DE1150069B - Process for the production of an unsaturated 0, 0-dialkyl-thiono-thiol-phosphoric acid ester - Google Patents
Process for the production of an unsaturated 0, 0-dialkyl-thiono-thiol-phosphoric acid esterInfo
- Publication number
- DE1150069B DE1150069B DEA36478A DEA0036478A DE1150069B DE 1150069 B DE1150069 B DE 1150069B DE A36478 A DEA36478 A DE A36478A DE A0036478 A DEA0036478 A DE A0036478A DE 1150069 B DE1150069 B DE 1150069B
- Authority
- DE
- Germany
- Prior art keywords
- thiono
- thiol
- acid ester
- phosphoric acid
- bis
- 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
- 238000000034 method Methods 0.000 title claims description 14
- 239000002253 acid Substances 0.000 claims description 25
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- -1 alkali metal acetylene compound Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- OFUICLLNJWZMHW-UHFFFAOYSA-M magnesium;ethenylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH-]=CC1=CC=CC=C1 OFUICLLNJWZMHW-UHFFFAOYSA-M 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- GNSLYOGEBCFYDE-UHFFFAOYSA-N lithium;ethynylbenzene Chemical compound [Li+].[C-]#CC1=CC=CC=C1 GNSLYOGEBCFYDE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- ATKCLEUSJFRRKA-UHFFFAOYSA-N lithium;prop-1-yne Chemical compound [Li+].CC#[C-] ATKCLEUSJFRRKA-UHFFFAOYSA-N 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 150000003014 phosphoric acid esters Chemical class 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 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 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000208241 Tropaeolum Species 0.000 description 2
- 235000004424 Tropaeolum majus Nutrition 0.000 description 2
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OZPUDFCGMLVMJY-UHFFFAOYSA-M [Cl-].CC=C[Mg+] Chemical compound [Cl-].CC=C[Mg+] OZPUDFCGMLVMJY-UHFFFAOYSA-M 0.000 description 1
- JHRRZPXFDKRWJS-UHFFFAOYSA-N [K]C=C Chemical compound [K]C=C JHRRZPXFDKRWJS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- PMXVCJYTFXNQEX-UHFFFAOYSA-N sodium;but-1-yne Chemical compound [Na+].CCC#[C-] PMXVCJYTFXNQEX-UHFFFAOYSA-N 0.000 description 1
- VFSRCMUUHLBQPY-UHFFFAOYSA-N sodium;ethene Chemical compound [Na+].[CH-]=C VFSRCMUUHLBQPY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- PGOLTJPQCISRTO-UHFFFAOYSA-N vinyllithium Chemical compound [Li]C=C PGOLTJPQCISRTO-UHFFFAOYSA-N 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
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
-
- 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
-
- 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
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines ungesättigten 0,0-Dialkyl-thiono-thiol-phosphorsäureesters der allgemeinen FormelThe invention relates to a process for the preparation of an unsaturated 0,0-dialkyl-thiono-thiol-phosphoric acid ester the general formula
Verfahren zur Herstellung eines ungesättigten 0,0-Dialkyl-thiono-tWol-phosphorsäureestersProcess for the preparation of an unsaturated 0,0-dialkyl-thiono-tWol-phosphoric acid ester
= C-S-P-(ORj)2 S= CSP- (ORj) 2 S
R''R ''
worin R eine niedere Alkyl- oder eine Arylgruppe, R1 eine niedere Alkylgruppe und R' ein Wasserstoffatom, eine niedere Alkyl- oder eine Arylgruppe bedeutet. Das Verfahren ist dadurch gekennzeichnet, daß man ein Bis-(O,O-dialkyl-thiono-phosphorsäure)-disulfid der allgemeinen Formelwherein R is a lower alkyl or an aryl group, R 1 is a lower alkyl group and R 'is a hydrogen atom, a lower alkyl or an aryl group. The process is characterized in that a bis (O, O-dialkyl-thionophosphoric acid) disulfide of the general formula
Anmelder:Applicant:
American Cyanamid Company,
New York, N. Y. (V. St. A.)American Cyanamid Company,
New York, NY (V. St. A.)
Vertreter: Dr. F. Zumstein,Representative: Dr. F. Zumstein,
Dipl.-Chem. Dr.rer.nat. E. AssmannDipl.-Chem. Dr.rer.nat. E. Assmann
und Dipl.-Chem. Dr. R. Koenigsberger,and Dipl.-Chem. Dr. R. Koenigsberger,
Patentanwälte, München 2, Bräuhausstr. 4Patent Attorneys, Munich 2, Bräuhausstr. 4th
Beanspruchte Priorität:Claimed priority:
V. St. v. Amerika vom 11. Mai und 2. September 1960
(Nr. 28 236 und Nr. 53 613)V. St. v. America May 11th and September 2nd 1960
(No. 28 236 and No. 53 613)
(R1O)2-P- S-S -P-(OR1),(R 1 O) 2 -P- SS -P- (OR 1 ),
mit etwa äquivalenten Mengen entweder vonwith approximately equivalent amounts of either
a) einer Alkalimetallacetylenverbindung der Formel Bernard Miller, Stamford, Conn. (V. St. Α.),
ist als Erfinder genannt wordena) an alkali metal acetylene compound of the formula Bernard Miller, Stamford, Conn. (V. St. Α.),
has been named as the inventor
RC == C — MRC == C - M
oderor
b) einer Grignardverbindung der Formelb) a Grignard compound of the formula
= CH-Mg-X= CH-Mg-X
R'R '
oderor
c) einer Alkalimetall-vinylverbindung der Formelc) an alkali metal vinyl compound of the formula
.C = CH-M.C = CH-M
R'R '
umsetzt, in welchen Formeln R, R' und R1 die obenstehende Bedeutung haben und M ein Alkalimetall darstellt.converts, in which formulas R, R 'and R 1 have the above meaning and M represents an alkali metal.
Die Vermischung der Substanzen kann man in beliebiger, gewünschter Reihenfolge durchführen. Die Umsetzung wird im allgemeinen in einem inerten organischen Lösungsmittel ausgeführt und tritt bei etwa 0 bis etwa 50°C, vorzugsweise bei etwa 30 bis 400C, ein. Das Alkalimetall M bedeutet in den obigen Formeln z. B. Natrium, Kalium oder Lithium, das Halogenatom X z. B. Chlor oder Brom.The substances can be mixed in any desired order. The reaction is generally carried out in an inert organic solvent and occurs in about 0 to about 50 ° C, preferably at about 30 to 40 0 C, a. The alkali metal M in the above formulas means e.g. B. sodium, potassium or lithium, the halogen atom X z. B. chlorine or bromine.
Folgende Bis-(0,0-dialkyl-thiono-phosphorsäure)-disulfide können z. B. erfindungsgemäß verwendet werden:The following bis (0,0-dialkyl-thionophosphoric acid) disulfides can be, for. B. used according to the invention will:
Bis-(O,O-dimethyl-thiono-phosphorsäure)-disulfid, Bis-(O,O-diäthyl-thiono-phosphorsäure)-disulfid, Bis-(O,O-dibutyl-thiono-phosphorsäure)-disulfid, Bis-(0,0-diphenyl-thiono-phosphorsäure)-disulfid, Bis-(0,0-dinaphthyl-thiono-phosphorsäure)-Bis- (O, O-dimethyl-thionophosphoric acid) disulfide, Bis (O, O-diethyl-thionophosphoric acid) disulfide, Bis- (O, O-dibutyl-thionophosphoric acid) disulfide, Bis- (0,0-diphenyl-thionophosphoric acid) -disulfide, bis- (0,0-dinaphthyl-thionophosphoric acid) -
disulfid,
Bis-(O,O-di-n-propyl-thiono-phosphorsäure)-disulfide,
Bis- (O, O-di-n-propyl-thionophosphoric acid) -
disulfid,
Bis-(O,O-dipentyl-thiono-phosphorsäure)-disulfid.disulfide,
Bis- (O, O-dipentyl-thionophosphoric acid) disulfide.
