DE953878C - Process for the preparation of insecticidal derivatives of tetrahydrofuran - Google Patents
Process for the preparation of insecticidal derivatives of tetrahydrofuranInfo
- Publication number
- DE953878C DE953878C DEB35699A DEB0035699A DE953878C DE 953878 C DE953878 C DE 953878C DE B35699 A DEB35699 A DE B35699A DE B0035699 A DEB0035699 A DE B0035699A DE 953878 C DE953878 C DE 953878C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- tetrahydrofuran
- preparation
- formula
- 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.)
- Expired
Links
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 7
- 230000000749 insecticidal effect Effects 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 235000013405 beer Nutrition 0.000 claims 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000007858 starting material Substances 0.000 description 11
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 229940081310 piperonal Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 150000001241 acetals Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- -1 heterocyclic radicals Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JXNORPPTKDEAIZ-QOCRDCMYSA-N O-4''-alpha-D-mannosylqueuosine Chemical compound NC(N1)=NC(N([C@@H]([C@@H]2O)O[C@H](CO)[C@H]2O)C=C2CN[C@H]([C@H]3O)C=C[C@@H]3O[C@H]([C@H]([C@H]3O)O)O[C@H](CO)[C@H]3O)=C2C1=O JXNORPPTKDEAIZ-QOCRDCMYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 240000004460 Tanacetum coccineum Species 0.000 description 1
- 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 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- 229940015367 pyrethrum Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 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
- C07D407/04—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 directly linked by a ring-member-to-ring-member bond
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
- A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Verfahren zur Herstellung von Insektiziden Derivaten des Tetrahydrofurans Es wurde gefunden, daß man neue Derivate des Tetrahydrofurans (II) mit starker insektizider Wirkung erhält, wenn man Verbindungen der allgemeinen Formel I, in der R und R' Wasserstoffatome, Alkyl-, Cycloalkyl-, Aralkyl-, Aryl oder heterocyclische Reste bedeuten oder Glieder eines gemeinsamen gesättigten Ringes sind und R" ein Wasserstoffatom oder einen Acylrest oder einen äther- oder acetalartig gebundenen Alkylrest bedeutet, nach an sich bekannten Methoden an der Dreifachbindung katalytisch hydriert und die erhaltenen gesättigten Verbindungen mit wasserabspaltenden Mitteln behandelt. Die Ausgangsstoffe I für das Verfahren erhält man nach an sich bekannten Verfahren, indem man z. B. entweder Piperonal zunächst mit Acetylen zum Piperonyläthinylcarbinol und dieses mit Carbonylverbindungen, wie Formaldehyd, Acetaldehyd, Benzaldehyd, Aceton oder Cyclohexanon, umsetzt oder indem man Piperonal auf Acetylenalkohole, wie Propargylalkohol, Butin-(i)-01-(3), 2-Methylbutin-(3)-01-(2), 3-Methylpentin-(i)-01-(3), i-Äthinylcyclohexanol-(i) oder Phenyläthinylcarbinol, einwirken läßt. An Stelle der genannten Alkohole kann man auch ihre Ester, Äther oder Acetale, z. B. CH.-CH(OCH3)-O-CH,-C-CH, oder Pyranderivate, wie Die Hydrierung der Dreifachbindung der so erhaltenen Verbindungen der Formel I - erfolgt mit Wasserstoff bei erhöhtem Druck und mäßig erhöhten Temperaturen in Gegenwart der üblichen Katalysatoren, wie Nickel, Kobalt, Kupfer oder Edelmetalle, rasch und vollständig.Process for the preparation of insecticidal derivatives of tetrahydrofuran It has been found that new derivatives of tetrahydrofuran (II) with a strong insecticidal action are obtained if compounds of the general formula I in which R and R 'are hydrogen atoms, alkyl, cycloalkyl, aralkyl -, aryl or heterocyclic radicals or are members of a common saturated ring and R "denotes a hydrogen atom or an acyl radical or an ether or acetal-like bonded alkyl radical, catalytically hydrogenated at the triple bond by methods known per se and the saturated compounds obtained with dehydrating agents treated. The starting materials I for the process are obtained by methods known per se by z. B. either piperonal first with acetylene to Piperonyläthinylcarbinol and this with carbonyl compounds, such as formaldehyde, acetaldehyde, benzaldehyde, acetone or cyclohexanone, or by converting piperonal to acetylene alcohols, such as propargyl alcohol, butyne- (i) -01- (3), 2- Methylbutin- (3) -01- (2), 3-methylpentin- (i) -01- (3), i-ethynylcyclohexanol- (i) or phenylethinylcarbinol, allowed to act. Instead of the alcohols mentioned, you can also use their esters, ethers or acetals, eg. B. CH.-CH (OCH3) -O-CH, -C-CH, or pyran derivatives, such as The triple bond of the compounds of the formula I thus obtained is hydrogenated quickly and completely with hydrogen at elevated pressure and moderately elevated temperatures in the presence of the customary catalysts, such as nickel, cobalt, copper or noble metals.
