DE1057131B - Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafole - Google Patents
Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafoleInfo
- Publication number
- DE1057131B DE1057131B DEB46331A DEB0046331A DE1057131B DE 1057131 B DE1057131 B DE 1057131B DE B46331 A DEB46331 A DE B46331A DE B0046331 A DEB0046331 A DE B0046331A DE 1057131 B DE1057131 B DE 1057131B
- Authority
- DE
- Germany
- Prior art keywords
- hydroxy
- parts
- dihydrosafole
- preparation
- active 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
- C07D317/64—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von insektizid wirksamen Derivaten des 6-Hydroxy-dihydrosafrols Es ist bekannt, daß einige Derivate des 3,4-Methylendioxyphenols (Sesamol) synergistisch die insektizide Wirksamkeit von Pyrethrum und Allethrin erhöhen. [J. Agric. Food. Chem.> Bd. 4 (1956) Nr. 10, S. 858 bis 862].Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafole It is known that some derivatives of 3,4-methylenedioxyphenol (sesamol) synergistically increase the insecticidal effectiveness of pyrethrum and allethrin. [J. Agric. Food. Chem.> Vol. 4 (1956) No. 10, pp. 858 to 862].
Es wurde nun gefunden, daß man besonders stark synergistisch wirksame Insektizide erhält, wenn man 6-Hydroxy-dihydrosafrol (6-Hydroxy-3,4-methylendioxy-1-n-propylbenzol) mit cyclischen oder offenkettigen Vinyläthern in Gegenwart von sauren Katalysatoren umsetzt, wobei Acetale gebildet werden.It has now been found that there are particularly strong synergistic effects Insecticides are obtained by using 6-hydroxy-dihydrosafrol (6-hydroxy-3,4-methylenedioxy-1-n-propylbenzene) with cyclic or open-chain vinyl ethers in the presence of acidic catalysts converts, whereby acetals are formed.
Besonders geeignet für die Herstellung der Acetale sind cyclische Vinyläther, wie 2,3-Dihydrofuran, 2,3-Dihydropyran, 2-Alkoxy-2,3-dihydrofuran, 2-Alkoxy-2,3-dihydropyran und 2-Alkoxy-4-methyl-2,3-dihydropyran. Auch offenkettige Vinyläther, wie Vinylbutyläther, Vinyläthylglykoläther, Vinyläthyldiglykoläther, Vinylbutyldiglykoläther und Vinylmethyltriglykoläther, führen zu den stark synergistisch wirksamen Acetalen.Cyclic ones are particularly suitable for the production of the acetals Vinyl ethers such as 2,3-dihydrofuran, 2,3-dihydropyran, 2-alkoxy-2,3-dihydrofuran, 2-alkoxy-2,3-dihydropyran and 2-alkoxy-4-methyl-2,3-dihydropyran. Open-chain vinyl ethers, such as vinyl butyl ether, Vinyl ethyl glycol ether, vinyl ethyl diglycol ether, vinyl butyl diglycol ether and vinyl methyl triglycol ether, lead to the highly synergistic acetals.
Als saure Katalysatoren werden z. B. Mineralsäuren, Bortrifluorid und sein Ätherat, Aluminiumchlorid und Zinnchlorid verwendet. Die Umsetzung kann in Gegenwart oder Abwesenheit von Verdünnungsmitteln bei gewöhnlicher oder erhöhter Temperatur ausgeführt werden.As acidic catalysts, for. B. mineral acids, boron trifluoride and its etherate, aluminum chloride and tin chloride are used. The implementation can in the presence or absence of diluents at ordinary or increased Temperature.
Das zur Umsetzung benötigte 6-Hydroxy-dihydrosafrol ist bisher nicht beschrieben, es kann aber leicht aus Dihydrosafrol, z. B. durch Nitrieren, Reduzieren zum Amin und weiter über die Diazoniumverbindung, in an sich bekannter Weise hergestellt werden.The 6-hydroxy-dihydrosafrol required for the implementation is not yet described, but it can easily be made from dihydrosafrol, e.g. B. by nitriding, reducing to the amine and further via the diazonium compound, prepared in a manner known per se will.
Die in den Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the examples are parts by weight.
Beispiel 1 In die Mischung von 600 Teilen Vinylbutyldiglykoläther und 3 Teilen konzentrierter Salzsäure werden unter Rühren bei Raumtemperatur 360 Teile 6-Hydroxydihydrosafrol innerhalb von 20 Minuten eingetragen. Die Mischung, die sich auf ungefähr 35°C erwärmt, wird noch 2 Stunden weitergerührt, mit Natriumcarbonatlösung neutralisiert und getrocknet.Example 1 In the mixture of 600 parts of vinyl butyl diglycol ether and 3 parts of concentrated hydrochloric acid are stirred at room temperature 360 Parts of 6-hydroxydihydrosafrol entered within 20 minutes. The mixture, which warms up to about 35 ° C, is stirred for a further 2 hours, with sodium carbonate solution neutralized and dried.
Bei der Destillation erhält man 890 Teile des 2-(4',5'-Methylendioxy-2'-n-propyl-phenoxy) -3,6,9-trioxa-tridecan vom Kp. 0,i 160 bis 165°C.The distillation gives 890 parts of 2- (4 ', 5'-methylenedioxy-2'-n-propyl-phenoxy) -3,6,9-trioxa-tridecane with a boiling point of 0.1 160 to 165 ° C.
Beispiel 2 Die Mischung von 360 Teilen 6-Hydroxy-dihydrosafrol und 3 Teilen Borfluoridätherat in 300 Teilen Äther wird bei Raumtemperatur unter Rühren mit 700 Teilen 2,3-Dihydrofuran versetzt und nach fünfstündigem Rühren neutralisiert.Example 2 The mixture of 360 parts of 6-hydroxy-dihydrosafrol and 3 parts of boron fluoride ether in 300 parts of ether are stirred at room temperature 700 parts of 2,3-dihydrofuran are added and the mixture is neutralized after stirring for five hours.
Man erhält nach dem Abdestillieren des Äthers 500 Teile 2-(4',5'-Methylendioxy-2'-n-propyl-phenoxy)-tetrahydrofuran vom Kp. 0,3 130 bis 135°C. Beispiel 3 In eine Lösung von 360 Teilen 6-Hydroxy-dihydrosafrol und 3 Teilen konzentrierter Salzsäure in 500 Teilen Tetrahydrofuran werden bei Siedetemperatur (ungefähr 64°C) 250 Teile 2,3-Dihydropyran eingetragen. Man läßt die Mischung noch ungefähr 3 Stunden unter Rückflußkühlung sieden. Nach Abkühlen wird mit Natronlauge neutralisiert und destilliert.After distilling off the ether, 500 parts of 2- (4 ', 5'-methylenedioxy-2'-n-propyl-phenoxy) -tetrahydrofuran are obtained from bp 0.3 130 to 135 ° C. Example 3 In a solution of 360 parts of 6-hydroxy-dihydrosafrol and 3 parts of concentrated hydrochloric acid in 500 parts of tetrahydrofuran are at boiling temperature (about 64 ° C) 250 parts of 2,3-dihydropyran entered. The mixture is still left reflux for about 3 hours. After cooling, it is washed with sodium hydroxide solution neutralized and distilled.
Man erhält nach dem Abdestillieren des Tetrahydrofurans 390 Teile 2-(4',5'-Methylendioxy-2'-n-propyl-phenoxy) -tetrahydropyran vom Siedepunkt 128°C bei 0,1 mm.After the tetrahydrofuran has been distilled off, 390 parts are obtained 2- (4 ', 5'-methylenedioxy-2'-n-propyl-phenoxy) -tetrahydropyran with a boiling point of 128 ° C at 0.1 mm.
Die Wirkung der erfindungsgemäß erhaltenen Derivate des 6-Hydroxy-dihydrosafrols
geht aus folgendem Versuch hervor: Glasgefäße von 250 ccm Inhalt werden mit 1 ccm
der acetonischen Lösung von Allethrin (0,00050/0) und Synergist (0,0025 0/0) ausgekleidet.
Nach dem Verdampfen des Lösungsmittels bringt man 4 Tage alte Stubenfliegen (Musca
domestica) in die Gefäße und bestimmt nach 2 Stunden die Zahl der in Rückenlage
befindlichen Tiere.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB46331A DE1057131B (en) | 1957-10-09 | 1957-10-09 | Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB46331A DE1057131B (en) | 1957-10-09 | 1957-10-09 | Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1057131B true DE1057131B (en) | 1959-05-14 |
Family
ID=6967908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB46331A Pending DE1057131B (en) | 1957-10-09 | 1957-10-09 | Process for the preparation of insecticidally active derivatives of 6-hydroxy-dihydrosafole |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1057131B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297369A (en) * | 2006-04-03 | 2007-11-15 | Sumitomo Chemical Co Ltd | 1,3-benzdioxole compounds and uses thereof |
-
1957
- 1957-10-09 DE DEB46331A patent/DE1057131B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297369A (en) * | 2006-04-03 | 2007-11-15 | Sumitomo Chemical Co Ltd | 1,3-benzdioxole compounds and uses thereof |
| CN101050210B (en) * | 2006-04-03 | 2012-12-05 | 住友化学株式会社 | 1,3-benzodioxol compound and use of same |
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