DE2133329A1 - 3,4,5-trisubstd-2,6-diamino-thiaphosphorin-4-thiones - - with miobicidal and fungicidal activity - Google Patents
3,4,5-trisubstd-2,6-diamino-thiaphosphorin-4-thiones - - with miobicidal and fungicidal activityInfo
- Publication number
- DE2133329A1 DE2133329A1 DE19712133329 DE2133329A DE2133329A1 DE 2133329 A1 DE2133329 A1 DE 2133329A1 DE 19712133329 DE19712133329 DE 19712133329 DE 2133329 A DE2133329 A DE 2133329A DE 2133329 A1 DE2133329 A1 DE 2133329A1
- Authority
- DE
- Germany
- Prior art keywords
- thiaphosphorine
- radical
- general formula
- diethylamino
- dimethyl
- 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
- 230000000855 fungicidal effect Effects 0.000 title description 2
- -1 methoxyphenyl Chemical group 0.000 claims abstract description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 125000005110 aryl thio group Chemical group 0.000 abstract 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 14
- 150000008064 anhydrides Chemical class 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FSTSWGNPHCPTNB-UHFFFAOYSA-N n,n-dimethyl-2-phenylethynamine Chemical group CN(C)C#CC1=CC=CC=C1 FSTSWGNPHCPTNB-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LBCUDSYWWDDMLK-UHFFFAOYSA-N 4-(2-phenylethynyl)morpholine Chemical group C1COCCN1C#CC1=CC=CC=C1 LBCUDSYWWDDMLK-UHFFFAOYSA-N 0.000 description 1
- GBYFPBOCGRQZKH-UHFFFAOYSA-N C(CCCCCCCCC)P(O)(O)=S Chemical compound C(CCCCCCCCC)P(O)(O)=S GBYFPBOCGRQZKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WXJXBKBJAKPJRN-UHFFFAOYSA-N Methanephosphonothioic acid Chemical compound CP(O)(O)=S WXJXBKBJAKPJRN-UHFFFAOYSA-N 0.000 description 1
- TZBPMRQPJBWOMU-UHFFFAOYSA-N N-(2-phenylethynyl)-N-propylpropan-1-amine Chemical group C(CC)N(CCC)C#CC1=CC=CC=C1 TZBPMRQPJBWOMU-UHFFFAOYSA-N 0.000 description 1
- HEMSMKNSXHLORG-UHFFFAOYSA-N OP(C1=CC=NC=C1)(O)=S Chemical compound OP(C1=CC=NC=C1)(O)=S HEMSMKNSXHLORG-UHFFFAOYSA-N 0.000 description 1
- CGBBPJLVNZRUGG-UHFFFAOYSA-N P(O)(O)=S.C1=CC=CC=C1 Chemical compound P(O)(O)=S.C1=CC=CC=C1 CGBBPJLVNZRUGG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DWNKWLFNYOZABF-UHFFFAOYSA-N butyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCP(O)(O)=S DWNKWLFNYOZABF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- BHBIHWVLITWUFQ-UHFFFAOYSA-N dihydroxy-(2-methylpropyl)-sulfanylidene-lambda5-phosphane Chemical compound CC(C)CP(O)(O)=S BHBIHWVLITWUFQ-UHFFFAOYSA-N 0.000 description 1
- KOXPAAQPVFDIKN-UHFFFAOYSA-N dihydroxy-propyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCP(O)(O)=S KOXPAAQPVFDIKN-UHFFFAOYSA-N 0.000 description 1
- QRPGQVSWYVYJKA-UHFFFAOYSA-N dodecyl-dihydroxy-sulfanylidene-lambda5-phosphane Chemical compound C(CCCCCCCCCCC)P(O)(O)=S QRPGQVSWYVYJKA-UHFFFAOYSA-N 0.000 description 1
- HGELWZQRZUOEOJ-UHFFFAOYSA-N ethyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCP(O)(O)=S HGELWZQRZUOEOJ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HUVCXZZDRLNTBJ-UHFFFAOYSA-N heptyl-dihydroxy-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCCP(O)(O)=S HUVCXZZDRLNTBJ-UHFFFAOYSA-N 0.000 description 1
- VHOXUGLCIBEVJT-UHFFFAOYSA-N hexyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCP(O)(O)=S VHOXUGLCIBEVJT-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UUQMJSGFWLACFD-UHFFFAOYSA-N n,n-diethyl-2-phenylethynamine Chemical group CCN(CC)C#CC1=CC=CC=C1 UUQMJSGFWLACFD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
-
- 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
- A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
Abstract
Description
Thiaphosphorine und Verfahren zu deren Herstellung" Die Erfindung betrifft Thiaphosphorine, eine neue Klasse von Phosphor und Schwefel enthaltenden organischen Verbindungen, sowie ein Verfahren zur Herstellung dieser Verbindungen. Thiaphosphorins and Processes for Their Preparation "The Invention relates to thiaphosphorins, a new class of phosphorus and sulfur containing organic compounds, as well as a process for the preparation of these compounds.
Die neuen Verbindungen haben die allgemeine Formel in der R1 einen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen, einen heterocyclischen Rest, einen Thioalkylrest oder einen Thioarylrest, R2 einen Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen sowie R3 und R4 Kohlenwasserstoff reste mit 1 bis 4 Kohlenstoffatomen bedeuten, wobei R3 und Rls auch zusalnmen eine Kohlenstoffkette darstellen können, die gegebenenfalls ein Heteroatom oder Heteroatome enthält und die mit dem Stickstoffatom einen heterocyclischen Ring bildet.The new compounds have the general formula in which R1 is a hydrocarbon radical with 1 to 12 carbon atoms, a heterocyclic radical, a thioalkyl radical or a thioaryl radical, R2 is a hydrocarbon radical with 1 to 12 carbon atoms and R3 and R4 are hydrocarbon radicals with 1 to 4 carbon atoms, with R3 and Rls also being a carbon chain may represent, which optionally contains a hetero atom or atoms and which forms a heterocyclic ring with the nitrogen atom.
Das Verfahren zur Herstellung der neuen Verbindungen ist dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel (R1PS2)2 (I) mit Inaminen der allgemeinen Formel R2 - C -C -NR3R4 (11) umsetzt.The process for the preparation of the new compounds is characterized by that one compounds of the general formula (R1PS2) 2 (I) with ynamines of the general Formula R2 - C -C -NR3R4 (11).
Als Ausgangsverbindungen der allgemeinen Formel (R1PS2)2 kommen Perthiophosphonsäureanhydride und Anhydride von Perthiophosphorsäuremono-S-estern infrage. Die Herstellung dieser Verbindungen erfolgt nach literaturbekannten Methoden. Geeignete Darstellungsverfahren sind u. a. in Gazz. Chem. Ital. 76, 227 (1946), J. Am. Chem. Soc. 2, 5020 (1956), J. Org. Chem. , 3829 (1962) und Chimia 18, 217 (1964) besehrieben. Für die Herstellung der neuen Thiaphosphorine können beispielsweise -die Anhydride folgender Perthiophosphonsäuren verwendet werden: Methanperthiophosphonsäure, Athanperthiophosphonsäure, n-Propanperthiophosphonsäure, 2-Methylpropanperthiophosphonsäure, n-Butanperthiophosphonsäure, n-Hexanperthiophosphonsäure, n-Heptanperthiophosphonsäure, n-Decanperthiophosphonsäureg n-Dodecanperthiophosphonsäure, 2-Phenyläthanperthiophosphonsäure, Cyclohexanperthiophosphonsäure, Benzolperthiophosphonsäure, 4-Methoxybenzolperthiophosphonsäure, l-Naphtalinperthiophosphonsäure, 2-Naphtalinperthiophosphonsäure, Thiofuranperthiophosphonsäure und 4-Pyridinperthiophosphonsäure. Weiterhin sind zur Darstellung von Thiaphosphorinen u. a. die Anhydride folgender Perthiophosphorsäuremono-S -ester geeignet: Perthiophosphorsäuremono -3 -methylester, Perthiophosphorsäuremono-S-äthylester, Perthiophosphorsäuremono-S-n-propylester, Perthiophosphorsäuremono-S-n-butylester, Perthiophosphorsäuremono-S-i-lJutylesters Perthiophosphorsäuremono-S-phenylester und Perthiophosphonsäuremono-S-naphthylester.Perthiophosphonic anhydrides are used as starting compounds of the general formula (R1PS2) 2 and anhydrides of perthiophosphoric acid mono-S-esters in question. The making of this Connections are made according to methods known from the literature. Appropriate presentation methods are i.a. in Gazz. Chem. Ital. 76, 227 (1946), J. Am. Chem. Soc. 2, 5020 (1956), J. Org. Chem., 3829 (1962) and Chimia 18, 217 (1964). For the production of the new thiaphosphorines can, for example, -the anhydrides of the following perthiophosphonic acids can be used: methane-thiophosphonic acid, ethane-thiophosphonic acid, n-propane-thiophosphonic acid, 2-methylpropane-thiophosphonic acid, n-butane-thiophosphonic acid, n-hexane-thiophosphonic acid, n-heptane-thiophosphonic acid, n-decane-thiophosphonic acid g n-dodecane-thiophosphonic acid, 2-phenylethane thiophosphonic acid, cyclohexane thiophosphonic acid, benzene thiophosphonic acid, 4-methoxybenzeneperthiophosphonic acid, l-naphthalene perthiophosphonic acid, 2-naphthalene perthiophosphonic acid, Thiofuran-thiophosphonic acid and 4-pyridine-thiophosphonic acid. Furthermore are for the preparation of thiaphosphorines and others. the anhydrides of the following perthiophosphoric acid mono-S -ester suitable: perthiophosphoric acid mono -3 -methyl ester, perthiophosphoric acid mono-S-ethyl ester, Perthiophosphoric acid mono-S-n-propyl ester, perthiophosphoric acid mono-S-n-butyl ester, Perthiophosphoric acid mono-S-i-l-butyl ester Perthiophosphoric acid mono-S-phenyl ester and perthiophosphonic acid mono-S-naphthyl ester.
Die bei der Herstellung der Thiaphosphorine verwendeten Inamine der allgemeinen Formel R2 -C=C-NRR4 können ebenfalls nach literaturbekannten Methoden erhalten werden. Geeignete Herstellungsverfahren sind u. a. in Angew. Chem. , 57) (1964) und Angew. Chem. 79, 744 (1967) beschrieben. Als Inaminkomponente sind beispielsweise folgende Verbindungen geeignet: 1-Dimethylaminopropin-1, 1-Diäthylaminopropin-1, 1-Dimethylaminobutin-1, 1-Diäthylaminobutin-1, 1-Din-propylaminobutin-1, 1-Diäthylaminopentin-1, l-Methylphenylaminohexin-1, 1-Dimethylamino-5,5-dimethylbutin-1, 1-Methylphenylamino-),3-dimethylbutin-1, Dimethylaminophenylacetylen, Diäthylaminophenylacetylen, Di-n-propylaminophenylacetylen und Morpholinophenylacetylen.The ynamines used in the preparation of the thiaphosphorines The general formula R2 -C = C-NRR4 can also be carried out using methods known from the literature can be obtained. Suitable manufacturing processes include: in Angew. Chem., 57) (1964) and Angew. Chem. 79, 744 (1967). The inamine components are, for example the following compounds are suitable: 1-dimethylaminopropin-1, 1-diethylaminopropin-1, 1-dimethylaminobutin-1, 1-diethylaminobutin-1, 1-din-propylaminobutin-1, 1-diethylaminopentin-1, l-methylphenylaminohexyne-1, 1-dimethylamino-5,5-dimethylbutyne-1, 1-methylphenylamino -), 3-dimethylbutyne-1, Dimethylaminophenylacetylene, diethylaminophenylacetylene, di-n-propylaminophenylacetylene and morpholinophenylacetylene.
Bei der Herstellung der Thiaphosphorine wird zweckmäßig die Verbindung der allgemeinen Formel (R1PS2)2 unter Rühren allmählich in das Inamin -eingebracht. Die Komponenten reagieren dabei rasch und unter Wärmeentwicklung miteinander, wobei ein zunächst flüssiges ReaktiQnsprodukt entsteht, das bei Erkalten kristallisiert. Säureanhydrid und Inamin werden bevorzugt im Molverhältnis 1:4 umgesetzt, jedoch ist dieses Molverhältnis nicht kritisch, so daß sowohl das Inamin wie auch das Säureanhydrid im Überschuß eingesetzt werden kann. In einzelnen Fällen ist es zweckmäßig, die Reaktion in geeigneten inerten Lösungsmitteln wie Diäthyläther, Methylenchlorid, Tetrachlorkohlenstoff, Toluol oder Petroläther durchzuführen. Gegebenenfalls kann man die Reaktion unter äußerer Kühlung ablaufen lassen.In the preparation of the thiaphosphorins, the compound is useful of the general formula (R1PS2) 2 gradually introduced into the ynamine with stirring. The components react with each other quickly and with development of heat, whereby an initially liquid reaction product is formed, which crystallizes when it cools down. Acid anhydride and ynamine are preferably reacted in a molar ratio of 1: 4, however this molar ratio is not critical, so that both the ynamine and the acid anhydride can be used in excess. In individual cases it is useful to use the Reaction in suitable inert solvents such as diethyl ether, methylene chloride, Carry out carbon tetrachloride, toluene or petroleum ether. If necessary, can the reaction is allowed to proceed with external cooling.
Die Komponenten können rauch durch Zugabe des Inamins zum Säureanhydrid in Abwesenheit oder in Gegenwart eines Lösungsmittels miteinander zur Reaktion gebracht werden.The components can be smoked by adding the ynamine to the acid anhydride reacted with one another in the absence or in the presence of a solvent will.
Beim Aufarbeiten des Reaktionsgemisches verfährt man zweckmäßigerweise so, daß man das Rohprodukt, gegebenenfalls nach-Entfernen des Lösungsmittels, in Petroläther oder Benzin löst. Etwa vorhandene Nebenprodukte bleiben dabei ungelöst und werden durch Filtration oder Abdekantieren abgetrennt. Das Thiaphosphorin bleibt nach dem Abdampfen des Lösungsmittels zurück, es kann aber auch aus dem Extrakt durch starke Abkühlung zur Kristallisation gebracht und abfiltriert werden.When working up the reaction mixture, one proceeds appropriately so that the crude product, optionally after removal of the solvent, in Petroleum ether or gasoline dissolves. Any by-products that may be present remain undissolved and are separated off by filtration or decanting. The thiaphosphorine remains back after evaporation of the solvent, but it can also come from the extract brought to crystallization by strong cooling and filtered off.
Bei den so hergestellten Thiaphosphorinen handelt es sich um neue Verbindungen, die sich durch mikrobizide und fungizide Wirksamkeit auszeichnen.The thiaphosphorines produced in this way are new Compounds that are characterized by microbicidal and fungicidal effectiveness.
Beispiel 1 Zu 22 g (0,2 Mol) Diäthylaminopropin-l wurden unter kräftigem Rühren portionsweise 11 g (0,05 Mol) Methanperthiophosphonsäureanhydrid zugegeben. Nach dem Abklingen der stark exothermen Reaktion wurde das kristalline Reaktionsprodukt in Petroläther gelöst. Die Petrolätherlösung wurde von ungelösten Bestandteilen abdekantiert und auf etwa 300 C abgekühlt. Dabei kristallisierte das 4-Methyl-3,5-dimethyl-2,6-diäthylamino-1,4-thiaphosphorin in fast farblosen Kristallen vom Schmelzpunkt 65 - 670 C aus.Example 1 To 22 g (0.2 mol) of diethylaminopropin-1 were added vigorously 11 g (0.05 mol) of methaneperthiophosphonic anhydride were added in portions, with stirring. After the strongly exothermic reaction had subsided, the crystalline reaction product became dissolved in petroleum ether. The petroleum ether solution was made of undissolved matter decanted and cooled to about 300 ° C. The 4-methyl-3,5-dimethyl-2,6-diethylamino-1,4-thiaphosphorine crystallized in almost colorless crystals with a melting point of 65 - 670 C.
Ausbeute: 28 g (85 ) 15 29 2 2 Ber. C 54.18 H 8.79 N 8.42 P 9.32 S 19.29 Gef. C 53.80 H 9.01 N 8.25 P 9.06 S 18.95 Beispiel 2 Zu 20 g (0,05 Mol) p-Methoxybenzolperthiophosphonsäureanhydrid wurden rasch 22 g (0,2 Mol) 1-Diäthylaminopropin-1 zugefügt. Dabei löste sich das Säureanhydrid sofort auf und die Mischung erwärmte sich auf etwa 1200. Nach dem Erkalten kristallisierte das braungefärbte Reaktionsprodukt vollständig. Zur Reinigung wurde in Petroläther gelöst, von Ungelöstem abdekantiert und die Lösung eingedampft. Dabei wurde das 4-(p-Methoxyphenyl)-3,5-dimethyl 2,6-diäthylamino-1,4-thiaphosphorin in gelben Kristallen vom 'ichrneizpunkt; 820 erhalten.Yield: 28 g (85) 15 29 2 2 calc. C 54.18 H 8.79 N 8.42 P 9.32 S. 19.29 Found C 53.80 H 9.01 N 8.25 P 9.06 S 18.95 Example 2 To 20 g (0.05 mol) of p-methoxybenzeneperthiophosphonic anhydride 22 g (0.2 mol) of 1-diethylaminopropyne-1 were quickly added. This dissolved Acid anhydride up immediately and the mixture warmed up to about 1200. After that The brown-colored reaction product crystallized completely when cooled. For cleaning was dissolved in petroleum ether, the undissolved material was decanted off and the solution was evaporated. The 4- (p-methoxyphenyl) -3,5-dimethyl 2,6-diethylamino-1,4-thiaphosphorine was thereby in yellow crystals from the point of focus; 820 received.
Ausbeute: 35 g (= 82 % d. Th.) C21H33N2OPS2 Ber. C 59.40 H 7.83 N 6.59 P 7.30 Gef. C 59.21 H 7.86 N 6.68 P 752 Beispiel 3 14,5 g (0,1 Mol) Dimethylaminophenylacetylen wurden mit 10 g (0,025 Mol) p-Methoxybenzolperthiophosphonsäureanhydrid vermischt, wobei eine deutliche Wärmeentwicklung zu beobachten war. Nachdem das Reaktionsprodukt kristallin erstarrt war, wurde in Äther gelöst, von Ungelöstem abdekantiert und die Ätherlösung im Vakuum eingedampft. Das gelbe 4-p-Methoxyphenyl-3,5-diphenyl-2,6-dimethylamino-1 ,4-thiaphosphorin blieb kristallin zurück. Es zersetzte sich ab 950 C.Yield: 35 g (= 82% of theory) C21H33N2OPS2 calc. C 59.40 H 7.83 N 6.59 P 7.30 Found C 59.21 H 7.86 N 6.68 P 752 Example 3 14.5 g (0.1 mol) of dimethylaminophenylacetylene were mixed with 10 g (0.025 mol) of p-methoxybenzeneperthiophosphonic anhydride, a significant development of heat was observed. After the reaction product was solidified in crystalline form, was dissolved in ether, decanted from undissolved matter and the ether solution evaporated in vacuo. The yellow 4-p-methoxyphenyl-3,5-diphenyl-2,6-dimethylamino-1 , 4-thiaphosphorine remained crystalline. It decomposed from 950 C.
Ausbeute: 8 g (32 %) 27 29 2 2 Ber. C 65.91 H 5.94 N 13.03 P 6.29 Gef. C 65.44 H 6.03 N 12.87 P 6.01 Beispiel 4 Zu 22 g (Q,2 Mol) 1-Diäthylaminopropin-1 wurden unter kräftigem Rühren portionsweise 18 g (0,05 Mol) Thiofuranphosphonsäureanhydrid zugegeben, und zwar in der Weise, daß bei der exothermen Reaktion die Temperatur nicht über 50 - 600 C anstieg. Das beim Abkühlen kristallisierte Reaktionsgemisch wurde mit kaltem Petroläther durchgerührt und die Petrolätherlösung -nach dem Abdekantieren von ungelösten Bestandteilen -im Vakuum eingedampft. Das 4-Thiofuryl-3,5-dimethyl-2,6-diäthylamino-1,4-hiaphosphorin blieb in gelben Kristallen vom Schmelzpunkt 74 - 750 C zurück.Yield: 8 g (32%) 27 29 2 2 calc. C 65.91 H 5.94 N 13.03 P 6.29 Found C 65.44 H 6.03 N 12.87 P 6.01 Example 4 To 22 g (Q, 2 mol) 1-Diethylaminopropin-1 was added in portions with vigorous stirring 18 g (0.05 mol) Thiofuranphosphonic anhydride added, in such a way that at the exothermic Reaction the temperature did not rise above 50 - 600 C. That crystallized on cooling The reaction mixture was stirred with cold petroleum ether and the petroleum ether solution - after decanting off undissolved components - evaporated in vacuo. That 4-Thiofuryl-3,5-dimethyl-2,6-diethylamino-1,4-hiaphosphorine remained in yellow crystals from melting point 74-750 C.
Ausbeute: 20 g (= 50 ffi d. Th.) 18 29 2 3 Ber. C 5).97 H 7.30 N 6.99 P 7.73 S 24.01 Gef. C 53.52 H 7.23 N 6.91 P 7.43 s 23.28 Beispiel 5 Zu 20 g (0,05 Mol) Phenylperthiophosphorsäureanhydrid, in 40 ml Äther suspendiert, wurden bei -780 C unter Rühren 22 g (0,2 Mol) 1-Diäthylaminopropin-l zugetropft.Yield: 20 g (= 50 ffi of theory) 18 29 2 3 calc. C 5) .97 H 7.30 N 6.99 P 7.73 S 24.01 Found C 53.52 H 7.23 N 6.91 P 7.43 s 23.28 Example 5 For 20 g (0.05 Mol) phenylperthiophosphoric anhydride, suspended in 40 ml of ether, were at -780 C with stirring 22 g (0.2 mol) of 1-diethylaminopropin-1 was added dropwise.
Anschließend wurde die Kühlung entfernt und bei Raumtemperatur 2 Stunden weitergerührt, wobei sich eine klare Lösung bildete.The cooling was then removed and at room temperature for 2 hours stirred further, a clear solution being formed.
Nach neuerlichem Abkühlen auf etwa -250 C kristallisierte das entstandene 4-Phenylmercapto-7,5-dimethyl-2,6-diäthylamino-1,4-thiaphosphorin in gelben Kristallen aus. Die Substanz zersetzte sich ab 530 C, Ausbeute: 31 g (= 72 d. Th.) C20H3 1N2PS3 Ber. C 56.30 H 7.32 N 6-57 P 7.26 Gef. C 59.97 H 7.01 N 6.22 P 7.01After cooling again to about -250 ° C., the resulting crystallized 4-Phenylmercapto-7,5-dimethyl-2,6-diethylamino-1,4-thiaphosphorine in yellow crystals the end. The substance decomposed from 530 C, yield: 31 g (= 72 d. Th.) C20H3 1N2PS3 Ber. C 56.30 H 7.32 N 6-57 P 7.26 Found C 59.97 H 7.01 N 6.22 P 7.01
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712133329 DE2133329A1 (en) | 1971-07-05 | 1971-07-05 | 3,4,5-trisubstd-2,6-diamino-thiaphosphorin-4-thiones - - with miobicidal and fungicidal activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712133329 DE2133329A1 (en) | 1971-07-05 | 1971-07-05 | 3,4,5-trisubstd-2,6-diamino-thiaphosphorin-4-thiones - - with miobicidal and fungicidal activity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2133329A1 true DE2133329A1 (en) | 1973-01-25 |
Family
ID=5812688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712133329 Pending DE2133329A1 (en) | 1971-07-05 | 1971-07-05 | 3,4,5-trisubstd-2,6-diamino-thiaphosphorin-4-thiones - - with miobicidal and fungicidal activity |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2133329A1 (en) |
-
1971
- 1971-07-05 DE DE19712133329 patent/DE2133329A1/en active Pending
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