DE1250429B - Process for the production of thiolphosphorus (phosphonic) acid esters - Google Patents
Process for the production of thiolphosphorus (phosphonic) acid estersInfo
- Publication number
- DE1250429B DE1250429B DENDAT1250429D DE1250429DA DE1250429B DE 1250429 B DE1250429 B DE 1250429B DE NDAT1250429 D DENDAT1250429 D DE NDAT1250429D DE 1250429D A DE1250429D A DE 1250429DA DE 1250429 B DE1250429 B DE 1250429B
- Authority
- DE
- Germany
- Prior art keywords
- thiolphosphorus
- phosphonic
- acid esters
- acid
- production
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 12
- 150000002148 esters Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 241000251730 Chondrichthyes Species 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 O-methyl-O-ethyl- Chemical group 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 2
- RUHJZSZTSCSTCC-UHFFFAOYSA-N 2-(bromomethyl)naphthalene Chemical compound C1=CC=CC2=CC(CBr)=CC=C21 RUHJZSZTSCSTCC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002464 fungitoxic effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 241000213004 Alternaria solani Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000196324 Embryophyta 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241001518731 Monilinia fructicola Species 0.000 description 1
- 208000031888 Mycoses Diseases 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
- 241000209094 Oryza Species 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RPSWUJJTYUNDDU-UHFFFAOYSA-N hydroxy-di(propan-2-yloxy)-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(O)(=S)OC(C)C RPSWUJJTYUNDDU-UHFFFAOYSA-N 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000590 parasiticidal effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F9/1653—Esters of thiophosphoric acids with arylalkanols
-
- 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
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing aromatic 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
- C07F9/28—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
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4087—Esters with arylalkanols
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
BUNDESREPUBLIK DEUTSCHLAND DEUTSCHES ^W^SS PATENTAMT Int. CL:FEDERAL REPUBLIC OF GERMANY GERMAN ^ W ^ SS PATENT OFFICE Int. CL:
C07fC07f
'■::<>■ P'■ :: <> ■ P
PESTPEST
Deutsche Kl.: 12 ο - 23/03 German class: 12 ο - 23/03
UZlUZl
IvIv
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag: Number:
File number:
Registration date:
Display day:
F 49434IV b/12 οF 49434IV b / 12 ο
10. Juni 1966June 10, 1966
21. September 1967September 21, 1967
S-CP03S-CP03
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Thiolphosphor-(phosphon-) säureester der allgemeinen KonstitutionThe present invention relates to a process for the preparation of new thiolphosphorus (phosphonic) acid esters of general constitution
RiOn
R2'RiOn
R 2 '
1 — S — CH2 1 - S - CH 2
(I)(I)
welche fungitoxische Eigenschaften besitzen.which have fungitoxic properties.
In vorgenannter Formel stehen Ri und Ro für gleiche oder verschiedene Alkylreste mit 1 bis 4 Kohlenstoffatomen, Rz stellt darüber hinaus auch einen niederen Alkoxyrest dar.In the above formula, Ri and Ro stand for identical or different alkyl radicals with 1 to 4 carbon atoms, Rz also represents a lower alkoxy radical.
In der USA.-Patentschrift 2 690 450 werden bereits Thiolphosphorsäurearylester beschrieben, die parasitizide, insbesondere insektizide, aber auch fungizide Eigenschaften besitzen. Aus dieser Veröffentlichung geht jedoch nur hervor, daß sich die obengenannten Verbindungen als Fungizide zur Bekämpfung von Braunfaule (Sclerotinia fructicola) und der Dörrfleckenkrankheit (Alternaria solani) eignen. Dagegen ist der USA.-Patentschrift 2 690 450 nicht zu entnehmen, ob die dort offenbarten Verbindungen auch eine für die Praxis ausreichende Wirksamkeit gegen pilzliche Krankheitserreger an Reispflanzen, besonders der durch den Pilz Piricularia oryzae verursachten, besitzen.US Pat. No. 2,690,450 already describes aryl thiolphosphorate, which is parasiticidal, in particular have insecticidal, but also fungicidal properties. From this publication However, it only emerges that the above compounds can be used as fungicides for combating Brown rot (Sclerotinia fructicola) and dry spot disease (Alternaria solani) are suitable. On the other hand, the US Pat. No. 2,690,450 does not reveal that whether the compounds disclosed there also have an effectiveness against which is sufficient in practice fungal pathogens on rice plants, especially those caused by the fungus Piricularia oryzae, own.
Es wurde nun gefunden, daß Thiolphosphor-(-phosphon-) -säureester der oben angegebenen Konstitution (I) glatt und mit guten Ausbeuten erhalten werden, wenn man in an sich bekannter Weise Halogenmethylnaphthaline der FormelIt has now been found that thiolphosphorus (- phosphonic) acid esters of the above constitution (I) can be obtained smoothly and with good yields if one works in a manner known per se Halomethylnaphthalenes of the formula
Hai — CH2 Shark - CH 2
(Π)(Π)
mit Thiolphosphor- (-phosphon-)säuren der allgemeinen Strukturwith thiolphosphorus (-phosphonic) acids of the general structure
IlIl
P —SHP-SH
(III)(III)
in Form der entsprechenden Salze oder in Gegenwart von Säurebindemitteln umsetzt.in the form of the corresponding salts or in the presence of acid binders.
Der Verlauf des erfindungsgemäßen Verfahrens kann durch das folgende Reaktionsschema wieder-The course of the process according to the invention can be repeated by the following reaction scheme.
Verfahren zur Herstellung von
Thiolphosphor-(phosphon-)säureesternProcess for the production of
Thiolphosphorus (phosphonic) acid esters
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,Paint factories Bayer Aktiengesellschaft,
LeverkusenLeverkusen
Als Erfinder benannt:Named as inventor:
Dr. Reimer Colin, Wuppertal-Elberfeld;Dr. Reimer Colin, Wuppertal-Elberfeld;
Dr. Hans Scheinpflug, LeverkusenDr. Hans Scheinpflug, Leverkusen
gegeben werden:
0are given:
0
Wie weiterhin gefunden wurde, zeichnen sich die neuen Thiolphosphor- (-phosphon-)säureester durch hervorragende fungitoxische Eigenschaften, insbesondere gegenüber pilzlichen Krankheitserregern an Reispflanzen, aus. überraschenderweise sind sie in dieser Hinsicht den bekannten und für den gleichen Zweck bereits vorgeschlagenen Wirkstoffen analoger Konstitution eindeutig überlegen. Die Verfahrensprodukte stellen somit eine echte Bereicherung der Technik dar.As was also found, the new thiolphosphorus (-phosphonic) acid esters are characterized by excellent fungitoxic properties, especially against fungal pathogens Rice plants, from. Surprisingly, in this regard, they are the most well-known and for the same Purpose of already proposed active ingredients of analogous constitution clearly superior. The process products are a real asset to the Technology.
Die verfahrensgemäß zu verwendenden Halogenmethylnaphthaline sind aus der Literatur bekannt und können auch in technischem Maßstab leicht hergestellt werden.The halomethylnaphthalenes to be used according to the process are known from the literature and can also be easily produced on an industrial scale.
An thiolphosphor- (-phosphofljj.JÄiaren Salzen sind beispielsweise die folgenden afc Awegangssubstanzen geeignet: 0,0-dimethyl-, -difithyl-, -diisopropyl-, -di-sec. -butyl-, O-methyl-O-äthyl-, O-methyl- und O-äthyl-0-n- und -isopropyl-, O-methyl-0-n- und sec.-butyl-, O-äthyl-0-n- und sec.-butyl-, O-isopropyl-O-sec.-butyl-thiolphosphorsaures Ammonium, Kalium oder Natrium.The following substances are suitable for thiolphosphorus (-phosphoflj.JÄiaren salts: 0,0-dimethyl-, -difithyl-, -diisopropyl-, -di-sec. -Butyl-, O-methyl-O-ethyl-, O-methyl- and O-ethyl-0-n- and -isopropyl-, O-methyl-0-n- and sec-butyl-, O-ethyl-0-n- and sec-butyl-, O- isopropyl-O-sec.-butyl-thiolphosphoric acid ammonium, potassium or sodium.
Das erfindungsgemäße Verfahren wird im allgemeinen in Gegenwart von Lösungs- oder Verdünnungsmitteln durchgeführt. Als solche habenThe inventive method is generally carried out in the presence of solvents or diluents. As such have
648/369648/369
sich vor allem Kohlenwasserstoffe, wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Benzol, Toluol, Xylol, Chlorbenzol, femer Äther, beispielsweise Diäthyl- und Dibutyläther, Dioxan, Tetrahydrofuran, ferner niedrigsiedende aliphatische Ketone und Nitrile, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- und Methylisobutylketon sowie Aceto- und Propionitril, bewährt.mainly hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, benzene, Toluene, xylene, chlorobenzene, and ether, for example Diethyl and dibutyl ethers, dioxane, tetrahydrofuran, and also low-boiling aliphatic Ketones and nitriles, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone as well as aceto- and propionitrile, proven.
Weiterhin dienen — wie oben bereits erwähnt — die Salze, im allgemeinen die Alkali- oder Ammoniumsalze der vorgenannten Thiolphosphorsäuren, als Ausgangssubstanzen für die erfindungsgemäße Reaktion. As already mentioned above, the salts, generally the alkali metal or ammonium salts, also serve the aforementioned thiol phosphoric acids, as starting substances for the reaction according to the invention.
Statt von den betreffenden Salzen auszugehen kann man auch die entsprechenden freien Säuren verwenden und diese in Anwesenheit von Säurebindemitteln im Sinne der vorliegenden Erfindung umsetzen. Als Säureakzeptoien kommen insbesondere Alkalicarbonate und -alkoholate, wie Kalium- bzw. Natriumcarbonat, -methylat oder -äthylat, ferner aber auch tertiäre Basen, wie Triäthylamin, Dimethylanilin oder Pyridin, in Betracht.Instead of starting from the salts in question, one can also use the corresponding free acids use and these in the presence of acid binders for the purposes of the present invention realize. In particular, alkali metal carbonates and alcoholates, such as potassium or Sodium carbonate, methylate or ethylate, but also tertiary bases such as triethylamine, dimethylaniline or pyridine.
Die Reaktionstemperaturen können bei der verfahrensgemäßen Umsetzung innerhalb eines größeren Bereichs variiert werden. Im allgemeinen arbeitet man zwischen 30 und 8O0C, vorzugsweise bei 40 bis 700CThe reaction temperatures can be varied within a substantial range in the process according to the implementation. In general, the reaction is preferably carried out at between 30 and 8O 0 C, at 40 to 70 0 C.
Femer werden bei Durchführung des erfindungsgemäßen Verfahrens im allgemeinen äquimolare Mengen Halogenmethylnaphthalin und thiolphosphor- (-phosphon-)saures Salz (bzw. eine Mischung aus der entsprechenden freien Säure und dem Säurebindemittel) eingesetzt. Es hat sich dabei als zweckmäßig erwiesen, das Halogenmethylnaphthalin unter Rühren bei den oben angegebenen Temperaturen zu der vorgelegten Lösung bzw. Suspension des thiolphosphorsäuren Salzes in einem geeigneten Lösungsoder Verdünnungsmittel zu fügen und das Gemisch zur Vervollständigung der Umsetzung anschließend noch längere Zeit (1 bis 3 Stunden), gegebener i'·■·■]',> unter Erwärmen, zu rühren.Furthermore, when carrying out the process according to the invention, equimolar amounts of halomethylnaphthalene and thiolphosphorus (-phosphonic) acid salt (or a mixture of the corresponding free acid and the acid-binding agent) are generally used. It has proven to be expedient to add the halomethylnaphthalene with stirring at the temperatures indicated above to the solution or suspension of the thiolphosphoric acid salt in a suitable solvent or diluent and then to add the mixture for a longer time (1 to 3 hours) to complete the reaction ), given r i '· ■ · ■]',> while heating, stir.
Die Aufarbeitung des Ansatzes erfolgt in prinzipiell bekannter Weise durch Filtrieren der Mischung, Verdampfen des Lösungsmittels, Aufnehmen des ölig ausgeschiedenen Reaktionsproduktes in einem neuen, mit Wasser nicht mischbaren organischen Lösungsmittel, etwa einem der obengenannter,, chlorierten Kohlenwasserstoffe, Waschen der organischen Schicht bis zur neutralen Reaktion, Trennen der Phasen, Trocknen der Lösung und erneutes Abdestillieren des Lösungsmittels sowie gegebenenfalls fraktionierte Destillation des Rückstandes unter vermindertem Druck.The batch is worked up in a manner known in principle by filtering the mixture and evaporating of the solvent, taking up the oily reaction product in a new one water-immiscible organic solvents, such as one of the above-mentioned, chlorinated solvents Hydrocarbons, washing of the organic layer until neutral reaction, separation of the phases, Drying the solution and again distilling off the solvent and optionally fractional Distillation of the residue under reduced pressure.
Die erfindungsgemäß herstellbaren Thiolphosphor-(-phosphon-) -säureester fallen meist in Form farbloser oder schwachgelb- bis bräunljchgefärbter wasserunlöslicher öle an, die sich zum Teil unter stark vermindertem Druck -unzersetzt destillieren lassen und manchmal nach längerem Stehen kristallin erstarren.The thiolphosphorus (- phosphonic) acid esters which can be prepared according to the invention are mostly in the form of colorless ones or pale yellow to brownish colored water-insoluble oils, some of which are strongly Allow to distill under reduced pressure - undecomposed and sometimes crystalline after standing for a long time freeze.
Wie oben 'xrcio erwähnt, zeichnen sich die Verfahrens produkte durch eine starke fungitoxiscbe Wirksamkeit und ein breites Wirkungsspektrum aus. überraschenderweise besitzen sie trotz dieser hervorragenden Wirkung gegen phytopatogene Pilze eine nur geringe Warmblütertoxizitat (mittlere Giftigkeit DL50 an der Ratte per os 100 bis 1000 mg pro Kilogramm Tier). Hinzu kommt die ausgezeichnete Verträglichkeit der erfindungsgemäß herstellbaren Verbindungen für höhere Pflanzen. Auf Grund dieser Eigenschaften sind die Verfahrensprodukte als Pflanzenschutzmittel gegen pilzliche Krankheiten hervorrager d geeignet.As mentioned above 'xrcio, the procedures stand out products are characterized by a strong fungitoxic activity and a broad spectrum of activity. Surprisingly, despite this excellent action against phytopathogenic fungi, they have one only low toxicity to warm blooded animals (mean toxicity DL50 in rats per os 100 to 1000 mg per Kilograms of animal). In addition, there is the excellent compatibility of those which can be prepared according to the invention Connections for higher plants. Because of these properties, the process products are excellent as pesticides against fungal diseases d suitable.
Beispiel 1 Oexample 1 O
/P-SCH2 / P-SCH 2
C2H5OsC 2 H 5 Os
'5 Ein Gemisch aus 61,0 g des Ammoniumsalzes der 0,0-Diäthylthiol-phosphorsäure, 250 ecm Methyläthylketon und 44,2 g (0,25 Mol) 1-Chlormethylnaphthalin (Kp.2 1220C) wird 2 Stunden lang bei einer Innentemperatur von 7O0C gerührt und im abgekühlten Zustand filtriert. Das Filtrat befreit man unter vermindertem Druck vom Lösungsmittel, löst den Rückstand in Tetrachlorkohlenstoff und wäscht die Lösung bis zur neutralen Reaktion. Nach dem Trocknen desselben über Natriumsulfat und Entfernung des Lösungsmittels unter vermindertem Druck hinterbleiben 71,2 g (91,7% der Theorie) des O,O - Diäthylthiol - phosphorsäure-S-[naphthyl-(l)-methyl]-esters in Form eines bräunlichgefärbten Öles. Brechungsindex η" — 1,5784.'5 A mixture of 61.0 g of the ammonium salt of 0,0-diethylthiol-phosphoric acid, 250 ecm of methyl ethyl ketone and 44.2 g (0.25 mol) of 1-chloromethylnaphthalene (boiling point 2 122 0 C) is for 2 hours at stirred an internal temperature of 7O 0 C and filtered in a cooled state. The filtrate is freed from the solvent under reduced pressure, the residue is dissolved in carbon tetrachloride and the solution is washed until it reacts neutral. After drying the same over sodium sulfate and removing the solvent under reduced pressure, 71.2 g (91.7% of theory) of the O, O-diethylthiol-phosphoric acid S- [naphthyl- (l) -methyl] ester remain in the form of a brownish colored oil. Refractive index η "- 1.5784.
Analyse für ein Molgewicht von 310,34:Analysis for a molecular weight of 310.34:
Berechnet... P 9,98%, S 10.33%; gefunden ... P 10,20%, S 10,35%.Calculated ... P 9.98%, S 10.33%; found ... P 10.20%, S 10.35%.
C2HsOs
C2H5O'C 2 HsOs
C 2 H 5 O '
Beispiel 2 OExample 2 O
)P —S-CHo) P-S-CHo
In analoger Weise, wie im vorhergehenden Beispiel beschrieben, erhält man aus 61,0 g des Ammoniumsalzes der 0,0-Diäthylthiol-phosphorsäure und 55,3 g (0,25 Mol) 2-Brommethyl-naphthalin (Fp. 62 bis 630C) 69,2 g (89% der Theorie) Ο,Ο-Diäthylthiolphosphorsäure-S-[naphthyl-(2)-methyl]-ester in Form eines bräunlichgefärbten, zähen Öles, das beim Stehen allmählich kristallisiert und dann einen Schmelzpunkt von 43 bis 450C besitzt. Durch Umkristallisieren des Rohproduktes aus Petroläther werden farblose Kristalle vom Schmelzpunkt 47 bis 48 0C erhalten.In an analogous manner as described in the previous example, one 62 obtained from 61.0 g of the ammonium salt of 0,0-Diäthylthiol-phosphoric acid and 55.3 g (0.25 mol) of 2-bromomethyl-naphthalene (mp. 0 to 63 C) 69.2 g (89% of theory) Ο, Ο-diethylthiolphosphoric acid S- [naphthyl- (2) -methyl] -ester in the form of a brownish, viscous oil which gradually crystallizes on standing and then has a melting point of 43 to 45 0 C possesses. Recrystallization of the crude product from petroleum ether colorless crystals of melting point 47-48 0 C.
Analyse für ein Molgewicht von 310,34:Analysis for a molecular weight of 310.34:
Berechnet P 9,98%, S 10,33%;Calculated P 9.98%, S 10.33%;
Rohprodukt gefunden ... P 10,00%, S 10,66%; Umkristallisiertes ProduktCrude product found ... P 10.00%, S 10.66%; Recrystallized product
gefunden P 10,10%, S 10,58 o/0.found P 10.10%, S 10.58 o / 0 .
Beispiel 3 OExample 3 O
(CH3O)2P — SCH2 —^ y (CH 3 O) 2 P - SCH 2 - ^ y
Ein Gemisch aus 52,5 g des Ammoniumsalzes der 0,0-Dimcthylthiol-phosphorsäure, 150 ecm Acetonitril und 53,0 g (0,3 Mol) 1-Chlormethyl-naphthalin wird 2 Stunden lang bei einer Innentemperatur von 7O0C gerührt und anschließend im abgekühlten Zustand nitriert. Nach Entfernung des Lösungsmittels unter vermindertem Druck nimmt man den Rückstand in 100 ecm Methylenchlorid auf und wäscht die Lösung bis zur neutralen Reaktion. Sie wird dann über Natriumsulfat getrocknet und unter vermindertem Druck vom Lösungsmittel befreit. Es hinterbleiben 62,0 g (73,3°/0 der Theorie) des O,O - Dimethylthiol - phosphorsäure - S - [naphthyl - (2)-methyl]-esters in Form eines gelblichen Öles mit dem Brechungsindex η "g = 1,5898.A mixture of 52.5 g of the ammonium salt of 0,0-Dimcthylthiol-phosphoric acid, 150 cc of acetonitrile and 53.0 g (0.3 mol) of 1-chloromethyl-naphthalene was stirred at an inner temperature of 7O 0 C for 2 hours and then nitrided in the cooled state. After the solvent has been removed under reduced pressure, the residue is taken up in 100 ecm of methylene chloride and the solution is washed until it reacts neutral. It is then dried over sodium sulfate and freed from the solvent under reduced pressure. There remain behind 62.0 g (73.3 ° / 0 of theory) of O, O - Dimethylthiol - phosphoric acid - S - [naphthyl - (2) methyl] ester in the form of a yellowish oil having a refractive index η "g = 1.5898.
Analyse für ein Molgewicht von 282,30:Analysis for a molecular weight of 282.30:
Berechnet ... P 11,0%. S 11,4%;
gefunden ... P 11,0%, S 11,1%. Beispiel 4 OCalculated ... P 11.0%. S 11.4%;
found ... P 11.0%, S 11.1%. Example 4 O
IlIl
(JC3H7O)2P- SCH2 (JC 3 H 7 O) 2 P- SCH 2
In analoger Weise, wie im vorhergehenden Beispiel beschrieben, erhält man durch Umsetzung von 39,0 g des Ammoniumsalzes der Ο,Ο-Diisopropylthiol-phosphorsäure mit 33,2 g (0,15 Mol) 2-Brommethyl-naphthalin 47,0 g (92,5% der Theorie) des O,O - Diisopropylthiol - phosphorsäure - S - [naphthyl-(2)-methyl]-esters in Form eines gelblichen Öles mit dem Brechungsindex η *\s = 1,5650. 1S Analyse für ein Molgewicht von 338,41:In an analogous manner to that described in the previous example, by reacting 39.0 g of the ammonium salt of Ο, Ο-diisopropylthiol-phosphoric acid with 33.2 g (0.15 mol) of 2-bromomethyl-naphthalene, 47.0 g ( 92.5% of theory) of the O, O - diisopropylthiol - phosphoric acid - S - [naphthyl (2) methyl] ester in the form of a yellowish oil with the refractive index η * \ s = 1.5650. 1 S analysis for a molecular weight of 338.41:
Berechnet ... P 9,2%, S 9,5%; gefunden ... P 9,4%, S 9,6%. In analoger Weise, wie im Beispiel 3 beschrieben, sind die folgenden Verbindungen erhältlich:Calculated ... P 9.2%, S 9.5%; found ... P 9.4%, S 9.6%. In an analogous manner to that described in Example 3, the following connections are available:
Konstitutionconstitution
C2H5
C2H5OC 2 H 5
C 2 H 5 O
(IC3H7O)2P — S — CH2 (IC 3 H 7 O) 2 P-S-CH 2
CH;
C2H5OCH;
C 2 H 5 O
(CH3O)2P — S — CH2 (CH 3 O) 2 P-S-CH 2
MolgewichtMolecular weight
294,36294.36
310,36310.36
338,41338.41
280,33280.33
282,30 Brechungsindex282.30 index of refraction
η ff = 1.5998 η ff = 1.5998
= 1,5831= 1.5831
„ff = 1,5649"Ff = 1.5649
η ff = 1,6076 η ff = 1.6076
η "ό5 = 1,5942 η "ό 5 = 1.5942
Analyseanalysis
berechnet (%) P Scalculated (%) P S
10,510.5
10,010.0
9,29.2
11,011.0
10,910.9
10,310.3
9,59.5
11,411.4
11,411.4
gefunden (1Vd) P Sfound ( 1 Vd) PS
10,810.8
10,210.2
9,39.3
11,211.2
11,111.1
11,211.2
10,010.0
11,611.6
11,511.5
Claims (1)
>P —SHO
> P — SH
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0049434 | 1966-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1250429B true DE1250429B (en) | 1967-09-21 |
Family
ID=7103021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1250429D Pending DE1250429B (en) | 1966-06-10 | Process for the production of thiolphosphorus (phosphonic) acid esters |
Country Status (6)
| Country | Link |
|---|---|
| AT (1) | AT267547B (en) |
| BE (1) | BE699714A (en) |
| DE (1) | DE1250429B (en) |
| ES (1) | ES341592A1 (en) |
| GB (1) | GB1168317A (en) |
| NL (1) | NL6708075A (en) |
-
0
- DE DENDAT1250429D patent/DE1250429B/en active Pending
-
1967
- 1967-06-09 GB GB2668567A patent/GB1168317A/en not_active Expired
- 1967-06-09 NL NL6708075A patent/NL6708075A/xx unknown
- 1967-06-09 ES ES341592A patent/ES341592A1/en not_active Expired
- 1967-06-09 BE BE699714D patent/BE699714A/xx unknown
- 1967-06-12 AT AT543367A patent/AT267547B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| ES341592A1 (en) | 1968-09-16 |
| BE699714A (en) | 1967-12-11 |
| GB1168317A (en) | 1969-10-22 |
| AT267547B (en) | 1969-01-10 |
| NL6708075A (en) | 1967-12-11 |
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