DE1188596B - Process for the production of thiol or thionothiolphosphonic acid esters - Google Patents
Process for the production of thiol or thionothiolphosphonic acid estersInfo
- Publication number
- DE1188596B DE1188596B DEF42461A DEF0042461A DE1188596B DE 1188596 B DE1188596 B DE 1188596B DE F42461 A DEF42461 A DE F42461A DE F0042461 A DEF0042461 A DE F0042461A DE 1188596 B DE1188596 B DE 1188596B
- Authority
- DE
- Germany
- Prior art keywords
- cyanobenzyl
- thiol
- thionothiolphosphonic
- ethyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 10
- 150000003573 thiols Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000002148 esters Chemical class 0.000 title description 8
- -1 isopropyl - O - ethyl - thionothiolphosphonic acid potassium Chemical compound 0.000 claims description 11
- 125000006504 o-cyanobenzyl group Chemical group [H]C1=C([H])C(C#N)=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- ZSHNOXOGXHXLAV-UHFFFAOYSA-N 2-(chloromethyl)benzonitrile Chemical compound ClCC1=CC=CC=C1C#N ZSHNOXOGXHXLAV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- BPFSFNIQPNIIQH-UHFFFAOYSA-N CC(C)C1=C(S(=S)C=C1)P(=O)(O)O Chemical compound CC(C)C1=C(S(=S)C=C1)P(=O)(O)O BPFSFNIQPNIIQH-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 150000003008 phosphonic acid esters Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- FFGQZCJMOFFGND-UHFFFAOYSA-N (3-methyl-1-sulfanylidenethiophen-2-yl)phosphonic acid Chemical compound CC1=C(S(C=C1)=S)P(O)(=O)O FFGQZCJMOFFGND-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HFVYUQVSWQURMK-UHFFFAOYSA-N (3-ethyl-1-sulfanylidenethiophen-2-yl)phosphonic acid Chemical compound C(C)C1=C(S(C=C1)=S)P(O)(=O)O HFVYUQVSWQURMK-UHFFFAOYSA-N 0.000 description 1
- LOQLDQJTSMKBJU-UHFFFAOYSA-N 4-(chloromethyl)benzonitrile Chemical compound ClCC1=CC=C(C#N)C=C1 LOQLDQJTSMKBJU-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003564 m-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(C#N)=C1[H])C([H])([H])* 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4087—Esters with arylalkanols
-
- 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
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
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
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C07fC07f
Deutsche Kl.: 12 ο-26/01 German class: 12 ο -26/01
Nummer: 1188 596Number: 1188 596
Aktenzeichen: F 42461IV b/12 οFile number: F 42461IV b / 12 ο
Anmeldetag: 28. März 1964Filing date: March 28, 1964
Auslegetag: 11. März 1965Opening day: March 11, 1965
Gegenstand der Hauptpatentanmeldung F 39668 IVb/ 12o ist ein Verfahren zur Herstellung von Thiol- bzw. Thionothiolphosphonsäureestern, das dadurch gekennzeichnet ist, daß man Thiol- bzw. Thionothiolphosphonsäuren der allgemeinen Formel (I)The subject of the main patent application F 39668 IVb / 12o is a process for the production of thiol or thionothiolphosphonic acid esters, which is characterized in that thiol or thionothiolphosphonic acids are used of the general formula (I)
P-SHP-SH
R2O-R 2 O-
(D(D
Ri\ll
;pRi \ ll
; p
O(S)O (S)
llll
p —s —CH2 p -s -CH 2
(ΠΙ)(ΠΙ)
CNCN
in der Ri und R2 für gleiche oder verschiedene niedere Alkylgruppen stehen und Ri darüber hinaus auch einen Aryl-, bevorzugt Phenylrest bedeutet, entweder in Form der entsprechenden Alkali-, Erdalkali-bzw. Ammoniumsalze oder in Gegenwart von Säurebindemitteln in an sich bekannter Weise mit 4-Cyanobenzylhalogeniden umsetzt.in which Ri and R 2 are identical or different lower alkyl groups and Ri also denotes an aryl, preferably phenyl, radical, either in the form of the corresponding alkali metal, alkaline earth metal or. Ammonium salts or in the presence of acid binders in a manner known per se with 4-cyanobenzyl halides.
Die nach dem in der Hauptpatentanmeldung beanspruchten Verfahren erhältlichen Verbindungen zeichnen sich durch hervorragende pestizide, insbesondere insektizide und akarizide Eigenschaften aus; sie sind in dieser Hinsicht den aus der USA.-Patentschrift 2 992158 bekannten Produkten analoger Zusammensetzung eindeutig überlegen.The compounds obtainable by the process claimed in the main patent application are characterized by excellent pesticidal, especially insecticidal and acaricidal properties the end; in this respect they are more analogous to the products known from US Pat. No. 2,992,158 Composition clearly superior.
Im Verlaufe der weiteren Bearbeitung des obigen Erfindungsgegenstandes wurde nun gefunden, daß ebenfalls biologisch hochwirksame Thiol- bzw. Thionothiolphosphonsäureester hergestellt werden können, wenn man Thiol- bzw. Thionothiolphosphonsäuren der oben angegebenen Zusammensetzung entweder in Form der entsprechenden Alkali-, Erdalkali bzw. Ammoniumsalze oder in Gegenwart von Säurebindemitteln in an sich bekannter Weise mit 2- oder 3-Cyanobenzylhalogeniden umsetzt.In the course of further processing of the above subject matter of the invention it has now been found that also biologically highly effective thiol or thionothiolphosphonic acid esters are produced can, if one thiol or thionothiolphosphonic acids of the composition given above either in the form of the corresponding alkali, alkaline earth or ammonium salts or in the presence of acid binders in a manner known per se with 2- or 3-cyanobenzyl halides.
Die dabei erhaltenen Verbindungen besitzen die allgemeine Formel (III)The compounds obtained have the general formula (III)
In letztgenannter Formel haben die Symbole Ri und R2 die weiter oben angegebene Bedeutung; die Cyanogruppe steht entweder in der 2- oder 3-Stellung des Benzylrestes.In the last-mentioned formula, the symbols Ri and R 2 have the meaning given above; the cyano group is either in the 2- or 3-position of the benzyl radical.
Die Umsetzung wird vorzugsweise in Gegenwart inerter organischer Lösungsmittel vorgenommen.
Bewährt haben sich für diesen Zweck vor allem aromatische Kohlenwasserstoffe, z. B. Benzol, Toluol,
Verfahren zur Herstellung von Thiol- bzw.
ThionothiolphosphonsäureesternThe reaction is preferably carried out in the presence of inert organic solvents. Aromatic hydrocarbons such. B. benzene, toluene, process for the production of thiol or
Thionothiolphosphonic acid esters
Zusatz zur Anmeldung: F 39668 IV b/12 ο ■
Auslegeschrift 1183 081Addition to registration: F 39668 IV b / 12 ο ■
Interpretation document 1183 081
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,Paint factories Bayer Aktiengesellschaft,
LeverkusenLeverkusen
Als Erfinder benannt:Named as inventor:
Dr. Karl-Julius Schmidt, Wuppertal-VohwinkelDr. Karl-Julius Schmidt, Wuppertal-Vohwinkel
Xylol, sowie vor allem niedrigsiedende aliphatische Ketone oder Nitrile, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- oder Methylisobutylketon und Aceto- oder Propionitril, sowie weiterhin auch Dimethylformamid.Xylene, and especially low-boiling aliphatic ketones or nitriles, for example acetone, methylethyl, Methyl isopropyl or methyl isobutyl ketone and aceto or propionitrile, as well as furthermore Dimethylformamide.
Ferner hat es sich als zweckmäßig erwiesen, das erfindungsgemäße Verfahren bei Temperaturen zwischen 20 und 1500C, vorzugsweise 60 bis 8O0C, durchzuführen und außerdem das Reaktionsgemisch nach Vereinigung der Ausgangskomponenten noch 2 bis 5 Stunden, gegebenenfalls unter weiterem Erwärmen, nachzurühren.Furthermore, it has proven advantageous to the inventive process at temperatures between 20 and 150 0 C, preferably 60 to 8O 0 C, to carry out and also the reaction mixture after combining the starting components for 2 to 5 hours, optionally with further heating to continue to stir.
Die gemäß der Erfindung herstellbaren Thiol- bzw. Thionothiolphosphonsäureester fallen meist in Form farbloser bis schwach gelbgefärbter öle an, die sich auch unter stark vermindertem Druck nicht ohne Zersetzung destillieren lassen, jedoch durch sogenanntes Andestillieren, d. h. längeres Erhitzen im Vakuum auf schwach bis mäßig erhöhten Temperaturen von den letzten flüchtigen Anteilen befreit und auf diese Weise gereinigt werden können.The thiol or thionothiolphosphonic acid esters which can be prepared according to the invention are mostly included Form of colorless to pale yellow-colored oils, which do not dissolve even under greatly reduced pressure Allow to distill without decomposition, but by so-called incipient distillation, d. H. prolonged heating freed from the last volatile constituents in vacuo to slightly to moderately elevated temperatures and can be cleaned in this way.
