CH332474A - Process for the preparation of new compounds containing phosphorus and sulfur - Google Patents
Process for the preparation of new compounds containing phosphorus and sulfurInfo
- Publication number
- CH332474A CH332474A CH332474DA CH332474A CH 332474 A CH332474 A CH 332474A CH 332474D A CH332474D A CH 332474DA CH 332474 A CH332474 A CH 332474A
- Authority
- CH
- Switzerland
- Prior art keywords
- alkylene
- formula
- alkyl
- compound
- carbon atoms
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 4
- 239000011574 phosphorus Substances 0.000 title claims description 4
- 229910052717 sulfur Inorganic materials 0.000 title claims description 4
- 239000011593 sulfur Substances 0.000 title claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- 230000001419 dependent effect Effects 0.000 claims 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- -1 cyeloalkyl Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical group N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 230000001225 therapeutic 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have 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)
Description
<Desc/Clms Page number 1>
Verfahren zur Herstellung von neuen, Phosphor und Schwefel enthaltenden Verbindungen Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung von neuen, Phosphor und Schwefel enthaltenden Verbin- dungen der Formel:
EMI1.7
worin R, 11,1 und R3 organische Reste, wie ge- gebenenfalls substituierte Alkyl-, Cyeloalkyl-, Aralkyl-, Aryl- oder heterocyclische Reste bedeuten, wobei R und R1 auch unter sich verbunden sein können und worin R2 einen zweiwertigen aliphatischen Rest, wie einen gegebenenfalls durch Heteroatome unterbrochenen Alkylenrest, und X und Y -0-, -S-, -NI-I- oder >NU bedeuten, welches dadurch gekennzeichnet ist,
dass man eine Verbindung der Formel
EMI1.26
mit einer solchen der Formel CCI3COOR2SR3 umsetzt, wobei in diesen Formeln R, R i, R2, R3, X und Y die oben gegebene Bedeutung haben und R4 für einen niedrigen Alkylrest steht.
Die nach dem erfindungsgemässen Verfahren erhaltenen neuen Verbindungen stellen wertvolle Schädlingsbekämpfungsmittel dar. Zum Teil besitzen sie innertherapeutische, sog. systemische Wirkung.
Die organischen Reste, die durch die Sym- bole R, R1 und R3 in den oben angegebenen Formeln dargestellt werden, können geradket- tige, verzweigte, gesättigte oder ungesättigte, ferner substituierte oder ursubstituierte ali- phatische Reste sein. Genannt seien z.
B. folgende Gruppen: Methyl-, Äthyl-,. Propyl-, Iso- propyl-, Butyl-, Hexyl-, 2-Äthyl-butyl-, Octyl-, 2-Butyl-octyl-, Lauryl-, Octadecyl-, Allyl-, 2- Chlor-äthyl-, ferner Radikale mit Hydroxyl-, Rhodan-, Cyan- oder Estergruppen. Die Reste R, Ri und R3 können gleich oder verschieden sein.
Aromatische Radikale, die durch R, R1 und R3 dargestellt werden, können ein- oder mehrkernig sein und können gegebenenfalls noch Kernsubstituenten tragen; erwähnt seien Phenyl-, 2- oder 4-Chlor-phenyl, 2,4-Diehlor- phenyl-, 4-lllethoxy-phenyl-, 4-Nitro-phenyl-, Naphthyl- oder 4-Diphenylreste. Unter den araliphatischen Radikalen, die durch R, R1' und R3 dargestellt werden, sei der Benzyl-,
unter den cycloaliphatischen der Cyclohexyl- und unter den heterocyclischen der Tetra- hydrofurfurylrest erwähnt. Vorzugsweise sind die Reste R, R.1 und R3 niedrigm.olekulare Alkylreste. Die Symbole X und Y stellen bevorzugt -0- oder >NRi dar. Für den Rest R2 kommen insbesondere niedrigmolekulare, gegebenenfalls durch Heteroatome unterbrochene Alkvlenreste in Betracht.
Genannt seien beispielsweise folgende:
<Desc/Clms Page number 2>
EMI2.1
Verbindungen mit besonders wertvollen Eigenschaften werden erhalten, wenn man, entweder a) Eine Verbindung der Formel
EMI2.5
mit einer Verbindung der Formel CC13C00-alkylen-S-alkyl umsetzt, wobei in den Formeln alliyl für lUkylreste mit 1-4 Kohlenstoffatomen und alkylen für einen Alkylenrest mit 2-4 Koh- lenstoffatomen stehen, oder b)
eine Verbindung der Formel
EMI2.20
mit einer Verbindung der Formel CC13C00-alkylen-S-alkyl umsetzt, wobei in den Formeln alkyl für Alkylreste mit 1-4 Kohlenstoffatomen und alkylen für einen Alkylenrest mit 2-4 Kohlenstoffatomen stehen, oder c) eine Verbindung der Formel
EMI2.34
mit einer Verbindung der Formel CC13C00-alkylen-S-ällz:
yl iunsetzt, wobei in den Formeln alkyl für Alkylreste mit 1-4 Kohlenstoffatomen und alkylen für einen Alkylenrest mit 2-4 Koh- lenstoffatomen stehen.
eil beim erfindungsgemässen Verfahren die.Reaktion oft exotherm verläuft, ist es gegebenenfalls notwendig, die Komponenten Butter Kühlung zu vereinigen und mit inerten Lösungsmitteln, wie Benzol, Toluol, Äther, Dioxan, Hexan oder tiefsiedendem Benzin, zu verdünnen. Die Reaktion wird vorteilhaft durch Erwärmen auf etwa 50-120 beendet.- Unter den Kondensationsprodukten gibt es solche, die sich unter vermindertem Druck destillieren lassen.
Die netten Verbindungen können als einzige Wirkstoffe in einem Schädlingsbekämp- fungsmittel vorhanden sein oder auch in Kom; bination mit andern Insekticiden und/oder Fingiciden. Die Verwendung solcher Präparate im Pflanzenschutz erfolgt nach den üblichen Spritz- und Stäubeverfahren.
In den folgenden Beispielen bedeuten Teile Gewichtsteile. Das Verhältnis von Gewichtsteil zu Volumteil ist das gleiche wie dasjenige zwischen dem Kilogramm und dem Liter. Die Temperaturen sind in Celsiusgraden angegeben.
Beispiel 1 8 Teile des Esters aus Trichloressigsäure und ss-Oxyäthyl-methylsulfid werden mit 5,5 Teilen Triäthylphosphit vermischt. Die nach kurzer Zeit einsetzende Steigerung der Temperatur wird durch schwache Kühlung etwas gemildert, so dass die Reaktion bei etwa 70 vor sich geht.
Wenn die Temperatur zu sinken beginnt, wird während 15 Minuten auf dem Dampfbad erhitzt und das entstandene Chloräthyl abdestilliert. Nach kurzem Erhitzen des Rückstandes auf 90-100 im Vak.nim von 0,5 mm werden 9,8 Teile eines bräunlich gefärbten öls erhalten, das in den gebräuchlichen organischen Lösungsmitteln löslich ist. Beispiel 2 Ein Gemisch von 9,6 Teilen des Esters aus Trichloressigsäilre und ss-Oxy-diäthylsulfid und 9,1.5 Teilen Triäthylphosphit wird sieh
<Desc/Clms Page number 3>
selbst überlassen.
Nach kurzer Zeit steigt die Temperatur langsam auf 70-80 unter Gasentwicklung. Wenn die Temperatur zu fallen beginnt, wird während 10 Minuten auf dem Dampfbad erhitzt, worauf die Gasentwicklung beendet ist. Nach dem Entfernen der flüchtigen Anteile im Vakuum werden 12,9 Teile eines bräunlich gefärbten Öls erhalten.
<Desc / Clms Page number 1>
Process for the preparation of new, phosphorus and sulfur-containing compounds The present invention relates to a process for the preparation of new, phosphorus and sulfur-containing compounds of the formula:
EMI1.7
in which R, 11,1 and R3 represent organic radicals, such as optionally substituted alkyl, cyeloalkyl, aralkyl, aryl or heterocyclic radicals, where R and R1 can also be linked and where R2 is a divalent aliphatic radical, such as an alkylene radical optionally interrupted by heteroatoms, and X and Y mean -0-, -S-, -NI-I- or> NU, which is characterized by
that you can get a compound of the formula
EMI1.26
with one of the formula CCI3COOR2SR3, where in these formulas R, R i, R2, R3, X and Y have the meaning given above and R4 stands for a lower alkyl radical.
The new compounds obtained by the process according to the invention are valuable pesticides. Some of them have an internal therapeutic, so-called systemic effect.
The organic radicals which are represented by the symbols R, R1 and R3 in the formulas given above can be straight-chain, branched, saturated or unsaturated, further substituted or unsubstituted aliphatic radicals. For example
B. the following groups: methyl, ethyl ,. Propyl, isopropyl, butyl, hexyl, 2-ethyl-butyl, octyl, 2-butyl-octyl, lauryl, octadecyl, allyl, 2-chloro-ethyl, and also radicals Hydroxyl, rhodan, cyano or ester groups. The radicals R, Ri and R3 can be identical or different.
Aromatic radicals represented by R, R1 and R3 can be mononuclear or polynuclear and can optionally also carry nuclear substituents; Phenyl, 2- or 4-chlorophenyl, 2,4-diehlorphenyl, 4-III-ethoxyphenyl, 4-nitro-phenyl, naphthyl or 4-diphenyl radicals may be mentioned. Among the araliphatic radicals represented by R, R1 'and R3, let the benzyl,
among the cycloaliphatic the cyclohexyl and among the heterocyclic the tetrahydrofurfuryl radical. The radicals R, R.1 and R3 are preferably low molecular weight alkyl radicals. The symbols X and Y preferably represent -0- or> NRi. Particularly suitable for the radical R2 are low molecular weight alkylene radicals which may be interrupted by heteroatoms.
For example, the following are mentioned:
<Desc / Clms Page number 2>
EMI2.1
Compounds with particularly valuable properties are obtained when either a) A compound of the formula
EMI2.5
with a compound of the formula CC13C00-alkylene-S-alkyl, where in the formulas alliyl stands for alkyl radicals with 1-4 carbon atoms and alkylene stands for an alkylene radical with 2-4 carbon atoms, or b)
a compound of the formula
EMI2.20
with a compound of the formula CC13C00-alkylene-S-alkyl, where in the formulas alkyl stands for alkyl radicals with 1-4 carbon atoms and alkylene stands for an alkylene radical with 2-4 carbon atoms, or c) a compound of the formula
EMI2.34
with a compound of the formula CC13C00-alkylen-S-ällz:
yl, where in the formulas alkyl stands for alkyl radicals with 1-4 carbon atoms and alkylene stands for an alkylene radical with 2-4 carbon atoms.
Since the reaction in the process according to the invention is often exothermic, it may be necessary to combine the butter cooling components and to dilute them with inert solvents such as benzene, toluene, ether, dioxane, hexane or low-boiling gasoline. The reaction is advantageously terminated by heating to about 50-120. Among the condensation products there are those which can be distilled under reduced pressure.
The nice compounds can be present as the only active ingredients in a pesticide or in com; combination with other insecticides and / or fingicides. The use of such preparations in crop protection takes place according to the usual spray and dusting methods.
In the following examples, parts mean parts by weight. The ratio of part by weight to part by volume is the same as that between the kilogram and the liter. The temperatures are given in degrees Celsius.
Example 1 8 parts of the ester of trichloroacetic acid and ß-oxyethyl methyl sulfide are mixed with 5.5 parts of triethyl phosphite. The rise in temperature that sets in after a short time is somewhat mitigated by weak cooling, so that the reaction takes place at around 70.
When the temperature begins to drop, the mixture is heated on the steam bath for 15 minutes and the chloroethyl formed is distilled off. After briefly heating the residue to 90-100 in a vacuum of 0.5 mm, 9.8 parts of a brownish oil are obtained, which is soluble in common organic solvents. Example 2 A mixture of 9.6 parts of the ester of trichloroacetic acid and β-oxy-diethyl sulfide and 9.1.5 parts of triethyl phosphite is shown
<Desc / Clms Page number 3>
left to yourself.
After a short time the temperature rises slowly to 70-80 with evolution of gas. When the temperature begins to fall, the steam bath is heated for 10 minutes, after which the evolution of gas ceases. After removing the volatile components in vacuo, 12.9 parts of a brownish oil are obtained.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH332474T | 1954-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH332474A true CH332474A (en) | 1958-09-15 |
Family
ID=4502451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH332474D CH332474A (en) | 1954-11-17 | 1954-11-17 | Process for the preparation of new compounds containing phosphorus and sulfur |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH332474A (en) |
-
1954
- 1954-11-17 CH CH332474D patent/CH332474A/en unknown
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