à l'eau. Après séchage et enlèvement du solvant par distillation on chauffe pendant peu de temps le rési�
<EMI ID = 1.1>
pylic of the following constitution:
<EMI ID = 2.1>
<EMI ID = 3.1>
Pyliques thus obtained can, also by known methods, be chlorinated with thionyl chloride, obtaining from the secondary alcohol the corresponding secondary chloride. In the case of the ethylmercapto compound, the following compounds A and B are obtained
<EMI ID = 4.1>
The reaction products of the dialkylthionophosphoric acid chlorides with the A-alcohols can easily be obtained in the presence of an acid scavenger (eg pyridine). Chlorides B easily react with dialkylthiol- or dialkoylthionothiolphosphoric acids, or their salts, in this case obtaining thiol- or thiol-thionophosphoric isomeric esters which are analogous.
The products of the process, obtainable in a simple manner in accordance with the invention, are characterized by excellent contact insecticidal activity. At the same time these new compounds develop an ac-
<EMI ID = 5.1>
active in the case of species of spinning moths which already show some resistance to phosphoric esters. The application of the new compounds is carried out in the usual way for phosphoric esters of similar constitution, namely most often in combination with the usual solid or liquid spreading or diluting agents.
The following examples explain the process.
EXAMPLE 1.
<EMI ID = 6.1>
<EMI ID = 7.1> <EMI ID = 8.1>
times. The chloroform solution is separated, dried with sodium sulfate and the solvent is removed by distillation. 42 g of the new ester are thus obtained in the form of a light brown oil, insoluble in water. Even under high vacuum the new ester does not distill.
<EMI ID = 9.1>
EXAMPLE 2.
<EMI ID = 10.1>
<EMI ID = 11.1>
60 [deg.] C) while stirring at 45 [deg.] C to a solution of 35 g of ammonium diethylthiolphosphate in 150 cm3 of anhydrous alcohol. The reaction product is maintained for 20 hours at 60 ° C. while stirring. After this period it is cooled to room temperature. The precipitated ammonium salt is separated by filtration and then the solvent is removed by distillation. The residue obtained is taken up in 100 cm3 of ether and washed twice each time with 40 cm3 of water. The ethereal solution is dried with sodium sulfate. After having removed the ether by distillation, 36 g of the new ester are obtained in the form of a yellow oil insoluble in water, which cannot be distilled even under a high vacuum.
<EMI ID = 12.1>
Spinning moths are still 100% killed at 0.001% concentrations. Aphids likewise are killed 100% at concentrations of 0.001%. In addition, the compound exhibits pronounced systemic activity.
EXAMPLE 3.
<EMI ID = 13.1>
29 g of diethyldithiophosphoric acid are dissolved in a solution of
<EMI ID = 14.1>
room temperature, the sodium chloride obtained is filtered off under vacuum and the solvent is distilled off. The crude product obtained is clarified by filtration through activated carbon. 34 g of the new ester are obtained in the form of a light brown oil insoluble in water. The compound is not distillable, even under! high vacuum,
Yield 72.5% of theory.
<EMI ID = 15.1>
Spinning moths are killed 100% with aqueous solutions that contain 0.01% of the compound. In addition, the compound exerts a marked ovicidal action on the eggs of the spinning moths. Aphids are still killed at
60% at concentrations of 0.0001%.
EXAMPLE 4.
<EMI ID = 16.1>
38 g of diethylthionophosphoric acid monochloride are mixed with
<EMI ID = 17.1>
Support the reaction product in 120 cm3 of chloroform. The chloroform solution is extracted by stirring with 100 cm3 of ice-cold water and 15 cm3 of concentrated hydrochloric acid. The aqueous phase is then separated and
<EMI ID = 18.1>
of water. After drying the chloroform solution over sodium sulfate, the solvent is distilled off. The residue is still maintained for 2 hours at a bath temperature of 110 [deg.] C under a pressure of 2.5 mm. 65 g of the new ester are thus obtained in the form of a brown oil insoluble in water which cannot be distilled, even
<EMI ID = 19.1>
LD 0 in the rat per os: 100 mg / kg.
Spinning mites and aphids are killed 100% with 0.01% solutions. 0.1% solutions also kill 100% caterpillars.
EXAMPLE 5.
<EMI ID = 20.1>
32 g of diethylthionophosphoric acid monochloride and 27
<EMI ID = 21.1>
3-chloro-1-cyano-isopropyl alcohol and sodium salt of isopropylmercaptan in alcoholic solution;
P.E. 0.01 mm / 87-88 [deg.] C). While stirring, 15 g of anhydrous pyridine is added dropwise to this mixture. Then the reaction product is stirred for 5 hours at 55 ° C. After the reaction has declined, the mixture is added
reaction mixture to 120 g of ice to which 10 g of concentrated hydrochloric acid was added. The oil which has separated is taken up in methylene chloride and washed several times with water. After drying and removing the solvent by distillation, the residue is heated for a short time.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF21987A DE1036846B (en) | 1956-12-21 | 1956-12-21 | Process for the preparation of thiophosphoric acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
BE563341A true BE563341A (en) |
Family
ID=7090278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
BE563341D BE563341A (en) | 1956-12-21 |
Country Status (4)
Country | Link |
---|---|
BE (1) | BE563341A (en) |
CH (1) | CH364773A (en) |
DE (1) | DE1036846B (en) |
FR (1) | FR1188859A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1191991B (en) * | 1959-11-10 | 1965-04-29 | Basf Ag | Insecticides |
NL286054A (en) * | 1961-11-28 | |||
DE1192202B (en) * | 1963-06-24 | 1965-05-06 | Bayer Ag | Process for the production of (thiono) phosphorus (on, in) acid esters |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE836349C (en) * | 1950-05-10 | 1952-04-10 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
DE830509C (en) * | 1950-05-24 | 1952-02-04 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
DE917668C (en) * | 1952-08-01 | 1954-09-09 | Bayer Ag | Process for the preparation of neutral esters of dithiophosphoric acid |
NL191318A (en) * | 1953-10-07 |
-
0
- BE BE563341D patent/BE563341A/fr unknown
-
1956
- 1956-12-21 DE DEF21987A patent/DE1036846B/en active Pending
-
1957
- 1957-11-26 CH CH5308757A patent/CH364773A/en unknown
- 1957-12-20 FR FR1188859D patent/FR1188859A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CH364773A (en) | 1962-10-15 |
FR1188859A (en) | 1959-09-25 |
DE1036846B (en) | 1958-08-21 |
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