Wie die in der Hauptpatentanmeldung beschriebenen Verbindungen besitzen auch die erfindungsgemäß herstellbaren Produkte eine hervorragende pestizide, insbesondere insektizide und akarizide Wirksamkeit; sie sind hinsichtlich ihrer Wirkung gegen die verschiedenen Schädlinge den aus der USA.-Patentschrift 2 992 158 bekannten, analog gebauten und für den gleichen Zweck verwendbaren Verbindungen eindeutig überlegen. Diese technische Überlegenheit der Verfahrensprodukte geht aus den im folgendenLike the compounds described in the main patent application, those according to the invention also have producible products have an excellent pesticidal, especially insecticidal and acaricidal effectiveness; in terms of their action against the various pests, they are those from the United States patent 2,992,158 known, similarly built compounds that can be used for the same purpose clearly superior. This technical superiority of the process products is evident from the following
509 518/488509 518/488
tabellarisch zusammengestellten Ergebnissen von Vergleichsversuchen hervor.Results of comparative tests compiled in tabular form.
Lfd.
Nr.Serial
No.
Verbindung (Konstitution)Connection (constitution)
Insektizide Wirksamkeit bei Anwendung gegenInsecticidal effectiveness when used against
ZeckenTicks
Wirkstoffkonzen
trationActive ingredient concentrations
tration
Abtötung %Kill%
RaupenCaterpillars
Wirkstoffkonzen trationActive ingredient concentration
Abtötung %Kill%
SpinnmilbenSpider mites
Wirkstoffkonzentration Active ingredient concentration
Abtötung %Kill%
CH2-S —P(OCH3)2 0,05CH 2 -S -P (OCH 3 ) 2 0.05
0,00250.0025
0,0010.001
30 0 030 0 0
0,01 0,0040.01 0.004
100 0100 0
0,1 0,010.1 0.01
100 0100 0
CNCN
(bekannt aus USA.-Patentschrift 2 992 158)(known from US Pat. No. 2,992,158)
NC-NC-
V- CH2-S- P(OCH3)2 V- CH 2 -S- P (OCH 3 ) 2
(bekannt aus USA.-Patentschrift 2 992 158) O(known from U.S. Patent 2,992,158) O
CH2-S-P(OC2Hs)2 CH 2 -SP (OC 2 Hs) 2
0,05
0,00250.05
0.0025
15 015 0
75 075 0
0,01 0,0040.01 0.004
0,10.1
70 070 0
0,001 0,00080.001 0.0008
0,1 0,010.1 0.01
100 0100 0
(bekannt aus USA.-Patentschrift 2 992 158)(known from US Pat. No. 2,992,158)
V- CH2-S- P(OC2Hs)2 V- CH 2 -S- P (OC 2 Hs) 2
(bekannt aus USA.-Patentschrift 2 992 158) S(known from U.S. Patent 2,992,158) p
CH2-S-PCH 2 SP
CH3 OC2H5
0,025
0,01CH 3 OC 2 H 5 0.025
0.01
0,05
0,00250.05
0.0025
20 020 0
100 65100 65
0,10.1
0,01 0,0010.01 0.001
100 0100 0
0,0040.004
8080
0,00080.0008
100100
CNCN
(verfahrensgemäß, Beispiel 1) S(according to the procedure, example 1) p
CH2-S-PCH 2 SP
CH3 CH 3
OC2H5 0,0025
0,001OC 2 H 5 0.0025
0.001
100 50100 50
0,0040.004
100100
0,001 0,00010.001 0.0001
100 90100 90
(verfahrensgemäß, Beispiel 2)(according to the procedure, example 2)
Die folgenden Beispiele vermitteln einen Überblick über das beanspruchte Verfahren:The following examples provide an overview of the claimed method:
CH2-S-PCCH 2 -S-PC
XH3 * OC2H5 XH 3 * OC 2 H 5
stark vermindertem Druck zum Schluß bei einer Badtemperatur von 70° C und 0,01 Torr, eingedampft. Die Ausbeute beträgt 62 g (91% der Theorie) Methyl - thionothiolphosphonsäure- O - äthyl- S - (3 - cyanobenzyl)-ester. strongly reduced pressure at the end at a bath temperature of 70 ° C and 0.01 Torr, evaporated. The yield is 62 g (91% of theory) of methyl thionothiolphosphonic acid O - ethyl S - (3 - cyanobenzyl) ester.
Analyse für ein Molgewicht von 271,3: Berechnet ... N 5,16%, P 11,41%; gefunden ... N 5,54%, P 10,74%.Analysis for a molecular weight of 271.3: Calculated ... N 5.16%, P 11.41%; found ... N 5.54%, P 10.74%.
Man rührt 38 g (0,25 Mol) 3-Cyanobenzylchlorid und 49 g methyl-O-äthyl-thionothiolphosphonsaures Kalium in 200 ecm Acetonitril 3 Stunden bei 70° C. Anschließend wird das Reaktionsgemisch mit 400 ml Benzol versetzt, abgekühlt, mehrere Male mit Wasser gewaschen, über Natriumsulfat getrocknet und unter38 g (0.25 mol) of 3-cyanobenzyl chloride are stirred and 49 g of methyl-O-ethyl-thionothiolphosphonic acid Potassium in 200 ecm acetonitrile for 3 hours at 70 ° C. The reaction mixture is then with 400 ml Benzene added, cooled, washed several times with water, dried over sodium sulfate and under
Beispiel SExample p
IlIl
CH2-S-PCCH 2 -S-PC
XH3 X-C2H5 XH 3 XC 2 H 5
CNCN
38g (0,25MoI) 2-Cyanobenzylchlorid und 48,5 g methyl - O - äthyl - thionothiolphosphonsaures Kalium werden in 200 ecm Acetonitril 3 Stunden bei 700C gerührt. Anschließend gießt man das Reaktionsgemisch nach dem Abkühlen in 300 ml Benzol, wäscht die benzolische Lösung mehrere Male mit Wasser, trocknet sie über Natriumsulfat, dampft schließlich das Benzol unter vermindertem Druck, zum Schluß bei 700C und 0,01 Torr, ab und erhält 61 g (90% der Theorie) Methyl-thionothiolphosphonsäure-O-äthyl-S-(2-cyanobenzyl)-ester. 38g (0,25MoI) 2-cyanobenzyl chloride and 48.5 g of methyl - O - ethyl - thionothiolphosphonsaures potassium are stirred for 3 hours at 70 0 C in 200 cc of acetonitrile. Then, after cooling, the reaction mixture is poured into 300 ml of benzene, the benzene solution is washed several times with water, dried over sodium sulfate, and finally the benzene is evaporated under reduced pressure, finally at 70 ° C. and 0.01 torr, and obtained 61 g (90% of theory) of methyl thionothiolphosphonic acid O-ethyl-S- (2-cyanobenzyl) ester.
Analyse für ein Molgewicht von 271,3: Berechnet ... N 5,14%, P 11,42%; gefunden ... N 5,67%, P 10,13%.Analysis for a molecular weight of 271.3: Calculated ... N 5.14%, P 11.42%; found ... N 5.67%, P 10.13%.
CH2-S-P:CH 2 -SP:
-C2H5 ^ OC2H5 -C2H5 ^ OC 2 H 5
Beispiel 4 SExample 4 p
IlIl
CH2-S-P:CH 2 -SP:
-C3H7I OC2H5 -C 3 H 7 I OC 2 H 5
CNCN
Beispiel 5 SExample 5 p
IlIl
CH2-S-PCCH 2 -S-PC
X4H91 OC2H5X4H91 OC2H5
CNCN
rem Kalium in der im Beispiel 1 beschriebenen Weise erhält man 76 g (99% der Theorie) Isobutyl-thionothiolphosphonsäure-O-äthyl-S-(2-cyanobenzyl) - ester.rem potassium in the manner described in Example 1 gives 76 g (99% of theory) isobutyl-thionothiolphosphonic acid-O-ethyl-S- (2-cyanobenzyl) - ester.
Analyse für ein Molgewicht von 313,4:Analysis for a molecular weight of 313.4:
Berechnet ... N 4,45%, P 9,89%, S 20,46%;
gefunden ... N 4,59%, P 9,48%, S 20,55%.Calculated ... N 4.45%, P 9.89%, S 20.46%;
found ... N 4.59%, P 9.48%, S 20.55%.
OCH3 OCH 3
CNCN
2020th
76 g (0,5 Mol) 2-Cyanobenzylchlorid werden, wie im Beispiel 1 beschrieben, mit 104 g (0,5 Mol) äthyl - O - äthyl - thionothiolphosphonsaurem Kalium umgesetzt. Man erhält 127 g (90% der Theorie) Äthyl-thionothiolphosphonsäure - O - äthyl - S - (2 - cyanobenzyl)-ester. 76 g (0.5 mol) of 2-cyanobenzyl chloride are, as described in Example 1, with 104 g (0.5 mol) of ethyl - O - ethyl - thionothiolphosphonic acid potassium implemented. 127 g (90% of theory) of ethyl thionothiolphosphonic acid - O - ethyl - S - (2 - cyanobenzyl) ester are obtained.
Analyse für ein Molgewicht von 285,4: Berechnet ... P 10,85%, S 22,47%; gefunden ... P 10,70%, S 21,67%.Analysis for a molecular weight of 285.4: Calculated ... P 10.85%, S 22.47%; found ... P 10.70%, S 21.67%.
3030th
3535
40 Die Umsetzung von 38 g 2-Cyanobenzylchlorid mit 52 g phenyl-O-methyl-thionothiolphosphonsaurem Kalium analog Beispiel 1 liefert 69 g (86,5% der Theorie) Phenyl-thionothiolphosphonsäure-O-methyl-S-(2-cyanobenzyl)-ester. 40 The reaction of 38 g of 2-cyanobenzyl chloride with 52 g of phenyl-O-methyl-thionothiolphosphonic acid potassium analogously to Example 1 gives 69 g (86.5% of theory) phenyl-thionothiolphosphonic acid-O-methyl-S- (2-cyanobenzyl) - ester.
Analyse für ein Molgewicht von 319,4:
Berechnet ... N 4,39%, P 9,70%;
gefunden ... N 4,80%, P 8,88%.Analysis for a molecular weight of 319.4:
Calculated ... N 4.39%, P 9.70%;
found ... N 4.80%, P 8.88%.
Claims (1)
R2OBy reacting 38 g of 2-cyanobenzyl chloride with 59 g of isobutyl-O-ethyl-thionothiolphosphonsau-Ri
R 2 O
R2ORi
R 2 O
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF42461A DE1188596B (en) | 1964-03-28 | 1964-03-28 | Process for the production of thiol or thionothiolphosphonic acid esters |
| CH146565A CH452522A (en) | 1964-03-28 | 1965-02-03 | Process for the production of thiol or thionothiol phosphonic acid esters |
| IL22927A IL22927A (en) | 1964-03-28 | 1965-02-05 | Thionothiol-phosphonic-acid esters and their use for the control of pests |
| US442508A US3379795A (en) | 1964-03-28 | 1965-03-24 | S-cyanobenzyl thio and dithiophosphonic acid esters |
| NL6503902A NL6503902A (en) | 1964-03-28 | 1965-03-26 | |
| FR10952A FR1438386A (en) | 1964-03-28 | 1965-03-26 | Process for the production of esters of thiol- or thionothiolphosphonic acids |
| BE661681D BE661681A (en) | 1964-03-28 | 1965-03-26 | |
| GB12937/65A GB1034299A (en) | 1964-03-28 | 1965-03-26 | Dithiophosphonic acid esters |
| ES0311085A ES311085A1 (en) | 1964-03-28 | 1965-03-27 | S-cyanobenzyl thio and dithiophosphonic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF42461A DE1188596B (en) | 1964-03-28 | 1964-03-28 | Process for the production of thiol or thionothiolphosphonic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1188596B true DE1188596B (en) | 1965-03-11 |
Family
ID=7099108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF42461A Pending DE1188596B (en) | 1964-03-28 | 1964-03-28 | Process for the production of thiol or thionothiolphosphonic acid esters |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3379795A (en) |
| BE (1) | BE661681A (en) |
| CH (1) | CH452522A (en) |
| DE (1) | DE1188596B (en) |
| ES (1) | ES311085A1 (en) |
| GB (1) | GB1034299A (en) |
| IL (1) | IL22927A (en) |
| NL (1) | NL6503902A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE601788A (en) * | 1960-05-31 | |||
| NL271542A (en) * | 1960-11-19 |
-
1964
- 1964-03-28 DE DEF42461A patent/DE1188596B/en active Pending
-
1965
- 1965-02-03 CH CH146565A patent/CH452522A/en unknown
- 1965-02-05 IL IL22927A patent/IL22927A/en unknown
- 1965-03-24 US US442508A patent/US3379795A/en not_active Expired - Lifetime
- 1965-03-26 BE BE661681D patent/BE661681A/xx unknown
- 1965-03-26 NL NL6503902A patent/NL6503902A/xx unknown
- 1965-03-26 GB GB12937/65A patent/GB1034299A/en not_active Expired
- 1965-03-27 ES ES0311085A patent/ES311085A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH452522A (en) | 1968-03-15 |
| BE661681A (en) | 1965-09-27 |
| US3379795A (en) | 1968-04-23 |
| ES311085A1 (en) | 1965-07-01 |
| NL6503902A (en) | 1965-09-29 |
| IL22927A (en) | 1969-01-29 |
| GB1034299A (en) | 1966-06-29 |
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