CH498155A - compounds where R1 and R2=alkyl (1-4C) pref. ethyl R3=phenyl opt. substd. by Cl X=O or S Insecticides with low mammalian toxicity, suitable for use on pla - Google Patents
compounds where R1 and R2=alkyl (1-4C) pref. ethyl R3=phenyl opt. substd. by Cl X=O or S Insecticides with low mammalian toxicity, suitable for use on plaInfo
- Publication number
- CH498155A CH498155A CH1153870A CH1153870A CH498155A CH 498155 A CH498155 A CH 498155A CH 1153870 A CH1153870 A CH 1153870A CH 1153870 A CH1153870 A CH 1153870A CH 498155 A CH498155 A CH 498155A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- phenyl
- hydroxy
- ethyl
- alkyl
- Prior art date
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 4
- 150000001875 compounds Chemical class 0.000 title abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract 3
- 125000000217 alkyl group Chemical group 0.000 title abstract 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title abstract 2
- 239000002917 insecticide Substances 0.000 title abstract 2
- 231100001225 mammalian toxicity Toxicity 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- -1 alkaline earth metal carbonates Chemical class 0.000 claims description 5
- LZTSCEYDCZBRCJ-UHFFFAOYSA-N 1,2-dihydro-1,2,4-triazol-3-one Chemical class OC=1N=CNN=1 LZTSCEYDCZBRCJ-UHFFFAOYSA-N 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000003015 phosphoric acid halides Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 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 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 150000003852 triazoles Chemical class 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000706 filtrate Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 241001465754 Metazoa Species 0.000 abstract 1
- 244000079386 endoparasite Species 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- QCDMYEHBRNFUQG-UHFFFAOYSA-N 1-phenyl-1,2-dihydro-3H-1,2,4-triazol-3-one Chemical compound N1C(=O)N=CN1C1=CC=CC=C1 QCDMYEHBRNFUQG-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- KMJJJTCKNZYTEY-UHFFFAOYSA-N chloro-diethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OCC KMJJJTCKNZYTEY-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDZWWJBAKRLZOK-UHFFFAOYSA-N 2-(3-chlorophenyl)-1h-1,2,4-triazol-5-one Chemical compound N1=C(O)N=CN1C1=CC=CC(Cl)=C1 CDZWWJBAKRLZOK-UHFFFAOYSA-N 0.000 description 1
- UODODGAZACDCBX-UHFFFAOYSA-N 2-(4-chlorophenyl)-1h-1,2,4-triazol-5-one Chemical compound C1=CC(Cl)=CC=C1N1NC(=O)N=C1 UODODGAZACDCBX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XFBJRFNXPUCPKU-UHFFFAOYSA-N chloro-dimethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(Cl)(=S)OC XFBJRFNXPUCPKU-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- BLZPOKQADCMURG-UHFFFAOYSA-N diethyl (1-phenyl-1,2,4-triazol-3-yl) phosphate Chemical compound N1=C(OP(=O)(OCC)OCC)N=CN1C1=CC=CC=C1 BLZPOKQADCMURG-UHFFFAOYSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
Abstract
compounds where R1 and R2=alkyl (1-4C) pref. ethyl R3=phenyl opt. substd. by Cl X=O or S - Insecticides with low mammalian toxicity, suitable for use on plants or against ecto-and endoparasites of animals. - 32.2 g (II) R3=phenyl was suspended in acetone and treated with 38 g (III) R1=R2=Et,X=S, Hal=Cl. 22 g triethylamine was added dropwise and mixture stirred for 6 hours at 50 deg.C. Mixture was cooled, filtered, and the filtrate evaporated to give 60 g (I).
Description
Verfahren zur Herstellung von neuen Phosphorsäureestern Nach der deutschen Patentschrift Nr. 910 652 und der entsprechenden englischen Patentschrift Nr. 713 278 sind Phosphorsäureester bekannt, die einen enolisierbaren Heterocyclus enthalten und zur Schädlingsbekämpfung Verwendung finden können.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung der Phosphorsäureester der Formel I
EMI0001.0003
worin R, und R2 einen Alkylrest mit 1 bis 4 C-Ato- men, vorzugsweise den Äthylrest, R3 den Phenylrest oder durch Chlor substituierte Phenylreste und X Sauerstoff oder Schwefel bedeuten, das dadurch ge- kennzeichnet ist, dass man Phosphorsäurehalogenide der Formel Il
EMI0001.0006
worin Hal für ein Halogenatom, vorzugsweise ein Chloratom steht, mit der obigen Formel entsprechend R, -substituierten 3-Hydroxy-1,2,4-triazolen oder deren Metallsalzen, vorzugsweise deren Na- oder K-Salzen, umsetzt.
Die Umsetzung erfolgt im ersten Falle zweckmässig in Gegenwart von säurebindenden Mitteln, wie Alkali- karbonaten, z. B. Soda, Erdalkalikarbonaten, oder ter tiären Aminen, wie z. B.
Triäthylamin, Dimethylanilin oder Pynidin. Die Reaktion wird durch folgendes Formelschema veranschaulicht:
EMI0001.0015
Die Reaktion kann mit oder ohne Lösungsmittel durchgeführt werden.
Als Lösungsmittel eignen sich alle gebräuchlichen, unter den Reaktionsbedingungen inerten organischen Flüssigkeiten wie Flüssigkeiten wie Aceton, Methyläthylketon, Acetonitril, Essigsäureäthylester, Butylacetat, Tetrahydrofuran, Dioxan, Methylenchlorid, Tetrachlorkohlenstoff, Benzol, Xylol, Chlorbenzol usw. Die Umsetzung erfolgt im allgemeinen bei Tempe raturen von etwa 20-25 C bis zum Siedepunkt der einzelnen Lösungsmittel, vorzugsweise jedoch bei 50-80 C.
Zusatz von Kupferpulver, vorzugsweise zwi schen 1 und 20 Molprozent, kann. die Reaktionsge schwindigkeit günstig beeinflussen.
Die neuen Verbindungen fallen zum Teil als Öle, zum Teil kristallin an. Sie lassen sich nicht unzersetzt destillieren. <I>Beispiel 1</I> 32,2 g (0,2 Mol) 1-Phenyl-3-hydroxy-1,2,4-triazol werden in 250 ml Aceton suspendiert und mit 38 g (0,2 Mol) 0,0-Diäthoxythionophosphorylchlorid ver setzt. Danach werden 22 g (0,22 Mol) Triäthylamin zu getropft und das Gemisch 6 Stunden lang bei ca. 50 C gerührt. Nach dem Abkühlen wird das Triäthylaminhy- drochlorid abfiltriert und aus dem Filtrat das Lösungs mittel durch Verdampfen entfernt.
Man erhält 60 g 1-Phenyl-3-(Diäthoxythionophosphoryloxy)- 1,2,4-triazol als hellbraunes Öl.
EMI0002.0026
C12H16N3O3PS <SEP> Molgewicht <SEP> 313
<tb> berechnet: <SEP> N <SEP> 13,5 <SEP> % <SEP> P <SEP> 9,9 <SEP> %
<tb> gefunden: <SEP> N <SEP> 12,5 <SEP> % <SEP> P <SEP> 9,9 <SEP> % <I>Beispiel 2</I> 36,6 g (0;2 Mol) Natriumsalz des 1-Phenyl-3- hydroxy-1,2,4-triazols wenden in 200 ml Acetonitril suspendiert und mit 32,2 g (0,2 Mol) Dimethoxythio- nophosphorchlorid versetzt.
Nach 12-stündigem Rüh ren bei 50 C-60 C wird das Kochsalz abfiltriert und das Filtrat vom Lösungsmittel befreit. Es hinterbleiben 55 g 1-Phenyl-3-(dimethoxythionophosphoryloxy)- 1,2,4-triazol.
EMI0002.0033
C10H12N3O3PS <SEP> Molgewicht <SEP> 285
<tb> berechnet: <SEP> N <SEP> 14,75 <SEP> % <SEP> P <SEP> 10,85 <SEP> %
<tb> gefunden: <SEP> N <SEP> 14,20 <SEP> % <SEP> P <SEP> 10,80 <SEP> % <I>Beispiel 3</I> 64,4 g (0,4 Mol) 1-Phenyl-3-hydroxy-1,2,4-triazol wenden mit 400 ml Tetrahydrofuran und 69 g (0,4 Mol) Diäthoxyphosphorylchlorid versetzt und 44 g (0,44 Mol) Triäthylamin zugetropft.
Zur Vervollständi gung der exothermen Reaktion wird noch 3 Stunden lang bei 50 C gerührt und danach das Triäthylamin- hydrochlorid abfiltriert. Das Filtrat wird eingedampft, der Rückstand in Benzol gelöst und mit Wasser gewa schen. Nach dein Abdestillieren des Benzols erhält man 117 g 1-Phenyl-3-(diäthoxyphosphoryloxy)- 1,2,4-triazol als hellbraunes Öl.
EMI0002.0041
C12H16N3O4P <SEP> Molgewicht <SEP> 297
<tb> berechnet: <SEP> N <SEP> 14,1% <SEP> P <SEP> 10,4 <SEP> %
<tb> gefunden: <SEP> N <SEP> 13,9 <SEP> % <SEP> P <SEP> 10,0 <SEP> % <I>Beispiel 4</I> 25 g (0,127 Mol) 1-(3-Chlorphenyl)-3-hydroxy- 1,2,4-triazol, 24 g (0,127 Mol) Diäthoxythionophos- phorylchlorid, 15 g (0,15 Mol) Triäthylamin und 250 ml Benzol werden 10 Stunden bei 60 C gerührt. Nach dem Absaugen wird mit Wasser gewaschen und das Benzol abdestilliert.
Man erhält 39 g 1-(3-Chlorphenyl)-3-(diäthoxythionophosphoryloxy)- 1,2,4-triazol.
EMI0002.0054
C12H15ClN3O3PS <SEP> Molgewicht <SEP> 347,5
<tb> berechnet: <SEP> N <SEP> 12,1 <SEP> % <SEP> P <SEP> 8,9 <SEP> %
<tb> gefunden: <SEP> N <SEP> 12,1 <SEP> % <SEP> P <SEP> 8,7 <SEP> % <I>Beispiel 5</I> 43,4 g (0,2 Mal) Na-Salz des 1-(4-Chlorphenyl)- 3-hydroxy-1,2,4-triazol wenden in 300 m1 Benzol suspendiert und mit 38 g (0,2 Mal) Diäthoxythiono- phosphorylchlorid unte Rückfluss gekocht. Das NaCl wird abfiltriert und das Benzol abdestilliert.
Es hinter bleiben 64 g 1-(4-Chlorphenyl)-3-Diäthoxythionophosphoryloxy)- 1,2,4-triazol als gelbes Öl.
EMI0002.0062
C12H15CIN3O3PS <SEP> Molgewicht <SEP> 347,5
<tb> berechnet: <SEP> N <SEP> 12,1 <SEP> % <SEP> P <SEP> 8,9 <SEP> %
<tb> gefunden: <SEP> N <SEP> 12,0 <SEP> % <SEP> P <SEP> 8,9 <SEP> %
Process for the preparation of new phosphoric acid esters According to the German patent specification No. 910 652 and the corresponding English patent specification No. 713 278, phosphoric acid esters are known which contain an enolizable heterocycle and can be used for pest control.
The invention relates to a process for the preparation of the phosphoric acid esters of the formula I.
EMI0001.0003
where R, and R2 are an alkyl radical having 1 to 4 carbon atoms, preferably the ethyl radical, R3 is the phenyl radical or phenyl radicals substituted by chlorine and X is oxygen or sulfur, which is characterized in that phosphoric acid halides of the formula II
EMI0001.0006
where Hal represents a halogen atom, preferably a chlorine atom, with the above formula corresponding to R 1, -substituted 3-hydroxy-1,2,4-triazoles or their metal salts, preferably their Na or K salts.
In the first case, the reaction is expediently carried out in the presence of acid-binding agents such as alkali carbonates, e.g. B. soda, alkaline earth carbonates, or tertiary amines, such as. B.
Triethylamine, dimethylaniline or pynidine. The reaction is illustrated by the following equation:
EMI0001.0015
The reaction can be carried out with or without a solvent.
Suitable solvents are all common organic liquids which are inert under the reaction conditions, such as liquids such as acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, methylene chloride, carbon tetrachloride, benzene, xylene, chlorobenzene, etc. The reaction is generally carried out at temperatures of about 20-25 C to the boiling point of the individual solvents, but preferably 50-80 C.
Addition of copper powder, preferably between 1 and 20 mole percent, can. influence the speed of reaction favorably.
Some of the new compounds are produced as oils and others are crystalline. They cannot be distilled without decomposition. <I> Example 1 </I> 32.2 g (0.2 mol) of 1-phenyl-3-hydroxy-1,2,4-triazole are suspended in 250 ml of acetone and mixed with 38 g (0.2 mol) 0,0-diethoxythionophosphorylchlorid ver sets. Thereafter, 22 g (0.22 mol) of triethylamine are added dropwise and the mixture is stirred at approx. After cooling, the triethylamine hydrochloride is filtered off and the solvent is removed from the filtrate by evaporation.
60 g of 1-phenyl-3- (diethoxythionophosphoryloxy) 1,2,4-triazole are obtained as a light brown oil.
EMI0002.0026
C12H16N3O3PS <SEP> molecular weight <SEP> 313
<tb> calculated: <SEP> N <SEP> 13.5 <SEP>% <SEP> P <SEP> 9.9 <SEP>%
<tb> found: <SEP> N <SEP> 12.5 <SEP>% <SEP> P <SEP> 9.9 <SEP>% <I> Example 2 </I> 36.6 g (0; 2 Mol) sodium salt of 1-phenyl-3-hydroxy-1,2,4-triazole is suspended in 200 ml of acetonitrile and treated with 32.2 g (0.2 mol) of dimethoxythionophosphorus chloride.
After stirring for 12 hours at 50 ° -60 ° C., the common salt is filtered off and the filtrate is freed from the solvent. 55 g of 1-phenyl-3- (dimethoxythionophosphoryloxy) - 1,2,4-triazole remain.
EMI0002.0033
C10H12N3O3PS <SEP> molecular weight <SEP> 285
<tb> calculated: <SEP> N <SEP> 14.75 <SEP>% <SEP> P <SEP> 10.85 <SEP>%
<tb> found: <SEP> N <SEP> 14.20 <SEP>% <SEP> P <SEP> 10.80 <SEP>% <I> Example 3 </I> 64.4 g (0.4 Mol) 1-phenyl-3-hydroxy-1,2,4-triazole are mixed with 400 ml of tetrahydrofuran and 69 g (0.4 mol) of diethoxyphosphoryl chloride and 44 g (0.44 mol) of triethylamine are added dropwise.
To complete the exothermic reaction, stirring is continued for 3 hours at 50 ° C. and then the triethylamine hydrochloride is filtered off. The filtrate is evaporated, the residue is dissolved in benzene and washed with water. After distilling off the benzene, 117 g of 1-phenyl-3- (diethoxyphosphoryloxy) - 1,2,4-triazole are obtained as a light brown oil.
EMI0002.0041
C12H16N3O4P <SEP> molecular weight <SEP> 297
<tb> calculated: <SEP> N <SEP> 14.1% <SEP> P <SEP> 10.4 <SEP>%
<tb> found: <SEP> N <SEP> 13.9 <SEP>% <SEP> P <SEP> 10.0 <SEP>% <I> Example 4 </I> 25 g (0.127 mol) 1- (3-Chlorophenyl) -3-hydroxy-1,2,4-triazole, 24 g (0.127 mol) diethoxythionophosphoryl chloride, 15 g (0.15 mol) triethylamine and 250 ml benzene are stirred at 60 ° C. for 10 hours. After suctioning off, it is washed with water and the benzene is distilled off.
39 g of 1- (3-chlorophenyl) -3- (diethoxythionophosphoryloxy) -1,2,4-triazole are obtained.
EMI0002.0054
C12H15ClN3O3PS <SEP> molecular weight <SEP> 347.5
<tb> calculated: <SEP> N <SEP> 12.1 <SEP>% <SEP> P <SEP> 8.9 <SEP>%
<tb> found: <SEP> N <SEP> 12.1 <SEP>% <SEP> P <SEP> 8.7 <SEP>% <I> Example 5 </I> 43.4 g (0.2 Times) Na salt of 1- (4-chlorophenyl) -3-hydroxy-1,2,4-triazole suspended in 300 ml of benzene and refluxed with 38 g (0.2 times) diethoxythionophosphoryl chloride. The NaCl is filtered off and the benzene is distilled off.
64 g of 1- (4-chlorophenyl) -3-diethoxythionophosphoryloxy) - 1,2,4-triazole remain as a yellow oil.
EMI0002.0062
C12H15CIN3O3PS <SEP> molecular weight <SEP> 347.5
<tb> calculated: <SEP> N <SEP> 12.1 <SEP>% <SEP> P <SEP> 8.9 <SEP>%
<tb> found: <SEP> N <SEP> 12.0 <SEP>% <SEP> P <SEP> 8.9 <SEP>%
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0052591 | 1967-06-03 | ||
| DEF52593A DE1299924B (en) | 1967-06-03 | 1967-06-03 | Pest repellants |
| CH799468A CH498572A (en) | 1967-06-03 | 1968-05-30 | Pesticides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH498155A true CH498155A (en) | 1970-10-31 |
Family
ID=27175906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1153870A CH498155A (en) | 1967-06-03 | 1968-05-30 | compounds where R1 and R2=alkyl (1-4C) pref. ethyl R3=phenyl opt. substd. by Cl X=O or S Insecticides with low mammalian toxicity, suitable for use on pla |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH498155A (en) |
-
1968
- 1968-05-30 CH CH1153870A patent/CH498155A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |