CH566979A5 - (2,5)-Dichloro-(4)-alkyl-mercaptophenyl-thiophosphoric acid - and thiophosphonic acid esters as pesticides - Google Patents
(2,5)-Dichloro-(4)-alkyl-mercaptophenyl-thiophosphoric acid - and thiophosphonic acid esters as pesticidesInfo
- Publication number
- CH566979A5 CH566979A5 CH1440970A CH1440970A CH566979A5 CH 566979 A5 CH566979 A5 CH 566979A5 CH 1440970 A CH1440970 A CH 1440970A CH 1440970 A CH1440970 A CH 1440970A CH 566979 A5 CH566979 A5 CH 566979A5
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- dichloro
- alkyl
- methanol
- mercaptophenol
- Prior art date
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 4
- 239000002253 acid Substances 0.000 title abstract 2
- 150000002148 esters Chemical class 0.000 title abstract 2
- YGFPFLRARVYKBZ-UHFFFAOYSA-N 2,5-dichloro-4-methylsulfanylphenol Chemical compound CSC1=CC(Cl)=C(O)C=C1Cl YGFPFLRARVYKBZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- SXKBHOQOOGRFJF-UHFFFAOYSA-N 1,2,4-trichloro-5-methoxybenzene Chemical compound COC1=CC(Cl)=C(Cl)C=C1Cl SXKBHOQOOGRFJF-UHFFFAOYSA-N 0.000 claims description 2
- RWDHTEMSFGMSDP-UHFFFAOYSA-N 1,2,4-trichloro-5-methylsulfanylbenzene Chemical compound CSC1=CC(Cl)=C(Cl)C=C1Cl RWDHTEMSFGMSDP-UHFFFAOYSA-N 0.000 claims description 2
- JDAJYNHGBUXIKS-UHFFFAOYSA-N 2,3,4-trichlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C(Cl)=C1Cl JDAJYNHGBUXIKS-UHFFFAOYSA-N 0.000 claims description 2
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 claims description 2
- SAYWFORZGJPFPO-UHFFFAOYSA-N CC(C)C(C(Cl)=CC(O)=C1Cl)=C1S Chemical compound CC(C)C(C(Cl)=CC(O)=C1Cl)=C1S SAYWFORZGJPFPO-UHFFFAOYSA-N 0.000 claims description 2
- ZWBDFNUGHBEUIL-UHFFFAOYSA-N CCCCC(C(Cl)=CC(O)=C1Cl)=C1S Chemical compound CCCCC(C(Cl)=CC(O)=C1Cl)=C1S ZWBDFNUGHBEUIL-UHFFFAOYSA-N 0.000 claims description 2
- BHXWZXJAJRPIIB-UHFFFAOYSA-N CCSC(C(Cl)=C1)=CC(Cl)=C1O Chemical compound CCSC(C(Cl)=C1)=CC(Cl)=C1O BHXWZXJAJRPIIB-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 230000000895 acaricidal effect Effects 0.000 abstract 1
- 239000000642 acaricide Substances 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 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
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing aromatic radicals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- 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
- C07F9/4084—Esters with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(A) (2,5-dichloro-4-alkyl-mercaptophenyl)-thionophosphoric or-thionophosphonic acid esters R1 = C1-4 alkyl-R2 = C1-3 alkyl-, phenyl-n = 0 or 1 R3 = C1-3 alkyl-e.g. O-n-propyl O-(2,5-dichloro-4-methylmercap-tophenyl)methylthiophosphonate (B) Intermediate 2,5-dichloro-4-alkylmercapto-phenols (III) particularly 4-methylmercapto 2,5-dichlorophenol. Pesticides, particularly insecticides and acaricides.
Description
Es ist bekannt, dass 2,4,5-Trichloranisol bei der Einwirkung von Natronlauge/Methanol in der Hitze gemäss dem Reaktionsschema
EMI1.1
<tb> <SEP> Cl <SEP> al
<tb> <SEP> stranlauge,
<tb> OCH, <SEP> Natronlauge,
<tb> Methanol <SEP> 1
<tb> <SEP> 0
<tb> <SEP> 170 <SEP> 0
<tb> <SEP> al <SEP> Cl
<tb> in einer sehr guten Ausbeute 2,4,5-Trichlorphenol liefert.
Wie nun gefunden wurde, ergibt die entsprechende Behandlung von Thioanisol bzw. seinen Homologen gemäss dem Reaktionsschema
EMI1.2
<tb> <SEP> Ci <SEP> Cl
<tb> ol/\sR <SEP> Ä1kali/J4ethanol <SEP> HO <SEP> / <SEP> \ <SEP> SR
<tb> <SEP> \+ <SEP> etwa <SEP> 160-1700C
<tb> <SEP> Cl <SEP> ol <SEP> 1
<tb> (R: Alkylrest mit 1 bis 4 Kohlenstoffatomen) überraschenderweise 2,5-Dichlor-4-alkylmercaptophenole.
Die Nebenprodukte, z. B. Isomere, in denen ein anderes Chloratom durch die Hydroxygruppe ersetzt wurde, werden durch Umkristallisieren abgetrennt.
Die Ausgangsstoffe, 2,4,5-Trichlor-1 -alkylmercapto- benzole, werden nach üblichen Verfahren erhalten, beispielsweise durch Reduktion des entsprechenden Trichlorbenzolsulfochlorids mit Zink und Salzsäure und anschliessende Alkylierung.
Die Verbindungen der Formel I stellen wertvolle Zwischenprodukte für die Synthese von Schädlingsbekämpfungsmitteln dar, z. B. von insektizid wirkenden O,O-Dialkyl-O (2,5-dichlor4 -alkylmercaptophenyl) -thionophosphaten bzw.
-phosphonaten.
Einzelheiten des Verfahrens sind dem folgenden Beispiel zu entnehmen, das eine zweckmässige Ausführungsform beschreibt.
Beispiel
2,5 -Dichlor-4 -methylmercaptophenol
455 g 2.4,5-Trichlor-thioanisol werden mit 370 g 48 %iger Natronlauge in 1 Liter Methanol 6 Stunden bei 1600 C im Autoklav erhitzt. Danach wird abgesaugt, vom Methanol abdestilliert und der Rückstand mit Wasser verdünnt. Anschliessend wird über Kohle filtriert und nach dem Ansäuern mit konzentrierter Salzsäure mit Methylenchlorid ausgeschüttelt. Nach dem Trocknen der Methylenchloridlösung mit Natriumsulfat wird das Methylenchlorid abdestilliert und man erhält 355 g = 85% der Theoretischen Ausbeute 2,5-Dichlor4-methylmercapto-phenol vom Kposos :110 C. Aus Benzol umkristallisiert schmilzt die Substanz bei 110-112 C.
Analog erhält man: 2,5-Dichlor-4-äthylmercaptophenol, F. 420 C; 2,5-Dichlor-4-isopropylmercaptophenol, F. 48 C; 2,5 -D ichlor-4 -n -butylmercaptophenol, F. 550 C.
PATENTANSPRUCH
Verfahren zur Herstellung von 2,5-Dichlor-4-alkylmercaptophenolen der Formel I
EMI1.3
worin R einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeutet, dadurch gekennzeichnet, dass man ein entsprechendes 2,4,5-Trichlor-1 -alkylmercaptobenzol in der Hitze mit methanolischem Alkali umsetzt.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
It is known that 2,4,5-trichloroanisole when exposed to sodium hydroxide solution / methanol in the heat according to the reaction scheme
EMI1.1
<tb> <SEP> Cl <SEP> al
<tb> <SEP> stranlauge,
<tb> OCH, <SEP> caustic soda,
<tb> methanol <SEP> 1
<tb> <SEP> 0
<tb> <SEP> 170 <SEP> 0
<tb> <SEP> al <SEP> Cl
<tb> provides 2,4,5-trichlorophenol in a very good yield.
As has now been found, the corresponding treatment of thioanisole or its homologues according to the reaction scheme
EMI1.2
<tb> <SEP> Ci <SEP> Cl
<tb> ol / \ sR <SEP> Ä1kali / J4ethanol <SEP> HO <SEP> / <SEP> \ <SEP> SR
<tb> <SEP> \ + <SEP> about <SEP> 160-1700C
<tb> <SEP> Cl <SEP> ol <SEP> 1
<tb> (R: alkyl radical with 1 to 4 carbon atoms) surprisingly 2,5-dichloro-4-alkyl mercaptophenols.
The by-products, e.g. B. Isomers in which another chlorine atom has been replaced by the hydroxyl group are separated off by recrystallization.
The starting materials, 2,4,5-trichloro-1-alkylmercaptobenzenes, are obtained by customary processes, for example by reducing the corresponding trichlorobenzenesulfonyl chloride with zinc and hydrochloric acid and then alkylating.
The compounds of formula I are valuable intermediates for the synthesis of pesticides, e.g. B. of insecticidal O, O-dialkyl-O (2,5-dichlor4-alkyl mercaptophenyl) thionophosphates or
phosphonates.
Details of the method can be found in the following example, which describes an expedient embodiment.
example
2,5-dichloro-4-methyl mercaptophenol
455 g of 2,4,5-trichlorothioanisole are heated with 370 g of 48% sodium hydroxide solution in 1 liter of methanol in an autoclave at 1600 ° C. for 6 hours. It is then filtered off with suction, the methanol is distilled off and the residue is diluted with water. It is then filtered through charcoal and, after acidification with concentrated hydrochloric acid, extracted with methylene chloride. After the methylene chloride solution has been dried with sodium sulfate, the methylene chloride is distilled off and 355 g = 85% of the theoretical yield of 2,5-dichloro-4-methylmercaptophenol from Kposos: 110 C. Recrystallized from benzene, the substance melts at 110-112 C.
The following is obtained analogously: 2,5-dichloro-4-ethylmercaptophenol, mp 420 ° C .; 2,5-dichloro-4-isopropyl mercaptophenol, mp 48 ° C; 2,5-dichloro-4-n -butyl mercaptophenol, F. 550 C.
PATENT CLAIM
Process for the preparation of 2,5-dichloro-4-alkyl mercaptophenols of the formula I.
EMI1.3
wherein R denotes an alkyl radical having 1 to 4 carbon atoms, characterized in that a corresponding 2,4,5-trichloro-1-alkylmercaptobenzene is reacted with methanolic alkali in the heat.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB89951A DE1298990B (en) | 1966-11-22 | 1966-11-22 | O, O-Dialkyl-O- (2,5-dichloro-4-alkyl-mercapto-phenyl) -thionophosphates and processes for their preparation |
| DEB0093427 | 1967-07-11 | ||
| CH1617767A CH524957A (en) | 1966-11-22 | 1967-11-20 | Pesticides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH566979A5 true CH566979A5 (en) | 1975-09-30 |
Family
ID=27177435
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1440970A CH566979A5 (en) | 1966-11-22 | 1967-11-20 | (2,5)-Dichloro-(4)-alkyl-mercaptophenyl-thiophosphoric acid - and thiophosphonic acid esters as pesticides |
| CH1440870A CH567041A5 (en) | 1966-11-22 | 1967-11-20 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1440870A CH567041A5 (en) | 1966-11-22 | 1967-11-20 |
Country Status (1)
| Country | Link |
|---|---|
| CH (2) | CH566979A5 (en) |
-
1967
- 1967-11-20 CH CH1440970A patent/CH566979A5/en not_active IP Right Cessation
- 1967-11-20 CH CH1440870A patent/CH567041A5/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CH567041A5 (en) | 1975-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CH566979A5 (en) | (2,5)-Dichloro-(4)-alkyl-mercaptophenyl-thiophosphoric acid - and thiophosphonic acid esters as pesticides | |
| EP0176026A1 (en) | Process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid | |
| AT273923B (en) | Process for the preparation of new 2,5-dichloro-4-alkyl mercaptophenols | |
| DE935547C (en) | Process for the production of condensation products with organically bound phosphorus | |
| DE2717502C2 (en) | ||
| DE2123418A1 (en) | New compounds with insect juvenile hormone activity | |
| DE1643628A1 (en) | Process for the preparation of thionophosphonic acid esters | |
| DE3006983C2 (en) | Process for the preparation of a brassylic acid diester precursor and brassylic acid diester | |
| DE1154095B (en) | Process for the preparation of O, O-dialkyldithiophosphorylacetic acid esters | |
| AT214941B (en) | Process for the preparation of new bis (dialkylamido) chlorophenyl phosphates and thiol phosphates | |
| CH218361A (en) | Process for the production of a cyclopentano-dimethyl-polyhydro-phenanthrene-carboxylic acid. | |
| AT222653B (en) | Process for the production of new azepine derivatives | |
| DE1768419A1 (en) | Process for the selective decarbonylation of nuclear chlorinated di- and tri-formylbenzenes | |
| AT219605B (en) | Process for the preparation of new thioxanthene derivatives | |
| AT247859B (en) | Process for the production of new secondary-tertiary alkenediols | |
| AT281796B (en) | Process for the preparation of 2,3-dichloro-4-butyrylphenoxyacetic acid | |
| DE19832146B4 (en) | Process for the preparation of 3-methylpyrazole or its salts | |
| AT214434B (en) | Process for the production of nitriles | |
| AT257580B (en) | Process for the preparation of new aryloxy-3-hydroxy- or -oxoalkanoic acids, their esters and salts | |
| EP0051240B1 (en) | Acetylcycloundecane and acetylcycloundecene, their application and perfumed compositions containing them | |
| AT143642B (en) | Process for the preparation of 1-phenyl-2-aminopropanolen- (1) hydroxylated in the phenyl radical. | |
| EP0006572A1 (en) | 13,15 - Dioxabicyclo (10,5,0)-heptadecanes, their preparation and use as perfume, and odoriferous compositions containing them | |
| CH387018A (en) | Process for the preparation of the stereoisomers and the racemate of butane-1,2,3,4-tetrol-1,4-di- (methanesulfonate) | |
| CH369446A (en) | Process for the preparation of thiophosphoric acid esters | |
| DE3144765A1 (en) | METHOD FOR PRODUCING CHLORLACTONES FROM UNSATURATED CARBONIC ACIDS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |