DE917668C - Process for the preparation of neutral esters of dithiophosphoric acid - Google Patents
Process for the preparation of neutral esters of dithiophosphoric acidInfo
- Publication number
- DE917668C DE917668C DEF9629A DEF0009629A DE917668C DE 917668 C DE917668 C DE 917668C DE F9629 A DEF9629 A DE F9629A DE F0009629 A DEF0009629 A DE F0009629A DE 917668 C DE917668 C DE 917668C
- Authority
- DE
- Germany
- Prior art keywords
- dithiophosphoric acid
- water
- benzene
- acid
- diethyl
- 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.)
- Expired
Links
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 8
- 230000007935 neutral effect Effects 0.000 title claims description 8
- 150000002148 esters Chemical class 0.000 title description 11
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 45
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- XZCHJYXUPALGHH-UHFFFAOYSA-N chloromethylsulfanylethane Chemical compound CCSCCl XZCHJYXUPALGHH-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JWMLCCRPDOIBAV-UHFFFAOYSA-N chloro(methylsulfanyl)methane Chemical compound CSCCl JWMLCCRPDOIBAV-UHFFFAOYSA-N 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic 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
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material 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)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
AUSGEGEBEN AM 9. SEPTEMBER 1954ISSUED SEPTEMBER 9, 1954
DEUTSCHES PATENTAMTGERMAN PATENT OFFICE
PATENTSCHRIFTPATENT LETTERING
KLASSE 12o GRUPPE 23o3 CLASS 12o GROUP 23o3
jF g02Q IV d J12 jF g02Q IV d J12
Dr. Walter Lorenz, Wuppertal-Elberfeld und Dr. Gerhard Schrader, OpladenDr. Walter Lorenz, Wuppertal-Elberfeld and Dr. Gerhard Schrader, Opladen
sind als Erfinder genannt wordenhave been named as inventors
Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-BayerwerkPaint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk
Verfahren zur Herstellung von neutralen Estern der Dithiophosphorsäure Patentiert im Gebiet der Bundesrepublik Deutschland vom 2. August 1952 anProcess for the preparation of neutral esters of dithiophosphoric acid Patented in the territory of the Federal Republic of Germany on August 2, 1952
Patentanmeldung bekanntgemacht am 11. Februar 1954Patent application published February 11, 1954
Patenterteilung bekanntgemacht am 29. Juli 1954Patent issued July 29, 1954
Es wurde gefunden, daß man neutrale Ester der Dithiophosphorsäure erhält, wenn man o, o-Dialkyldithiophosphorsäuren in Form ihrer Alkalisalze oder in Gegenwart eines säurebindenden Mittels mit Verbindung der FormelIt has been found that neutral esters of phosphorodithioic acid are obtained if o, o-dialkyl phosphorodithioic acids are used in the form of their alkali salts or in the presence of an acid-binding agent with a compound the formula
HaI-(CH8),.. S -C,Hal- (CH 8 ), .. S -C,
worin χ und y ι oder 2 ist, umsetzt. Zweckmäßigerweise nimmt man die Umsetzung in einem geeigneten Lösungsmittel vor; als solche seien genannt: Benzol Und seine Homologen, Ketone, wie Aceton, Methylketon u. a., und Alkohole. Auch in wäßriger Lösung in Gegenwart eines säurebindenden Mittels können die Umsetzungen vorgenommen werden.wherein χ and y ι or 2 is implemented. The reaction is expediently carried out in a suitable solvent; as such are: Benzene and its homologues, ketones such as acetone, methyl ketone, etc., and alcohols. The reactions can also be carried out in aqueous solution in the presence of an acid-binding agent.
Die so erhaltenen neutralen Ester der o, o-Dialkyldithiophosphorsäuren sind meist farblose wasserunlösliche öle und zeichnen sich durch hervorragende kontaktinsekticide Eigenschaften aus; sie entfalten gleichzeitig eine sehr hohe systematische Wirkung bei lebenden Pflanzen. Aus der umstehenden Tabelle gehen die Eigenschaften dieser Ester hervor:The neutral esters of o, o-dialkyldithiophosphoric acids obtained in this way are mostly colorless, water-insoluble oils and are characterized by excellent contact insecticidal properties; at the same time they have a very high systematic effect living plants. The following table shows the properties of these esters:
Zusammensetzung Blattlauswirkung
Konzentration AbtötungComposition aphid effect
Concentration kill
Maus subcutan DL looMouse subcutaneous DL loo
SS.
CH3S · C2H4S-PCH 3 S • C 2 H 4 SP
S
Il
C2H5S · C2H4S — P — (OC2Hg)2 ...S.
Il
C 2 H 5 S · C 2 H 4 S - P - (OC 2 Hg) 2 ...
S
Il
C2H8S-CH2-S — P—(OCH3)2 ...S.
Il
C 2 H 8 S-CH 2 -S - P- (OCH 3 ) 2 ...
CH3S-CH2-S-P-(OC2Hg)2 ...CH 3 S-CH 2 -SP- (OC 2 Hg) 2 ...
S
11
ao C2H5S · CH2 · S — P — (OC2Hg)2 S.
11th
ao C 2 H 5 S • CH 2 • S - P - (OC 2 Hg) 2
S
Il
C2H5S-CH2-S-P—(OC3H7n)2 ..S.
Il
C 2 H 5 S-CH 2 -SP- (OC 3 H 7 n) 2 ..
SS.
Il
C2H5S · CH2 · S — P — (O-iso-C3H7)2 Il
C 2 H 5 S • CH 2 • S-P - (O-iso-C 3 H 7 ) 2
Es war bereits bekannt, neutrale Ester der Thiophosphorsäure dadurch herzustellen, daß man Alkalidialkylmonothiophosphate mit Verbindungen der allgemeinen Formel Cl — Alkyl — S — R, worin R für einen Alkyl-, Aryl- oder Aralkylrest steht, umsetzt. Vor diesen bekannten Estern der Thiophosphorsäure zeichnen sich die erfindungsgemäß erhältlichen Ester der Dithiophosphorsäure durch geringere Toxizität gegenüber Warmblütern aus. Ferner waren aber auch schon neutrale Dithiophosphorsäureester entsprechend den neuen Verbindungen bekannt, die sich jedoch von den letzteren in ihrer Zusammensetzung dadurch unterscheiden, daß in ihnen das Symbol y der eingangs genannten Formel größer als 2 ist und die außerdem nach einem anderen Verfahren hergestellt werden; in ihrer insekticiden Wirkung sind sie den neuen Verbindungen unterlegen.It was already known that neutral esters of thiophosphoric acid can be prepared by reacting alkali dialkyl monothiophosphates with compounds of the general formula Cl - alkyl - S - R, in which R is an alkyl, aryl or aralkyl radical. Before these known esters of thiophosphoric acid, the esters of dithiophosphoric acid obtainable according to the invention are distinguished by lower toxicity towards warm-blooded animals. Furthermore, neutral dithiophosphoric acid esters corresponding to the new compounds were also known, which, however, differ from the latter in their composition in that in them the symbol y of the formula mentioned above is greater than 2 and which are also prepared by a different process; in their insecticidal effect they are inferior to the new compounds.
102 g 0, o-Diäthyl-dithiophosphorsäure werden in 300 ecm Benzol gelöst und unter Kühlung mit 44 g Pyridin neutralisiert. Bei 50 bis 6o° tropft man 55 g ^-Chloräthyl-methyl-sulöd zu und erwärmt danach 2 Stunden bei 75°. Nach dem Erkalten saugt man vom salzsauren Pyridin ab, wäscht die Benzollösung mit Wasser und trocknet sie über Natriumsulfat. Durch Fraktionieren erhält man 107 g Dithiophosphorsäure - 0, 0 - diäthyl- S - methylmercaptoäthylester vom Kpli5127 bis 1280 als farbloses, wasserunlösliches öl von charakteristischem Geruch.102 g of 0, o-diethyl-dithiophosphoric acid are dissolved in 300 ecm of benzene and neutralized with 44 g of pyridine while cooling. At 50 to 60 °, 55 g of ^ -chloroethyl-methyl-sulod are added dropwise and the mixture is then heated at 75 ° for 2 hours. After cooling, the hydrochloric pyridine is filtered off with suction, the benzene solution is washed with water and dried over sodium sulfate. Fractionation gives 107 g of dithiophosphoric acid - 0, 0 - diethyl - S - methyl mercaptoethyl ester of bp li5 127 to 128 0 as a colorless, water-insoluble oil with a characteristic odor.
112 g (0,5 Mol) o, o-diäthyl-dithiophosphorsaures Kalium werden in 400 ecm Äthylalkohol gelöst. Bei 700 tropft man 55 g (0,5 Mol) /S-Chloräthyl-methyl-0,005 112 g (0.5 mol) of o, o-diethyl-dithiophosphoric acid potassium are dissolved in 400 ecm of ethyl alcohol. At 70 0 to 55 g (0.5 mol) / dropwise S-chloroethyl-methyl-0.005
0,0050.005
0,0050.005
0,0050.005
0,005
0,00050.005
0.0005
0,0050.005
0,0050.005
100%100%
10 mg/kg10 mg / kg
100%100%
100%
sulfid zu und rührt 2 Stunden bei 70 bis 750 nach. Nach dem Erkalten saugt man das Salz ab und destilliert den Alkohol ab. Das zurückbleibende öl wird mit Benzol aufgenommen und mit Wasser gewaschen. Nach kurzem Trocknen über Natriumsulfat wird destilliert. Der neue Ester der Dithiophosphorsäure siedet bei Kpli5 127 bis 128° (vgl. Beispiel 1); Ausbeute: 87 g.sulfide and stirred at 70 to 75 0 for 2 hours. After cooling, the salt is suctioned off and the alcohol is distilled off. The remaining oil is taken up with benzene and washed with water. After brief drying over sodium sulfate, it is distilled. The new ester of dithiophosphoric acid boils at bp li5 127 to 128 ° (see Example 1); Yield: 87 g.
102 g 0, o-Diäthyl-dithiophosphorsäure werden in 300 ecm Benzol gelöst und unter Kühlung mit 44 g Pyridin versetzt. Bei 70 bis 750 tropft man 64 g jS-Chloräthyl-äthyl-suMd zu und verfährt weiter, wie im Beispiel 1 beschrieben. Man erhält 94 g Dithiophosphorsäure-Oi o-diäthyl-S-äthylmercaptoäthylester vom Kpli5 132 bis 133° als farbloses, wasserunlösliches Öl.102 g of 0, o-diethyl-dithiophosphoric acid are dissolved in 300 ecm of benzene, and 44 g of pyridine are added while cooling. At 70 to 75 0 is added dropwise 64 g jS-chloroethyl-ethyl-Sumd to and the subsequent procedure is as described in Example. 1 94 g of dithiophosphoric acid Oi o-diethyl-S-ethyl mercaptoethyl ester with a boiling point of 132 to 133 ° are obtained as a colorless, water-insoluble oil.
112 g (0,5 Mol) o, o-diäthyl-dithiophosphorsaures Kalium werden in 400 ecm Äthylalkohol gelöst. Bei 70° tropft man 64 g (0,5 Mol) /J-Chloräthyl-äthylsulfid zu und erwärmt 2 Stunden bei dieser Temperatur. Nach dem Erkalten saugt man vom Salz ab, destilliert das Lösungsmittel ab, nimmt den Rückstand mit Benzol auf und wäscht mit Wasser. Nach dem Trocknen über Natriumsulfat wird fraktioniert. Man erhält 115 g Dithiophosphorsäure-o, o-diäthyl-S-äthylmercaptoäthylester vom Kp1)5 132 bis 133°.112 g (0.5 mol) of o, o-diethyl-dithiophosphoric acid potassium are dissolved in 400 ecm of ethyl alcohol. 64 g (0.5 mol) of I-chloroethyl ethyl sulfide are added dropwise at 70 ° and the mixture is heated at this temperature for 2 hours. After cooling, the salt is filtered off with suction, the solvent is distilled off, the residue is taken up in benzene and washed with water. After drying over sodium sulfate, it is fractionated. 115 g of dithiophosphoric acid-o, o-diethyl-S-ethyl mercaptoethyl ester with a boiling point of 1) 5 132 to 133 ° are obtained.
67.5 S °> o-diäthyl-dithiophosphorsaures Kalium werden in 200 ecm Aceton gelöst. Bei 200 tropft man 30 g Chlormethyl-methyl-sulfid (Liebigs Annalen der67.5 ° S> o-diethyl-dithiophosphorsaures potassium are dissolved in 200 cc acetone. At 20 0 , 30 g of chloromethyl methyl sulfide (Liebigs Annalen der
Chemie 563, 62 [1949]) ein. Die Temperatur steigt allmählich unter Veränderung der Salze auf 40°. Man rührt 2 Stunden bei 50 bis 55° und saugt nach dem Erkalten von den Salzen ab. Nach dem Abdestillieren des Lösungsmittels wird der Rückstand mit Benzol aufgenommen, mit Wasser gewaschen und über Natriumsulfat getrocknet. Durch Destillation erhält man 47 g Dithiophosphorsäure-o, o-diäthyl-S-methylmercaptomethylester vom Kpli5113 bis 114° als farbloses, wasserunlösliches Öl.Chemie 563, 62 [1949]). The temperature rises gradually to 40 ° with changes in the salts. The mixture is stirred for 2 hours at 50 to 55 ° and, after cooling, the salts are filtered off with suction. After the solvent has been distilled off, the residue is taken up in benzene, washed with water and dried over sodium sulfate. Distillation gives 47 g of dithiophosphoric acid-o, o-diethyl-S-methylmercaptomethyl ester with a boiling point of 113 ° to 114 ° as a colorless, water-insoluble oil.
224 g (1 Mol) o, 0-diäthyl-dithiophosphorsaures Kalium werden in 500 ecm Benzol suspendiert. Bei 50 bis 6o° tropft man 110 g (1 Mol) Chlormethyläthyl-sulfid (Berichte der Deutschen Chemischen Gesellschaft 69,1612 [1936]) zu und erwärmt 3 Stunden bei 70 bis 750. Nach dem Erkalten wird mit ungefähr 100 ecm Wasser das Natriumchlorid in eine filtrier-224 g (1 mol) of o, 0-diethyl-dithiophosphoric acid potassium are suspended in 500 ecm of benzene. At 50 to 6o ° is added dropwise to 110 g (1 mol) Chlormethyläthyl sulfide (Berichte der Deutschen Chemischen Gesellschaft 69.1612 [1936]) is added and heated for 3 hours at 70 to 75 0th After cooling down, the sodium chloride is poured into a filter with about 100 ecm of water.
ao bare Form gebracht. Das Filtrat wird fraktioniert. Man erhält 215 g Dithiophosphorsäure-o, o-diäthyl-S-äthylmercaptomethylester vom Kp2 125 bis 1270 als nahezu farbloses, wasserunlösliches öl.ao bare form. The filtrate is fractionated. 215 g of dithiophosphoric acid-o, o-diethyl-S-ethyl mercaptomethyl ester with a boiling point of 2 125 to 127 0 are obtained as an almost colorless, water-insoluble oil.
98 g 0, o-Diäthyl-dithiophosphorsäure (95%ig) tropft man bei 20 bis 300 zu einer Suspension von 70 g Kaliumcarbonat in 200 ecm Aceton. Anschließend tropft man 55 g Chlormethyl-äthyl-sulfid zu. Durch Kühlen mit Wasser hält man dabei die Temperatur bei 35 bis 40°, die man 2 Stunden hält. Nach dem Erkalten saugt man die Salze ab und verfährt weiter, wie im Beispiel 2 beschrieben. Man erhält 98 g Dithiophosphorsäure - o, 0 - diäthyl - S - äthylmercaptomethylester vom Kp2 125 bis 1270 als farbloses, wasserunlösliches öl.98 g 0, o-diethyl-dithiophosphoric acid (95% strength) are added dropwise at 20 to 30 0 g to a suspension of 70 potassium carbonate in 200 cc acetone. 55 g of chloromethyl ethyl sulfide are then added dropwise. By cooling with water, the temperature is kept at 35 to 40 °, which is maintained for 2 hours. After cooling, the salts are suctioned off and the procedure is continued as described in Example 2. 98 g of dithiophosphoric acid-o, 0-diethyl-S-ethyl mercaptomethyl ester with a boiling point of 2 125 to 127 0 are obtained as a colorless, water-insoluble oil.
98 g 0, o-Diäthyl-dithiophosphorsäure (95%ig) werden mit 45 g Natriumbicarbonat in 250 ecm Wasser gelöst. Bei 20 bis 25° tropft man unter Kühlen 55 g Chlormethyl-äthyl-sulfid zu. Durch Zugabe von etwas Natriumbicarbonat stellt man die kongosauer gewordene Lösung wieder neutral und rührt 3 Stunden bei 20 bis 250 weiter. Nach dieser Zeit hat sich die Lösung geklärt. Das öl wird mit Benzol aufgenommen und damit weiter verfahren, wie im Beispiel 1 beschrieben. Man erhält 71 g Dithiophosphorsäure-0, o-diäthyl-S-äthylmercaptomethylester vom Kp2i5 128 bis 1290.98 g of 0, o-diethyldithiophosphoric acid (95%) are dissolved with 45 g of sodium bicarbonate in 250 ecm of water. At 20 ° to 25 °, 55 g of chloromethylethyl sulfide are added dropwise with cooling. By addition of a little sodium bicarbonate provides one the Congo red solution had become neutral again and stirred for 3 hours at 20 to 25 0. After this time, the solution has been resolved. The oil is taken up with benzene and the procedure is continued as described in Example 1. 71 g of dithiophosphoric acid 0, o-diethyl-S-ethyl mercaptomethyl ester with a boiling point of 2 15 128 to 129 0 are obtained .
220 g 0, o-Di-n-propyl-dithiophosphorsäure werden220 g of 0, o-di-n-propyl-dithiophosphoric acid become
in 600 ecm Benzol gelöst und unter Kühlung mit 84 g Pyridin neutralisiert. Bei 70 bis 750 tropft man in g Chlormethyl-äthyl-sulfid zu und erwärmt danach 2 Stunden bei 750. Nach dem Erkalten saugt man vom salzsauren Pyridin ab, wäscht das Benzol mit Wasser und trocknet über Natriumsulfat. Durch Fraktionieren erhält man 249 g Dithiophosphorsäure-0,0-di-n-propyl-S-äthylmercaptomethylester vom Kpli6 132 bis 1330 als blaßgelbes, wasserunlösliches öl.dissolved in 600 ecm of benzene and neutralized with 84 g of pyridine while cooling. At 70 to 75 0 are added dropwise in g chloromethyl ethyl sulfide and then heated for 2 hours at 75 0th After cooling, the hydrochloric pyridine is filtered off with suction, the benzene is washed with water and dried over sodium sulfate. Fractionation gives 249 g of dithiophosphoric acid 0,0-di-n-propyl-S-ethyl mercaptomethyl ester with a boiling point of 132 to 133 0 as a pale yellow, water-insoluble oil.
220 g 0, o-Di-isopropyl-dithiophosphorsäure werden in 600 ecm Benzol gelöst und mit 84 g Pyridin neutralisiert. Bei 70 bis 750 tropft man in g Chlormethyläthyl-sulfid zu und erwärmt danach 2 Stunden bei 750. Nach dem Erkalten saugt man das salzsaure Pyridin ab, wäscht das Benzol mit Wasser und trocknet es über Natriumsulfat. Durch Fraktionieren erhält man 237 g Dithiophosphorsäure-o, o-di-isopropyl-S-äthylmercaptomethylester vom Kp2 126 bis 1280 als farbloses, wasserunlösliches öl.220 g of 0, o-di-isopropyl-dithiophosphoric acid are dissolved in 600 ecm of benzene and neutralized with 84 g of pyridine. At 70 to 75 0 are added dropwise in g Chlormethyläthyl sulfide and then heated for 2 hours at 75 0th After cooling, the hydrochloric pyridine is filtered off with suction, the benzene is washed with water and dried over sodium sulfate. Fractionation gives 237 g of dithiophosphoric acid-o, o-di-isopropyl-S-ethyl mercaptomethyl ester with a boiling point of 2 126 to 128 0 as a colorless, water-insoluble oil.
84 g o, o-Dimethyl-dithiophosphorsäure (95% ig) tropft man bei 20 bis 25 ° zu einer Anschlämmung von 70 g Kaliumcarbonat in 200 ecm Aceton. Danach tropft man 55 g Chlormethyl-äthyl-sulfid zu. Die Temperatur steigt allmählich auf 40°. Man rührt über Nacht bei Zimmertemperatur, saugt die Salze dann ab und destilliert das Lösungsmittel ab. Das zurückbleibende öl nimmt man mit Benzol auf und wäscht es mit Wasser. Nach kurzem Trocknen über Natriumsulfat erhält man durch Fraktionieren 70 g Dithiophosphorsäure-o, o-dimethyl-S-äthylmercaptomethylester vom Kp1>5 114 bis ii6° (unter geringer Zersetzung) als farbloses, wasserunlösliches 01.84 go, o-dimethyl-dithiophosphoric acid (95%) is added dropwise at 20 to 25 ° to a suspension of 70 g of potassium carbonate in 200 ecm of acetone. 55 g of chloromethyl ethyl sulfide are then added dropwise. The temperature gradually rises to 40 °. The mixture is stirred overnight at room temperature, the salts are then filtered off with suction and the solvent is distilled off. The remaining oil is taken up in benzene and washed with water. After brief drying over sodium sulfate, 70 g of dithiophosphoric acid-o, o-dimethyl-S-ethylmercaptomethyl ester with a boiling point of 1> 5 114 to 116 ° (with little decomposition) are obtained as colorless, water-insoluble oil.
84 g 0, o-Dimethyl-dithiophosphorsäure werden in 300 ecm Benzol gelöst und mit 44 g Pyridin neutralisiert. Bei 700 tropft man 65 g ^-Chloräthyl-äthyl-sulfid zu und erwärmt danach 2 Stunden bei 75°. Nach dem Erkalten verfährt man, wie im Beispiel 1 beschrieben. Durch Fraktionieren erhält man jy g Dithiophosphorsäure - o, 0 - dimethyl - S - äthylmercaptoäthylester als hellgelbes, wasserunlösliches öl vom Kp2i5 135 bis 1400.84 g of 0, o-dimethyl-dithiophosphoric acid are dissolved in 300 ecm of benzene and neutralized with 44 g of pyridine. At 70 0 to 65 g ^ dropwise -Chloräthyl-ethyl sulfide to and then heated for 2 hours at 75 °. After cooling, the procedure is as described in Example 1. Fractionation gives jy g of dithiophosphoric acid - 0.0 - dimethyl - S - ethyl mercaptoethyl ester as a pale yellow, water - insoluble oil with a boiling point of 2.5 135 to 140 0 .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF9629A DE917668C (en) | 1952-08-01 | 1952-08-02 | Process for the preparation of neutral esters of dithiophosphoric acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE748299X | 1952-08-01 | ||
| DEF9629A DE917668C (en) | 1952-08-01 | 1952-08-02 | Process for the preparation of neutral esters of dithiophosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE917668C true DE917668C (en) | 1954-09-09 |
Family
ID=25947511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF9629A Expired DE917668C (en) | 1952-08-01 | 1952-08-02 | Process for the preparation of neutral esters of dithiophosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE917668C (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1006417B (en) * | 1955-10-13 | 1957-04-18 | Bayer Ag | Process for the preparation of O, O-dialkyl-thiolthionophosphoric acid-S-aralkyl mercaptoalkyl esters |
| DE1010960B (en) * | 1955-10-13 | 1957-06-27 | Bayer Ag | Process for the production of neutral thionothiolphosphoric acid esters |
| DE1014105B (en) * | 1955-09-07 | 1957-08-22 | Bayer Ag | Process for the preparation of O, O-dialkyl-thiophosphoric acid triesters |
| DE1014107B (en) * | 1954-12-28 | 1957-08-22 | Wolfen Filmfab Veb | Process for the preparation of esters of phosphorus-containing acids |
| DE1014987B (en) * | 1954-08-02 | 1957-09-05 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1018053B (en) * | 1955-10-29 | 1957-10-24 | Bayer Ag | Process for the preparation of S-chlorobenzyl esters of O, O-dialkyl-thiolphosphoric acid |
| DE1032247B (en) * | 1954-12-04 | 1958-06-19 | Bayer Ag | Process for the production of organic phosphorus compounds |
| DE1036846B (en) * | 1956-12-21 | 1958-08-21 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1045391B (en) * | 1956-12-07 | 1958-12-04 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1046393B (en) * | 1956-03-12 | 1958-12-11 | Bayer Ag | Pest repellants |
| DE1056121B (en) * | 1957-02-27 | 1959-04-30 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1062239B (en) * | 1956-07-28 | 1959-07-30 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1063155B (en) * | 1957-10-09 | 1959-08-13 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1068699B (en) * | 1955-01-21 | 1959-11-12 | Sandoz A.G., Basel (Schweiz) | Process for the preparation of thiol or thionothiol phosphoric acid esters |
| DE1083808B (en) * | 1957-06-05 | 1960-06-23 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
| DE1098762B (en) * | 1953-10-07 | 1961-02-02 | Sandoz Ag | Pest repellants |
| DE1106317B (en) * | 1959-08-21 | 1961-05-10 | Bayer Ag | Process for the preparation of esters of the thioic acids of phosphorus |
| DE1139492B (en) * | 1959-09-03 | 1962-11-15 | Bayer Ag | Process for the production of dithiolphosphonic acid esters |
| DE1148549B (en) * | 1959-06-27 | 1963-05-16 | Bayer Ag | Process for the preparation of thionothiolphosphonic acid esters |
| DE1187849B (en) * | 1955-11-22 | 1965-02-25 | Bayer Ag | Insecticides |
| DE1212777B (en) * | 1963-11-07 | 1966-03-17 | Bayer Ag | Fungitoxic agents |
| US6818670B2 (en) | 1999-11-09 | 2004-11-16 | Bayer Aktiengesellschaft | Active ingredient combination having insecticidal and acaricidal characteristics |
| US6900190B2 (en) | 2000-03-28 | 2005-05-31 | Bayer Aktiengesellschaft | Active substance combinations having insecticidal and acaricidal properties |
| DE102007045955A1 (en) | 2007-09-26 | 2009-04-09 | Bayer Cropscience Ag | Active agent combination, useful e.g. for combating animal pests and treating seeds of transgenic plants, comprises substituted amino-furan-2-one compound and at least one compound e.g. diazinon, isoxathion, carbofuran or aldicarb |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE830509C (en) * | 1950-05-24 | 1952-02-04 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
| DE833807C (en) * | 1948-03-26 | 1952-03-13 | American Cyanamid Co | Process for the preparation of dithiophosphoric acid triesters |
-
1952
- 1952-08-02 DE DEF9629A patent/DE917668C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE833807C (en) * | 1948-03-26 | 1952-03-13 | American Cyanamid Co | Process for the preparation of dithiophosphoric acid triesters |
| DE830509C (en) * | 1950-05-24 | 1952-02-04 | Bayer Ag | Process for the preparation of neutral esters of thiophosphoric acid |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1098762B (en) * | 1953-10-07 | 1961-02-02 | Sandoz Ag | Pest repellants |
| DE1014987B (en) * | 1954-08-02 | 1957-09-05 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1032247B (en) * | 1954-12-04 | 1958-06-19 | Bayer Ag | Process for the production of organic phosphorus compounds |
| DE1014107B (en) * | 1954-12-28 | 1957-08-22 | Wolfen Filmfab Veb | Process for the preparation of esters of phosphorus-containing acids |
| DE1068699B (en) * | 1955-01-21 | 1959-11-12 | Sandoz A.G., Basel (Schweiz) | Process for the preparation of thiol or thionothiol phosphoric acid esters |
| DE1014105B (en) * | 1955-09-07 | 1957-08-22 | Bayer Ag | Process for the preparation of O, O-dialkyl-thiophosphoric acid triesters |
| DE1006417B (en) * | 1955-10-13 | 1957-04-18 | Bayer Ag | Process for the preparation of O, O-dialkyl-thiolthionophosphoric acid-S-aralkyl mercaptoalkyl esters |
| DE1010960B (en) * | 1955-10-13 | 1957-06-27 | Bayer Ag | Process for the production of neutral thionothiolphosphoric acid esters |
| DE1018053B (en) * | 1955-10-29 | 1957-10-24 | Bayer Ag | Process for the preparation of S-chlorobenzyl esters of O, O-dialkyl-thiolphosphoric acid |
| DE1187849B (en) * | 1955-11-22 | 1965-02-25 | Bayer Ag | Insecticides |
| DE1046393B (en) * | 1956-03-12 | 1958-12-11 | Bayer Ag | Pest repellants |
| DE1062239B (en) * | 1956-07-28 | 1959-07-30 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1045391B (en) * | 1956-12-07 | 1958-12-04 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1036846B (en) * | 1956-12-21 | 1958-08-21 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1056121B (en) * | 1957-02-27 | 1959-04-30 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1096671B (en) * | 1957-05-10 | 1961-01-05 | Bayer Ag | Pest repellants |
| DE1083808B (en) * | 1957-06-05 | 1960-06-23 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1063155B (en) * | 1957-10-09 | 1959-08-13 | Bayer Ag | Process for the preparation of thiophosphoric acid esters |
| DE1148549B (en) * | 1959-06-27 | 1963-05-16 | Bayer Ag | Process for the preparation of thionothiolphosphonic acid esters |
| DE1106317B (en) * | 1959-08-21 | 1961-05-10 | Bayer Ag | Process for the preparation of esters of the thioic acids of phosphorus |
| DE1139492B (en) * | 1959-09-03 | 1962-11-15 | Bayer Ag | Process for the production of dithiolphosphonic acid esters |
| DE1212777B (en) * | 1963-11-07 | 1966-03-17 | Bayer Ag | Fungitoxic agents |
| US6818670B2 (en) | 1999-11-09 | 2004-11-16 | Bayer Aktiengesellschaft | Active ingredient combination having insecticidal and acaricidal characteristics |
| US6900190B2 (en) | 2000-03-28 | 2005-05-31 | Bayer Aktiengesellschaft | Active substance combinations having insecticidal and acaricidal properties |
| DE102007045955A1 (en) | 2007-09-26 | 2009-04-09 | Bayer Cropscience Ag | Active agent combination, useful e.g. for combating animal pests and treating seeds of transgenic plants, comprises substituted amino-furan-2-one compound and at least one compound e.g. diazinon, isoxathion, carbofuran or aldicarb |
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