Für die Umwandlung der so erhaltenen gesättigten Verbindungen 1 in die gewünschten Derivate des Tetrahydrofurans (II) erhitzt man erstere zweckmäßig in einem Lösungs- oder Verdünnungsmittel, das die abgespaltene Verbindung H O R", z. B. Wasser; azeotrop entfernt, und unter Zusatz eines sauren Mittels, wie Toluolsulfonsäure, Oxal-, Schwefel- oder Phosphorsäure und ihre sauren Salze, Essigsäure, Salzsäure oder Jod. Die Abspaltung von H O R" kann auch in der Ggsphase an Katalysatoren, wie Tonerde, Kieselgel oder Thoriumoxyd, erfolgen.For the conversion of the saturated compounds 1 obtained in this way into the desired derivatives of tetrahydrofuran (II) are expediently heated in a solvent or diluent that removes the compound H O R ", z. B. water; removed azeotropically, and with the addition of an acidic agent such as toluenesulfonic acid, Oxalic, sulfuric or phosphoric acid and their acid salts, acetic acid, hydrochloric acid or iodine. The elimination of H O R "can also be carried out in the gas phase on catalysts, such as clay, silica gel or thorium oxide.
Die so erhaltenen Derivate des Tetrahydrofurans entfalten, insbesondere im Gemisch mit Pyrethrum und bzw. oder Allethrin, eine starke Insektizide Wirkung.The tetrahydrofuran derivatives thus obtained unfold, in particular in a mixture with pyrethrum and / or allethrin, a strong insecticidal effect.
Die in den Beispielen genannten Teile sind Gewichtsteile. Beispiel i Zur Herstellung des Ausgangsstoffes trägt man in ein Gemisch aus 7ö Teilen Ngtriumpulver und 16oo Teilen trockenem Tetrahydrofuran 45o Teile des gemischten Acetals der Formel CH,-CH (OCH3)-O-CHZ-C=CH ein, das durch Umsetzen von Propargylalkohol mit Vinylmethyläther in Gegenwart eines sauren Katalysators hergestellt werden kann. Dabei geht das Natrium unter Entwicklung von Wasserstoff allmählich in Lösung, während sich das Gemisch bis zum Sieden erwärmt. Wenn nach etwa 4stündigem Rühren alles Natrium gelöst ist, trägt man bei etwa 35° eine Lösung von 4oo Teilen Piperonal in 6oo Teilen Tetrahydrofuran ein und rührt einige Stunden bei gewöhnlicher Temperatur.The parts mentioned in the examples are parts by weight. example To prepare the starting material, a mixture of 70 parts of nitrium powder is added and 1600 parts dry tetrahydrofuran 45o parts of the mixed acetal of the formula CH, -CH (OCH3) -O-CHZ-C = CH a, obtained by reacting propargyl alcohol with vinyl methyl ether can be prepared in the presence of an acidic catalyst. This is where the sodium goes with evolution of hydrogen gradually dissolving as the mixture moves heated to boiling point. When all the sodium has dissolved after stirring for about 4 hours, a solution of 400 parts of piperonal in 600 parts of tetrahydrofuran is carried at about 35 ° and stir for a few hours at ordinary temperature.
Dann fügt man 5oo Teile Wasser hinzu, trennt die das Ausgangsmaterial für die Hydrierung enthaltende organische Schicht ab, verdünnt sie mit 5oo Teilen Methanol, setzt 25 Teile eines Nickelkatalysators hinzu und hydriert bei 8o° mit Wasserstoff von Zoo Atmosphären. Nach Abfiltrieren des Katalysators und Abdestillieren der Lösungsmittel erhält man 31o Teile eines schwach gelblichen öles, das unter o,i mm Druck zwischen 145 und 151° übergeht und im wesentlichen aus der Verbindung der Formel besteht. 225 Teile dieses Öls werden in 75o Teilen Benzol gelöst und nach Zugabe von o,o5 Teilen p-Toluolsulfonsäure in einem Kreislaufgerät zum Sieden erhitzt. Dabei gehen mit dem Benzol 26 Teile Wasser und der abgespaltene Acetaldehyd über. Das Benzol wird durch einen Abscheider stets wieder in das Siedegefäß zurückgeleitet.500 parts of water are then added, the organic layer containing the starting material for the hydrogenation is separated off, diluted with 500 parts of methanol, 25 parts of a nickel catalyst are added and the mixture is hydrogenated at 80 ° with hydrogen from zoo atmospheres. After filtering off the catalyst and distilling off the solvent, 31o parts of a pale yellowish oil are obtained, which under 0.1 mm pressure passes over between 145 and 151 ° and essentially consists of the compound of the formula consists. 225 parts of this oil are dissolved in 750 parts of benzene and, after the addition of 0.05 parts of p-toluenesulfonic acid, heated to the boil in a circulatory device. In this case, 26 parts of water and the split off acetaldehyde pass over with the benzene. The benzene is always returned to the boiling vessel through a separator.
Sobald kein Wasser und Acetaldehyd mehr übergehen, wäscht man mit verdünnter Natriumcarbonatlösung, destilliert das Benzol ab und unterwirft den öligen Rückstand der fraktionierten Destillation bei vermindertem Druck.As soon as no more water and acetaldehyde pass over, one washes with dilute sodium carbonate solution, the benzene is distilled off and subjected to the oily Fractional distillation residue under reduced pressure.
Man; erhält 115 Teile 2-(4, 5'-Methylendioxyphenyl)-tetrahydrofuran vom Kp. io7 bis io9° unter o,oi mm Druck.Man; receives 115 parts of 2- (4,5'-methylenedioxyphenyl) tetrahydrofuran from Kp. 107 to 109 ° under o.o mm pressure.
Beispiel 2 Man verwendet als Ausgangsstoff die Verbindung der folgenden Formel: die man aus 5oo Teilen des durch Umsetzen von Vinylmethyläther mit 2-Methyl-butin-(3)-01-(2) in Gegenwart eines sauren Katalysators erhältlichen gemischten Acetals der Formel H C - C-C (C H3)2-O-C H (C H3) -O C H3 7o Teilen Natrium und 45o Teilen Piperonal wie im Beispiel i hergestellt hat. Man löst dieses Ausgangsmaterial in 5oo Teilen Methanol und hydriert nach Zusatz von 2o Teilen eines Nickelkatalysators bei 5o° mit Wasserstoff von Zoo Atm. Druck.Example 2 The compound of the following formula is used as the starting material: obtained from 500 parts of the mixed acetal of the formula HC - CC (C H3) 2-OC H (C H3) obtainable by reacting vinyl methyl ether with 2-methyl-butyne- (3) -01- (2) in the presence of an acidic catalyst ) -O C H3 7o parts of sodium and 45o parts of piperonal as in Example i. This starting material is dissolved in 500 parts of methanol and, after addition of 20 parts of a nickel catalyst, hydrogenated at 50 ° with hydrogen from Zoo Atm. Pressure.
Nach Abfiltrieren des Katalysators und Abdestillieren des Lösungsmittels wird der Rückstand in 2ooo Teilen Toluol aufgenommen und nach Zugabe von 3 Teilen p-Toluolsulfonsäure in einem Kreislaufgerät zum Sieden erhitzt. Hierbei werden, wie im Beispiel i beschrieben, Wasser und Acetaldehyd abgespalten. Sobald kein Wasser und Acetaldehyd mehr übergehen, wird das Gemisch aufgearbeitet. Man erhält 482 Teile 2-(4', 5'-Methylendioxyphenyl) - 5, 5. - dimethyltetrahydrofuran vom Kp.15 = 121 bis r25°.After filtering off the catalyst and distilling off the solvent, the residue is taken up in 2,000 parts of toluene and, after addition of 3 parts of p-toluenesulfonic acid, heated to the boil in a circulatory device. Here, as described in Example i, water and acetaldehyde are split off. As soon as no more water and acetaldehyde pass over, the mixture is worked up. 482 parts of 2- (4 ', 5'-methylenedioxyphenyl) -5, 5-dimethyltetrahydrofuran with a boiling point of 15 = 121 to 25 ° are obtained.
Beispiel .3 Man verwendet als Ausgangsstoff die Verbindung der folgenden Formel: die man aus 70o Teilen des gemischten Acetals der Formel (erhältlich durch Umsetzen von 3-Methylpentin-(q.)-ol-(3) mit Vinylmethyläther), ioo Teilen Natriumpulver und 6oo Teilen Piperonal wie im Beispiel i hergestellt hat. Wenn man diese Verbindung wie im Beispiel e katalytisch hydriert und wie im Beispiel i in Toluol unter Zugabe von kleinen Mengen p-Toluolsulfonsäure in einem Kreislaufgerät zum Sieden erhitzt, bis keinWasser und Acetaldehyd mehr übergeht, erhält man 781 Teile 2-(4', 5'-MetÜylendioxyphenyl)-5-methyl-5-äthyltetrahydrofuran vom Kp.o,oos = 96 bis ioo°. Beispiel 4 Man verwendet als Ausgangsstoff die Verbindung der Formel die man aus 35o Teilen des gemischten Acetals der Formel (erhältlich durch Umsetzen von 2-Methylpentin-(4) -0l- (3) mit Vinylmethyläther, 46 Teilen Natrium und 3oo Teilen Piperonal wie im Beispiel i hergestellt hat. Bei der Hydrierung und Weiterverarbeitung wie im Beispiel i erhält man 297 Teile 2 - (4', 5'- Methylendioxyphenyl) - 5 - isopropyltetrahydrofuran vom Kp.1,Q5 =136 bis 142°. Beispiel 5 Man verwendet als Ausgangsstoff die Verbindung der Formel . die man aus Zoo Teilen des gemischten Acetals der Formel (erhältlich durch Umsetzen von i-Äthinylcyclohexanol-(i) und Vinylmethyläther), 23 Teilen Natrium und 15o Teilen Piperonal wie im Beispiel i hergestellt hat. Bei der Hydrierung und Weiterverarbeitung wie im Beispiel i erhält man 161 Teile 2 - (4, 5'- Methylendioxyphenyl) - 5, 5 - spiropentamethylentetrahydrofuran vom KP-0,005 = 120 bis 132°. Beispiel 6 Man verwendet als Ausgangsstoff das i -(q', 5'-Methylendioxyphenyl) - ¢, q. - dimethylbutin - (2) - diol -(1.4) der Formel Dieser Ausgangsstoff wird wie folgt hergestellt: Zu einer Suspension von i2o Teilen gepulvertem, wasserfreiem Kaliumhydroxyd in 5oo Teilen Tetrahydrofuran fügt man eine Lösung von 264 Teilen 5'-Methylendioxyphenyl)-propin.-(2)-ol-(i) in 7o Teilen trockenem Tetrahydrofuran, wobei die Temperatur nicht über -f- q.0° steigen soll.Example .3 The compound of the following formula is used as the starting material: which are obtained from 70o parts of the mixed acetal of the formula (obtainable by reacting 3-methylpentine- (q.) - ol- (3) with vinyl methyl ether), 100 parts of sodium powder and 600 parts of piperonal as in Example i. If this compound is catalytically hydrogenated as in example e and heated to boiling in toluene in toluene with the addition of small amounts of p-toluenesulfonic acid until no more water or acetaldehyde passes over, 781 parts of 2- (4 ', 5 '-MetÜylenedioxyphenyl) -5-methyl-5-ethyltetrahydrofuran from b.p. o, oos = 96 to 100 °. Example 4 The compound of the formula is used as the starting material which are obtained from 35o parts of the mixed acetal of the formula (Obtainable by reacting 2-methylpentine- (4) -0l- (3) with vinyl methyl ether, 46 parts of sodium and 300 parts of piperonal as in Example I. In the hydrogenation and further processing as in Example i, 297 parts of 2- (4 ', 5'-methylenedioxyphenyl) - 5 - isopropyltetrahydrofuran of boiling point 1, Q5 = 136 ° to 142 °. EXAMPLE 5 The compound of the formula is used as the starting material. which can be obtained from zoo parts of the mixed acetal formula (obtainable by reacting i-ethynylcyclohexanol (i) and vinyl methyl ether), 23 parts of sodium and 150 parts of piperonal as in Example i. In the hydrogenation and further processing as in Example i, 161 parts of 2- (4,5'-methylenedioxyphenyl) -5, 5-spiropentamethylenetetrahydrofuran of KP-0.005 = 120 to 132 ° are obtained. Example 6 The starting material used is i - (q ', 5'-methylenedioxyphenyl) - [, q. - dimethylbutyne - (2) - diol - (1.4) of the formula This starting material is prepared as follows: A solution of 264 parts of 5'-methylenedioxyphenyl) -propine .- (2) -ol- (i) in 70 parts of dry material is added to a suspension of 12o parts of powdered, anhydrous potassium hydroxide in 500 parts of tetrahydrofuran Tetrahydrofuran, whereby the temperature should not rise above -f- q.0 °.
Das i - (q.', 5' - Methylendioxyphenyl) -propin-(2)-ol-(i) kann in üblicher Weise durch Umsetzung von Piperonal mit Acetylen unter Zusatz eines alkalischen Katalysators erhalten werden.The i - (q. ', 5' - methylenedioxyphenyl) -propine- (2) -ol- (i) can in Usually by reacting piperonal with acetylene with the addition of an alkaline one Catalyst can be obtained.
Nach Abklingen der Reaktionswärme wird das Gemisch im Laufe einer Stunde mit i2o Teilen Aceton versetzt und gleichzeitig auf -f- q.0° erwärmt, worauf man q. Stunden bei -h qo° und io Stunden bei Raumtemperatur weiterrührt.After the heat of reaction has subsided, the mixture is in the course of a Hour with i2o parts of acetone and at the same time heated to -f- q.0 °, whereupon man q. Stirring for hours at -h qo ° and 10 hours at room temperature.
Man gießt- das Reaktionsgemisch, das nun das oben formulierte Ausgangsmaterial enthält, auf 25o Teile Eis, trennt die organische Schicht ab, neutralisiert sie mit Eisessig, verdünnt sie mit 75o Teilen Methanol und hydriert nach Zusatz von 2o Teilen eines Nickelkatalysators bei 5o° mit Wasserstoff von Zoo Atm. Druck. Dann, wird der Katalysator abfiltriert und das Filtrat eingedampft. Der Rückstand.wird wie im Beispiel i mit 75o Teilen Benzol unter Zusatz von 0,5 Teilen Benzolsulfonsäure im Kreislaufgerät zum Sieden erhitzt, bis kein Wasser mehr übergeht. Man erhält 225 Teile 2 - (4, 5'- Methylendioxyphenyl) - 5, 5 - dimethyltetrahydrofuran vom Kp.o,B = i io bis i 18°.The reaction mixture, which now contains the starting material formulated above, is poured onto 250 parts of ice, the organic layer is separated off, neutralized with glacial acetic acid, diluted with 750 parts of methanol and, after addition of 20 parts of a nickel catalyst, hydrogenated with hydrogen at 50 ° from Zoo Atm. Pressure. Then the catalyst is filtered off and the filtrate is evaporated. As in Example i, the residue is heated to boiling with 750 parts of benzene with the addition of 0.5 part of benzenesulphonic acid in a circulator until no more water passes over. This gives 225 parts of 2 - (4, 5'-methylenedioxyphenyl) - 5, 5 - dimethyltetrahydrofuran from Kp.o, B = i i io to 18 °.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB35699A DE953878C (en) | 1955-05-12 | 1955-05-12 | Process for the preparation of insecticidal derivatives of tetrahydrofuran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB35699A DE953878C (en) | 1955-05-12 | 1955-05-12 | Process for the preparation of insecticidal derivatives of tetrahydrofuran |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE953878C true DE953878C (en) | 1956-12-06 |
Family
ID=6964681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB35699A Expired DE953878C (en) | 1955-05-12 | 1955-05-12 | Process for the preparation of insecticidal derivatives of tetrahydrofuran |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE953878C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1058306B (en) * | 1957-11-19 | 1959-05-27 | Basf Ag | Pest repellants |
| EP1094805A4 (en) * | 1998-07-03 | 2002-08-28 | Millennium Pharm Inc | Substituted oxygen alicyclic compounds, including methods for synthesis thereof |
-
1955
- 1955-05-12 DE DEB35699A patent/DE953878C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1058306B (en) * | 1957-11-19 | 1959-05-27 | Basf Ag | Pest repellants |
| EP1094805A4 (en) * | 1998-07-03 | 2002-08-28 | Millennium Pharm Inc | Substituted oxygen alicyclic compounds, including methods for synthesis thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1793559C3 (en) | Process for the production of furan 3 carboxylic acid esters excretion from 1543804 | |
| EP0033928A2 (en) | Use of alkyl-substituted 1,3-dioxolanes as perfumes, and perfume compositions containing them | |
| DE19621703A1 (en) | Process for the preparation of 3-oxyalkylpropan-1-ols | |
| EP0014963B1 (en) | Process for the preparation of bicyclic enol ethers and ethers of 2-(3-hydroxyprop-1-yl)-cycloalkanones | |
| DE953878C (en) | Process for the preparation of insecticidal derivatives of tetrahydrofuran | |
| DE2715080A1 (en) | PROCESS FOR THE PRODUCTION OF CYCLOPENTENONE DERIVATIVES | |
| DE3122995C2 (en) | ||
| EP0278384A2 (en) | Alcohols and ethers with cyclododecyl and cyclododecenyl groups, their preparation and use as parfuming agents | |
| DE1193512B (en) | Process for the preparation of bicyclic delta-lactones | |
| DEB0035699MA (en) | ||
| EP0000478B1 (en) | Process for the preparation of acyloins | |
| Russell et al. | Polyhydroxyalkanes from Furfural Condensation Products | |
| DE2842715A1 (en) | 3-CHLORO-3-METHYL-BUTANE OR 3-METHYL-2-BUTEN-1,4-DIAL-BIS-ACETALS, A METHOD FOR MAKING THESE COMPOUNDS AND USES | |
| DE863197C (en) | Process for the preparation of substituted alcohols of the acetylene series | |
| AT233540B (en) | Process for the preparation of allene esters | |
| DE1812097A1 (en) | Process for the production of delta2-oxazolines | |
| DE2925043A1 (en) | NEW 2,4-DISUBSTITUTED PYRANE DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS A FRAGRANCE | |
| DE2820263C3 (en) | Process for the preparation of 9-methoxy-7H-furo [3.2g] [1] -benzopyran-7-one (8-methoxy-psoralen) | |
| DE1202286B (en) | Process for the production of beta-pyrones | |
| DE2231677C2 (en) | Process for the production of aldehydes, ketones and quinones | |
| DE1081898B (en) | Process for the preparation of ª ‡ - (2-propyl-4, 5-methylenedioxy-phenyl) -aethyl-acetals | |
| DE1543880C3 (en) | Process for the production of benzo- or naphtho-dioxoles or -oxathiols | |
| DE2228333B2 (en) | Process for the preparation of optionally substituted 2-butyn-4ols | |
| AT213861B (en) | Process for the preparation of new unsaturated, optionally esterified alcohols | |
| AT235271B (en) | Process for the preparation of 7-phenylheptanediol- (1,4) |