DE1056622B - Process for the preparation of insecticidal tetrahydrofuran derivatives - Google Patents
Process for the preparation of insecticidal tetrahydrofuran derivativesInfo
- Publication number
- DE1056622B DE1056622B DEB46070A DEB0046070A DE1056622B DE 1056622 B DE1056622 B DE 1056622B DE B46070 A DEB46070 A DE B46070A DE B0046070 A DEB0046070 A DE B0046070A DE 1056622 B DE1056622 B DE 1056622B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- insecticidal
- methylenedioxybenzene
- preparation
- tetrahydrofuran derivatives
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 4
- 230000000749 insecticidal effect Effects 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 3
- ZQHLMWUFVRLDRK-UHFFFAOYSA-N 2,3-dichlorooxolane Chemical compound ClC1CCOC1Cl ZQHLMWUFVRLDRK-UHFFFAOYSA-N 0.000 claims description 6
- -1 phenolic hydroxy compounds Chemical class 0.000 claims description 5
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002917 insecticide Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- LUSZGTFNYDARNI-UHFFFAOYSA-N Sesamol Natural products OC1=CC=C2OCOC2=C1 LUSZGTFNYDARNI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000005529 1,3-benzodioxoles Chemical class 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BHUIUXNAPJIDOG-UHFFFAOYSA-N Piperonol Chemical compound OCC1=CC=C2OCOC2=C1 BHUIUXNAPJIDOG-UHFFFAOYSA-N 0.000 description 2
- 240000004460 Tanacetum coccineum Species 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940015367 pyrethrum Drugs 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Verfahren zur Herstellung von insektizid wirkenden Tetrahydrofuranderivaten Es wurde gefunden, daß man insektizid wirkende Tetrahydrofuranderivate erhält, wenn man 2,3-Dichlortetrahydrofuran mit alkoholischen oder phenolischen Hydroxyverbindungen des 1,2-Methylendioxybenzols (Brenzcatechin-methylenäthers) in Gegenwart von säurebindenden Mitteln umsetzt.Process for the preparation of insecticidal tetrahydrofuran derivatives It has been found that insecticidal tetrahydrofuran derivatives are obtained if one 2,3-dichlorotetrahydrofuran with alcoholic or phenolic hydroxy compounds of 1,2-methylenedioxybenzene (pyrocatechol methylene ether) in the presence of acid-binding Implements funds.
Hydroxyverbindungen des 1,2-Methylendioxybenzols sind 1,2-Methylendioxybenzole, die am aromatischen Ring, an einem Ringsubstituenten oder an beiden Stellen Hydroxylgruppen enthalten, z. B. Piperonylalkohol, 3-(3',4'-Methylendioxyphenyl)-propin-(1)-ol-(3), 3-(3', 4'-Methylendioxyphenyl)-propen-(1)-ol-(3), 1-(3',4'-Methylendioxyphenyl)-propanol-(1), 1-a-Hydroxyäthyl-2-propyl-4,5-methylendioxybenzol, Sesamol (4-Hydroxy-1,2-methylendioxybenzol) und 6-Hydroxydihydrosafrol (1- Propyl - 6 - hydroxy - 3,4 - methylendioxybenzol). Als säurebindende Mittel werden beispielsweise organische Basen, Alkoholate, Alkali- und Erdalkalihydroxyde, Carbonate oder Ionenaustauscher verwendet.The hydroxy compounds of 1,2-methylenedioxybenzene are 1,2-methylenedioxybenzenes, those on the aromatic ring, on a ring substituent, or on both hydroxyl groups included, e.g. B. piperonyl alcohol, 3- (3 ', 4'-methylenedioxyphenyl) -propine- (1) -ol- (3), 3- (3 ', 4'-methylenedioxyphenyl) -propen- (1) -ol- (3), 1- (3', 4'-methylenedioxyphenyl) -propanol- (1), 1-a-hydroxyethyl-2-propyl-4,5-methylenedioxybenzene, sesamol (4-hydroxy-1,2-methylenedioxybenzene) and 6-hydroxydihydrosafrol (1-propyl - 6 - hydroxy - 3,4 - methylenedioxybenzene). As acid-binding agents, for example, organic bases, alcoholates, alkali and alkaline earth hydroxides, carbonates or ion exchangers are used.
Die Umsetzung wird in Gegenwart oder Abwesenheit eines inerten Verdünnungsmittels und zweckmäßig bei erhöhter Temperatur, gegebenenfalls in Druckgefäßen, ausgeführt. Als Verdünnungsmittel werden z. B. aliphatische und aromatische Kohlenwasserstoffe, Äther bzw. cyclische Äther, wie Tetrahydrofuran, verwendet.The reaction is carried out in the presence or absence of an inert diluent and expediently carried out at elevated temperature, optionally in pressure vessels. As a diluent, for. B. aliphatic and aromatic hydrocarbons, Ether or cyclic ethers, such as tetrahydrofuran, are used.
Die Verfahrensprodukte haben eine außerordentlich starke synergistische Wirkung mit Pyrethrum und Pyrethrumderivaten natürlicher und synthetischer Herkunft. Es ist zwar bekannt, daß verschiedene Abkömmlinge des 1,2-Methylendioxybenzols die insektizide Wirksamkeit von natürlichen und synthetischen Pyrethrumpräparaten steigern können. Diese synergistischen Eigenschaften sind aber auf einige Derivate des 1,2-Methylendioxybenzols beschränkt (s. J. agric. Food. Chem., Bd. 4 [1956], Nr.10, S.858 bis 862). Die nach der Erfindung hergestellten Stoffe kommen an synergistischer Wirkung bekannten Abkömmlingen des 1,2-Methylendioxybenzols mindestens gleich, größtenteils übertreffen sie diese jedoch. Ein besonderer Vorteil der erfindungsgemäßen Mittel gegenüber bekannten ist die wirtschaftlich günstigere Herstellung von sehr wirksamen Verbindungen, die außerdem eine sehr geringe Warmblütlertoxizität besitzen.The products of the process have an extremely strong synergistic effect Effect with pyrethrum and pyrethrum derivatives of natural and synthetic origin. Although it is known that various derivatives of 1,2-methylenedioxybenzene the Increase the insecticidal effectiveness of natural and synthetic pyrethrum preparations can. However, these synergistic properties are due to some derivatives of 1,2-methylenedioxybenzene limited (see J. agric. Food. Chem., Vol. 4 [1956], No. 10, pp. 858 to 862). The after Substances produced according to the invention come from derivatives known to have a synergistic effect of 1,2-methylenedioxybenzene at least equal, and for the most part they exceed this However. A particular advantage of the agents according to the invention over known ones is the more economical production of very potent compounds that also have a very low toxicity to warm blooded animals.
Die in den Ausführungsbeispielen genannten Teile sind Gewichtsteile.The parts mentioned in the exemplary embodiments are parts by weight.
Beispiel 1 152 Teile Piperonylalkohol, 141 Teile 2,3-Dichlortetrahydrofuran und 170 Teile trockenes Pyridin werden in 500 Teilen Benzol 12 Stunden unter Rückflußkühlung erhitzt. Das erkaltete Umsetzungsgemisch wird mit Wasser gewaschen, getrocknet und destilliert. Nach dem Abdestillieren des Benzols erhält man als gelbliches Öl 166 Teile der Verbindung vom Siedepunkt 0,1 mm 125 bis 130°C. Beispiel 2 300 Teile Benzol, 90 Teile 1-(3',4'-Methylendioxyphenyl)-propanol-(1), 80 Teile Piperidin und 80 Teile 2,3-Dichlortetrahydrofuran werden in einem Druckgefäß unter Rühren 20 Stunden auf 100°C erhitzt.Example 1 152 parts of piperonyl alcohol, 141 parts of 2,3-dichlorotetrahydrofuran and 170 parts of dry pyridine are refluxed in 500 parts of benzene for 12 hours. The cooled reaction mixture is washed with water, dried and distilled. After the benzene has been distilled off, 166 parts of the compound are obtained as a yellowish oil from the boiling point 0.1 mm 125 to 130 ° C. Example 2 300 parts of benzene, 90 parts of 1- (3 ', 4'-methylenedioxyphenyl) propanol- (1), 80 parts of piperidine and 80 parts of 2,3-dichlorotetrahydrofuran are heated to 100 ° C. for 20 hours with stirring in a pressure vessel .
Nach dem Erkalten wird mit Wasser gewaschen, getrocknet und destilliert. Man erhält 119 Teile eines schwach gelblichen Öles; Kp.o,3 136 bis 139°C. Die Verbindung hat die Formel Beispiel 3 300 Teile Tetrahydrofuran, 104 Teile 1-a-Hydroxyäthyl-2-propyl-4,5-methylendioxybenzol, 110 Teile Triäthylamin und 71 Teile 2,3-Dichlortetrahydrofuran werden in einem Druckgefäß unter Rühren 20 Stunden auf 100°C erhitzt. Nach dem Abdestillieren des Tetrahydrofurans wird mit Wasser verdünnt, die nicht wäßrige Schicht abgetrennt und destilliert.After cooling, it is washed with water, dried and distilled. 119 parts of a pale yellowish oil are obtained; B.p. 3136-139 ° C. The compound has the formula Example 3 300 parts of tetrahydrofuran, 104 parts of 1-a-hydroxyethyl-2-propyl-4,5-methylenedioxybenzene, 110 parts of triethylamine and 71 parts of 2,3-dichlorotetrahydrofuran are heated to 100 ° C. for 20 hours with stirring in a pressure vessel. After the tetrahydrofuran has been distilled off, it is diluted with water, and the non-aqueous layer is separated off and distilled.
Man erhält 106 Teile eines farblosen'Öles vom Kp.o,B 157 bis 162°C. Die Verbindung hat die Formel Beispiel 4 138 Teile 3,4-Methylendioxyphenol, 160 Teile trockenes Pyridin und 600 Teile Benzol werden mit 141 Teilen 2,3-Dichlortetrahydrofuran versetzt und 24 Stunden unter Rückflußkühlung erhitzt. Das erkaltete Umsetzungsgemisch wird mit Wasser und verdünnter Säure gewaschen, getrocknet, und das Benzol abdestilliert. Man erhält als Rückstand 200 Teile der Verbindung Bei der Reinigung durch Destillation (Kp.o,6 123 bis 127°C) wird sie als gelbes, zähes Öl erhalten, das zu farblosen Kristallen vom Schmelzpunkt 75 bis 76,5'C erstarrt.106 parts of a colorless oil with a boiling point of B 157 to 162 ° C. are obtained. The compound has the formula Example 4 138 parts of 3,4-methylenedioxyphenol, 160 parts of dry pyridine and 600 parts of benzene are mixed with 141 parts of 2,3-dichlorotetrahydrofuran and the mixture is refluxed for 24 hours. The cooled reaction mixture is washed with water and dilute acid, dried, and the benzene is distilled off. 200 parts of the compound are obtained as residue When purified by distillation (bp 6,123 to 127 ° C) it is obtained as a yellow, viscous oil that solidifies to form colorless crystals with a melting point of 75 to 76.5 ° C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB46070A DE1056622B (en) | 1957-09-14 | 1957-09-14 | Process for the preparation of insecticidal tetrahydrofuran derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB46070A DE1056622B (en) | 1957-09-14 | 1957-09-14 | Process for the preparation of insecticidal tetrahydrofuran derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1056622B true DE1056622B (en) | 1959-05-06 |
Family
ID=6967819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB46070A Pending DE1056622B (en) | 1957-09-14 | 1957-09-14 | Process for the preparation of insecticidal tetrahydrofuran derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1056622B (en) |
-
1957
- 1957-09-14 DE DEB46070A patent/DE1056622B/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2157048A1 (en) | ||
| DE2034128C2 (en) | Cyclopentenolone esters, cyclopentenones and the use of the cyclopentenolone esters as insecticides | |
| US2413803A (en) | 2-ethyl-2-butyl propanediol-1,3 | |
| EP0142741B1 (en) | Cyclohexane-1,3-dione derivatives, process for their preparation and their use in combating the growth of undesirable plants | |
| EP0107156B1 (en) | Cyclohexane-1,3-dione derivatives, process for their preparation and their use in the control of undesirable plant growth | |
| US3035969A (en) | Carbamate-pyrethrin insecticides | |
| DE2418343A1 (en) | PHENYL-ARALKYL AETHER, THIOAETHER AND AMINES, METHOD FOR THEIR PRODUCTION AND USE | |
| DE1056622B (en) | Process for the preparation of insecticidal tetrahydrofuran derivatives | |
| DE1543457B1 (en) | Cyclopropanecarboxylic acid esters | |
| US2891889A (en) | Insecticidal compositions containing cyclethrin | |
| DE3123165A1 (en) | "METHOD FOR PRODUCING 2-ALKOXY- (1,3) -DIOXOLANES" | |
| DE3032795C2 (en) | Disinfectant based on glutaraldehyde substituted in the 2-position | |
| DE2142653A1 (en) | Organic nitro compounds | |
| DE2166237A1 (en) | 5-PROPARGYL-2 ALPHA-AETHINYLFURFURYL ALCOHOL AND METHOD FOR ITS MANUFACTURING | |
| US2488501A (en) | 1, 4-di(alkenylphenoxy)-2-butenes | |
| DE1084733B (en) | Process for the production of bicyclic acetals | |
| US2755219A (en) | 2-(3, 4-methylenedioxyphenoxy) tetrahydropyran as a synergist for pyrethrins | |
| US2524107A (en) | Alkyl substituted piperonyl cyclohexenones | |
| DE69203526T2 (en) | Insecticides consist of three mixtures of methylenedioxylene benzene and process for their preparation. | |
| DE936572C (en) | Process for the preparation of spirocyclic esters of sulphurous acid | |
| DE1543880C3 (en) | Process for the production of benzo- or naphtho-dioxoles or -oxathiols | |
| DE1146883B (en) | Process for the preparation of dithiophosphinic acid esters | |
| AT319200B (en) | VZH OF NEW SUBSTITUTED 1,1-DIPHENYL-2-NITROPROPANES AND BUTANES | |
| DE2439104C3 (en) | Cyclohexane derivatives, process for their preparation and their use as herbicides | |
| AT393934B (en) | Fungicidal composition |