Folgende Alkalimetall-acetylenverbindungen können z. B. verwendet werden:The following alkali metal acetylene compounds can, for. B. can be used:
Natriumäthylacetylid,Sodium ethylacetylide,
Lithiumphenylacetylid,Lithium phenylacetylide,
Lithiummethylacetylid,Lithium methyl acetylide,
Kaliummethylacetylid,Potassium methyl acetylide,
Natriumbutylacetylid.Sodium butyl acetylide.
309 600/277309 600/277
Folgende Grignardverbindungen und Alkalimetallvinylverbindungen können z. B. verwendet werden:The following Grignard compounds and alkali metal vinyl compounds can e.g. B. can be used:
Vinylmagnesiumbromid,Vinyl magnesium bromide,
Vinylmagnesiumchlorid,Vinyl magnesium chloride,
Styrylmagnesiumbromid,Styryl magnesium bromide,
Propenylmagnesiumchlorid,Propenyl magnesium chloride,
Butenylmagnesiumbromid,Butenyl magnesium bromide,
Isobutylmagnesiumchlorid,Isobutyl magnesium chloride,
Vinyllithium,Vinyl lithium,
Vinylnatrium,Vinyl sodium,
Vinylkalium,Vinyl potassium,
Propenyllithium,Propenyllithium,
Butenyllithium,Butenyllithium,
Δ ^Pentenyllithium. Δ ^ pentenyllithium.
Geeignete inerte Lösungsmittel für die vorerwähnte Umsetzung sind z. B.: Hexan, Cyclohexan, Dioxan, Äther, Xylol, Toluol u. dgl.Suitable inert solvents for the aforementioned reaction are, for. E.g .: hexane, cyclohexane, dioxane, Ether, xylene, toluene and the like.
Die erfindungsgemäß hergestellten Verbindungen finden Anwendung als Schädlingsbekämpfungsmittel, insbesondere als Insektizide. Sie sind hochaktive Insektizide und können als Spray in organischen Lösungsmitteln, als Emulsion in Wasser oder anderen Nichtlösungsmitteln, oder auf festen Trägern, wie z. B. Talg, Ton, Diatomeenerde, verwendet werden. Man kann üblicherweise angewendete Mengen von inertem Träger benutzen. Das aktive Schädlingsbekämpfungsmittel ist jedoch in einer Menge von etwa 0,1 bis etwa 5%, bezogen auf das Gewicht des inerten Trägers, anwesend.The compounds prepared according to the invention are used as pesticides, especially as insecticides. They are highly active insecticides and can be used as a spray in organic Solvents, as an emulsion in water or other nonsolvents, or on solid supports, such as. B. Tallow, clay, diatomaceous earth can be used. You can usually used amounts of inert Use carrier. However, the active pesticide is in an amount of about 0.1 to about 5% based on the weight of the inert carrier is present.
In den folgenden Beispielen bedeuten die Teile Gewichtsteile, wenn nichts anderes gesagt ist.In the following examples, parts mean parts by weight, unless otherwise stated.
Ο,Ο-Diäthyl-S-phenyläthinyl-thiono-thiolphosphorsäureester Ο, Ο-diethyl-S-phenylethinyl-thiono-thiolphosphoric acid ester
Eine Lösung von 3,8 Teilen Phenylacetylen (0,03 Mol) in 15 Volumteilen wasserfreiem Äthyläther wird langsam mit 10 Volumteilen 3n-Butyllithium in Hexan versetzt, wobei in einem geeigneten Reaktionsgefäß gerührt wird. Bei der Umsetzung wird die Mischung in einem Eisbad gekühlt. Man gibt ausreichend Äther hinzu, um alle ausgefallene Lithiumverbindung aufzulösen. Dann wird die Lösung langsam zu 10 Teilen Bis-(O,O-diäthyl-thiono-phosphorsäure)-disulfid(0,003 Mol) zugegeben. Nach weiterem 1 stündigem Rühren wird die Ätherlösung mit Wasser gewaschen und über Magnesiumsulfat getrocknet. Beim Abdampfen des Lösungsmittels erhält man 7,3 Teile hellbraune Flüssigkeit. Diese wird bei 12 bis 18 mm Hg Druck destilliert, wobei man 4,9 Teile Ο,Ο-Diäthyl-S-phenyläthinylthiono-thiol-phosphorsäureester mit dem Brechungsindex η = 1,5903 bis 1,5918 bei 250C erhält.A solution of 3.8 parts of phenylacetylene (0.03 mol) in 15 parts by volume of anhydrous ethyl ether is slowly mixed with 10 parts by volume of 3n-butyllithium in hexane, stirring in a suitable reaction vessel. In the reaction, the mixture is cooled in an ice bath. Sufficient ether is added to dissolve any lithium compound that has precipitated out. The solution is then slowly added to 10 parts of bis (O, O-diethyl-thionophosphoric acid) disulfide (0.003 mol). After stirring for a further hour, the ethereal solution is washed with water and dried over magnesium sulfate. When the solvent is evaporated, 7.3 parts of light brown liquid are obtained. This pressure is distilled at 12 to 18 mm Hg, yielding 4.9 parts Ο, Ο-diethyl-S-phenyläthinylthiono-thiol-η organophosphate with refractive index = 1.5903 to 1.5918 at 25 0 C.
Analyse:
Berechnet
gefundenAnalysis:
Calculated
found
P 10,82, S 22,38%;
P 10,33, S 22,70%.P 10.82, S 22.38%;
P 10.33, S 22.70%.
Mischung wird rasch gerührt und in einem Eisbad gekühlt. Wenn die Bildung von Lithiummethylacetylid beendet ist, werden 25 Teile Bis-(0,0-diäthylthionophosphorsäure)-disulfid (0,06 Mol) in 50 Teilen Äther zugegeben. Die Mischung wird 1^ Stunde gerührt, dann 15 Minuten unter Rückfluß erhitzt, abgekühlt und mit Wasser gewaschen. Dann wird die Ätherlösung über Magnesiumsulfat getrocknet. Beim Abdampfen des Lösungsmittels bleiben 13,7 Teile hellbraune Flüssigkeit zurück. Diese wird bei 0,8 mm Hg Druck destilliert, wobei man 10,8 Teile O,O-Diäthyl-S-methyläthinyl-thiono-thiol-phosphorsäureester vom Kp. = 95 bis 1000C und vom Brechungsindex η = 1,5236 bei 25°C erhält.Mixture is stirred rapidly and cooled in an ice bath. When the formation of lithium methyl acetylide has ended, 25 parts of bis (0,0-diethylthionophosphoric acid) disulfide (0.06 mol) in 50 parts of ether are added. The mixture is stirred for 1 ^ hour, then refluxed for 15 minutes, cooled and washed with water. Then the ethereal solution is dried over magnesium sulfate. When the solvent evaporates, 13.7 parts of light brown liquid remain. This is distilled at 0.8 mm Hg pressure to yield 10.8 parts of O, O-diethyl-S-methyläthinyl-thiono-thiol-organophosphate from Kp. = 95 to 100 0 C and the refractive index η = 1.5236 in 25 ° C.
Analyse: PS2O2C7H13.Analysis: PS 2 O 2 C 7 H 13 .
Berechnet ... C 37,50, H 5,85, P 13,69, S 28,55%; gefunden ... C 37,59, H 6,09, P 13,75, S 28,85%.Calculated ... C 37.50, H 5.85, P 13.69, S 28.55%; Found ... C 37.59, H 6.09, P 13.75, S 28.85%.
Ο,Ο-Dimethyl-S-phenyläthinyl-thiono-thiolphosphorsäureester Ο, Ο-Dimethyl-S-phenyläthinyl-thiono-thiolphosphoric acid ester
Das Verfahren des Beispiels 1 wird wiederholt, as jedoch wirdBis-(O,O-dimethyl-thiono-phosphorsäure)-disulfid
an Stelle des entsprechenden Bis-(O,O-diäthyl-thiono-phosphorsäure)-disulfids
verwendet; man erhält mit 95%iger Ausbeute eine schwarze Flüssigkeit mit einem Brechungsindex n2i = 1,6104.
Andere typische nach der Verfahrensweise von Beispiel 1 hergestellte ungesättigte 0,0-Dialkyl-thionothiol-phosphorsäureester
sind:The procedure of Example 1 is repeated, except that bis (O, O-dimethyl-thionophosphoric acid) disulfide is used in place of the corresponding bis (O, O-diethyl-thionophosphoric acid) disulfide; a black liquid with a refractive index n 2 i = 1.6104 is obtained with a 95% yield.
Other typical unsaturated 0,0-dialkyl-thionothiol-phosphoric acid esters prepared according to the procedure of Example 1 are:
Ο,Ο-Diäthyl-S-naphthyläthinyl-thiono-thiol-Ο, Ο-diethyl-S-naphthylethinyl-thiono-thiol-
phosphorsäureester,
0,0-Diäthyl-S-isopropyläthinyl-thiono-thiol-phosphoric acid ester,
0,0-diethyl-S-isopropylethinyl-thiono-thiol-
phosphorsäureester,
Ο,Ο-Dimethyl-S-n-propyläthinyl-thiono-thiol-phosphoric acid ester,
Ο, Ο-dimethyl-Sn-propyläthinyl-thiono-thiol-
phosphorsäureester,
Ο,Ο-Diäthyl-S-n-butyläthinyl-thiono-thiol-phosphoric acid ester,
Ο, Ο-diethyl-Sn-butyläthinyl-thiono-thiol-
phosphorsäureester,
Ο,Ο-Diäthyl-S-tert.butyläthinyl-thiono-thiol-phosphoric acid ester,
Ο, Ο-diethyl-S-tert.butyläthinyl-thiono-thiol-
phosphorsäureester.phosphoric acid ester.
Die erfindungsgemäß hergestellten Verbindungen sind, wie erwähnt, hochaktive Insektizide. Um die erhebliche insektizide Wirksamkeit zu zeigen, werden alle Verbindungen der obigen Beispiele 1 bis 3 in einem Lösungsmittel aus 65% Aceton und 35% Wasser mit einer Konzentration von 0,01 %> bezogen auf das Gewicht der Verbindung, aufgelöst. Die Lösung wird auf Nasturtiumaphiden gesprüht; die Ergebnisse der Tests sind in der folgenden Tabelle wiedergegeben:As mentioned, the compounds prepared according to the invention are highly active insecticides. To the To show significant insecticidal activity, all of the compounds of Examples 1 to 3 above are shown in a solvent composed of 65% acetone and 35% water with a concentration of 0.01%> based on the weight of the compound, dissolved. The solution is sprayed on nasturtium aphids; the Results of the tests are given in the following table:
Verbindunglink
Ο,Ο-Diäthyl-S-methyläthmyl-thiono-thiol-Ο, Ο-diethyl-S-methyläthmyl-thiono-thiol-
phosphorsäureester g phosphoric acid ester g
In einem Reaktionsgefäß wird Methylacetylengas in eine Lösung von 25 Teilen 3,03n-Butyllithium in Hexan (0,076 Mol) und 150 Teile Äther geleitet. Die Ο,Ο-Diäthyl-S-phenyläthinyl-thionothiol-phosphorsäureester In a reaction vessel, methyl acetylene gas is dissolved in a solution of 25 parts of 3.03 n-butyllithium in Hexane (0.076 mol) and 150 parts of ether passed. The Ο, Ο-diethyl-S-phenyläthinyl-thionothiol-phosphoric acid ester
0,0-Diäthyl-S-methyläthinyl-thionothiol-phosphorsäureester 0,0-diethyl-S-methyläthinyl-thionothiol-phosphoric acid ester
Ο,Ο-Dimethyl-S-phenyläthinyl-thionothiol-phosphorsäureester Ο, Ο-Dimethyl-S-phenyläthinyl-thionothiol-phosphoric acid ester
Tötungkilling
100100
O,O-Diäthyl-S-(/3-styryl)-thiono-thiol-phosphorsäureester O, O-diethyl-S - (/ 3-styryl) -thiono-thiol-phosphoric acid ester
Eine Lösung von 10 Teilen Bis-(O,O-diäthyl-thionoph.osphorsäure)-disulfid (0,027 Mol) in 10 Volumteilen Äther wird mit 50 Volumteilen 0,69molarem Styrylmagnesiumbromid (0,035 Mol) versetzt. Nach 20 Minuten^ langem Rühren wird die Reaktionsmischung mit Äther verdünnt, in Wasser gegossen, mit verdünnter Salzsäure gewaschen und über Magnesiumsulfat getrocknet. Das Lösungsmittel wird abgedampft und das Produkt im Vakuum destilliert, wobei man 4,6 Teile oder 59%) bezogen auf die theoretische Menge des gewünschten Produkts, als gelbe Flüssigkeit vom Brechungsindex (n|5) = 1,582 bis 1,583 erhält.A solution of 10 parts of bis (O, O-diethylthionophosphoric acid) disulfide (0.027 mol) in 10 parts by volume of ether is mixed with 50 parts by volume of 0.69 molar styryl magnesium bromide (0.035 mol). After stirring for 20 minutes, the reaction mixture is diluted with ether, poured into water, washed with dilute hydrochloric acid and dried over magnesium sulfate. The solvent is evaporated off and the product is distilled in vacuo, 4.6 parts or 59%, based on the theoretical amount of the desired product, being obtained as a yellow liquid with a refractive index (n | 5 ) = 1.582 to 1.583.
Analyse: PS2O2C12H17.Analysis: PS 2 O 2 C 12 H 17 .
Berechnet ... C 49,90, H 5,94, S 20,20, P 10,73 %; gefunden ... C 50,35, H 6,20, S 22,45, P 10,98 %.Calculated ... C 49.90, H 5.94, S 20.20, P 10.73%; Found ... C 50.35, H 6.20, S 22.45, P 10.98%.
O,O-Dimethyl-S-(|8-styryl)-thiono-thiol-phosphorsäureester O, O-Dimethyl-S- (| 8-styryl) -thiono-thiol-phosphoric acid ester
Das Verfahren des Beispiels 4 wird in allen Einzelheiten wiederholt, außer daß Bis-(O,O-dimethylthiono-phosphorsäure)-disulfid an Stelle von Bis-(O,O-diäthyl-thiono-phosphorsäure)-disulfid verwendet wird. Man gewinnt O,O-Dimethyl-S-(/?-styryl)-thiono-thiol-phosphorsäureester mit guter Ausbeute; der Brechungsindex (m|5) beträgt 1,6190.The procedure of Example 4 is repeated in all details, except that bis (O, O-dimethylthionophosphoric acid) disulfide is used in place of bis (O, O-diethylthionophosphoric acid) disulfide. O, O-dimethyl-S - (/? - styryl) -thiono-thiol-phosphoric acid ester is obtained in good yield; the refractive index (m | 5 ) is 1.6190.
Analyse: PS2O2C10H13.Analysis: PS 2 O 2 C 10 H 13 .
Berechnet ... C 46,4, H 5,03, S 24,5, P 11,89%; gefunden ... C 46,6, H 5,10, S 25,5, P 12,27%.Calculated ... C 46.4, H 5.03, S 24.5, P 11.89%; found ... C 46.6, H 5.10, S 25.5, P 12.27%.
Ο,Ο-Diäthyl-S-vinyl-thiono-thiol-phosphorsäureester Eine Lösung von Bis-(O,O-dimethyl-thiono-phosphorsäure)-disulfid (9,5 Teile) in 25 Volumteilen Äther wird in einem geeigneten Reaktionsgefäß mit 25 Volumteilen l,5n-Vinylmagnesiumbromid in 60 Sekunden versetzt. Die Reaktionsmischung wird dann mit Äther verdünnt, in Wasser gegossen, mit verdünnter Salzsäure gewaschen und über Magnesiumsulfat getrocknet. Das Lösungsmittel wird abgedampft und das Produkt im Vakuum destilliert; man erhält 3,2 Teile oder 57,8%) bezogen auf die theoretische Menge an gewünschtem hellgelben flüssigen Produkt vom Brechungsindex (nf?) = 1,5331.Ο, Ο-diethyl-S-vinyl-thiono-thiol-phosphoric acid ester A solution of bis- (O, O-dimethyl-thionophosphoric acid) -disulfide (9.5 parts) in 25 parts by volume ether is in a suitable reaction vessel with 25 parts by volume L, 5n vinyl magnesium bromide added in 60 seconds. The reaction mixture is then washed with ether diluted, poured into water, washed with dilute hydrochloric acid and dried over magnesium sulfate. The solvent is evaporated and the product is distilled in vacuo; 3.2 parts are obtained or 57.8%) based on the theoretical amount of the desired light yellow liquid product from Refractive index (nf?) = 1.5331.
Analyse: PS2O2C4H8.
Berechnet ... C 26,05, H 4,92, S 34,7%;
gefunden ... C 26,38, H 5,20, S 35,03%.Analysis: PS 2 O 2 C 4 H 8 .
Calculated ... C 26.05, H 4.92, S 34.7%;
Found ... C 26.38, H 5.20, S 35.03%.
Ο,Ο-Diäthyl-S-l-butenyl-thiono-thiol-phosphor-Ο, Ο-diethyl-S-l-butenyl-thiono-thiol-phosphorus-
säureesteracid ester
10,45 Teile Bis - (0,0 - diäthyl - thiono - phosphorsäure)-disulfid (0,028 Mol) der Formel10.45 parts of bis (0.0 - diethyl - thiono - phosphoric acid) disulfide (0.028 moles) of the formula
(CH3CH2O)2P S(CH 3 CH 2 O) 2 PS
in 14 Volumteilen Äther werden langsam mit 10 Volumteilen (0,030 Mol) 3,03n-Butenyllithium in 20 Volumteilen Äther versetzt. Die Zugabe dauert etwa 15 Minuten. Die Mischung wird weitere 10 Minuten gerührt, mit Wasser gewaschen und über Magnesiumsulfat getrocknet. Beim Abdampfen des Lösungsmittels bleiben 5,85 Teile (86% der Theorie) hellbraune Flüssigkeit vom Brechungsindex («f) = 1,520 zurück. Folgende andere typische ungesättigte 0,0-Dialkylthiono-thiol-phosphorsäureester der vorliegenden Erfindung können nach der Verfahrensweise der Beispiele 4 bis 8 hergestellt werden:in 14 parts by volume of ether slowly add 10 parts by volume (0.030 mol) of 3,03n-butenyllithium in 20 parts by volume Ether shifted. The addition takes about 15 minutes. The mixture is stirred for a further 10 minutes, washed with water and dried over magnesium sulfate. When the solvent evaporates this leaves 5.85 parts (86% of theory) of light brown liquid with a refractive index («f) = 1.520. The following other typical unsaturated 0,0-dialkylthionothiol-phosphoric acid esters of the present invention can be prepared according to the procedure of Examples 4 to 8:
Ο,Ο-Diäthyl-S-naphthylvinyl-thiono-thiol-Ο, Ο-diethyl-S-naphthylvinyl-thiono-thiol-
phosphorsäureester,
0,0-Diäthyl-S-isopropenyl-tniono-thiol-phosphoric acid ester,
0,0-diethyl-S-isopropenyl-tniono-thiol-
phosphorsäureester,
0,0-Dimethyl-S-n-propenyl-thiono-thiol-phosphoric acid ester,
0,0-dimethyl-Sn-propenyl-thiono-thiol-
phosphorsäureester,
O,O-Diäthyl-S-1 -butenyl-thiono-thiol-phosphoric acid ester,
O, O-diethyl-S-1 -butenyl-thiono-thiol-
phosphorsäureester.phosphoric acid ester.
Die erfindungsgemäß hergestellten Verbindungen sind, wie erwähnt, hochaktive Insektizide. Um die erhebliche insektizide Wirksamkeit zu zeigen, werden alle Verbindungen der Beispiele 4 bis 8 in einem Lösungsmittel aus 65% Aceton und 35% Wasser bei einer 0,l%igen Konzentration, bezogen auf das Gewicht der Verbindung, aufgelöst. Die Lösung wird auf Nasturtiumaphiden gesprüht; die Ergebnisse der Tests sind in der folgenden Tabelle II wiedergegeben.As mentioned, the compounds prepared according to the invention are highly active insecticides. To the To show considerable insecticidal activity, all compounds of Examples 4 to 8 are in a solvent from 65% acetone and 35% water at a 0.1% concentration based on weight the connection, dissolved. The solution is sprayed on nasturtium aphids; the results of the Tests are given in Table II below.
Analyse: PS2O2C6H13.Analysis: PS 2 O 2 C 6 H 13 .
Berechnet ... C 33,95, H 6,17, P 14,59, S 30,19%; gefunden ... C 33,85, H 5,51, P 14,85, S 29,74%.Calculated ... C 33.95, H 6.17, P 14.59, S 30.19%; Found ... C 33.85, H 5.51, P 14.85, S 29.74%.
65 Verbindung65 connection
O,O-Diäthyl-S-(^-styryl)-thiono-thiol-O, O-diethyl-S - (^ - styryl) -thiono-thiol-
phesphorsäureester phosphoric acid ester
0,0-Diäthyl-S-vinyl-thiono-thiol-0,0-diethyl-S-vinyl-thiono-thiol-
phosphorsäureester phosphoric acid ester
O,O-Dimethyl-S-GS-styryl)-thiono-thiol-O, O-dimethyl-S-GS-styryl) -thiono-thiol-
phosphorsäureester phosphoric acid ester
0,0-Dimethyl-S-vinyl-thiono-thiol-0,0-dimethyl-S-vinyl-thiono-thiol-
phosphorsäureester phosphoric acid ester
0/ /00 / / 0
Tötungkilling
98
100
100
10098
100
100
100
Das Bis - (0,0 - dimethyl - thiono - phosphorsäure)-disulfid des Beispiels 6 wird durch Bis-(O,O-diäthylthiono-phosphorsäure)-disulfid ersetzt und die Verfahrensweise in jeder wesentlichen Einzelheit befolgt. Man erhält eine gute Ausbeute an O,O-Diäthyl-S-vinyl-thiono-thiol-phosphorsäureester (62% der Theorie). Die gewünschte Verbindung hat den Brechungsindex (n2 D 5) 1,512 bis 1,514.The bis (0,0-dimethyl-thionophosphoric acid) disulfide of Example 6 is replaced by bis (O, O-diethylthionophosphoric acid) disulfide and the procedure followed in every essential detail. A good yield of O, O-diethyl-S-vinyl-thiono-thiol-phosphoric acid ester (62% of theory) is obtained. The desired compound has an index of refraction (n 2 D 5 ) 1.512 to 1.514.
Claims (5)
(R1O)2-P-S-S-P-(OR1), 10 ii
(R 1 O) 2 -PSSP- (OR 1 ), 10
oder 35R '
or 35
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28236A US3019159A (en) | 1960-05-11 | 1960-05-11 | Novel phosphorodithioates and methods for preparing the same |
| US53613A US3021352A (en) | 1960-09-02 | 1960-09-02 | Preparation of s-(1-alkenyl) phosphorodithioates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1150069B true DE1150069B (en) | 1963-06-12 |
Family
ID=26703457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA36478A Pending DE1150069B (en) | 1960-05-11 | 1961-01-12 | Process for the production of an unsaturated 0, 0-dialkyl-thiono-thiol-phosphoric acid ester |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE598857A (en) |
| CH (1) | CH398554A (en) |
| DE (1) | DE1150069B (en) |
| GB (1) | GB926604A (en) |
| NL (1) | NL259863A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057235A (en) * | 1988-06-23 | 1991-10-15 | Mobil Oil Corporation | Sulfur-phosphorus adducts of chromium catalyzed polyalphaolefins |
-
0
- NL NL259863D patent/NL259863A/xx unknown
-
1961
- 1961-01-05 BE BE598857A patent/BE598857A/en unknown
- 1961-01-12 CH CH37461A patent/CH398554A/en unknown
- 1961-01-12 DE DEA36478A patent/DE1150069B/en active Pending
- 1961-01-13 GB GB148361A patent/GB926604A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB926604A (en) | 1963-05-22 |
| NL259863A (en) | |
| CH398554A (en) | 1966-03-15 |
| BE598857A (en) | 1961-07-05 |
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