CH676119A5 - 2,2-Di:chloro-1,3-benzodioxole derivs. prodn. - by reacting 2-unsubstituted cpd. with chlorine and phosphorus tri:chloride, useful as pesticide intermediates - Google Patents
2,2-Di:chloro-1,3-benzodioxole derivs. prodn. - by reacting 2-unsubstituted cpd. with chlorine and phosphorus tri:chloride, useful as pesticide intermediates Download PDFInfo
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- CH676119A5 CH676119A5 CH239888A CH239888A CH676119A5 CH 676119 A5 CH676119 A5 CH 676119A5 CH 239888 A CH239888 A CH 239888A CH 239888 A CH239888 A CH 239888A CH 676119 A5 CH676119 A5 CH 676119A5
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 11
- 239000000460 chlorine Substances 0.000 title claims description 11
- 229910052801 chlorine Inorganic materials 0.000 title claims description 11
- 239000000543 intermediate Substances 0.000 title abstract description 3
- 239000000575 pesticide Substances 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title 1
- 239000011574 phosphorus Substances 0.000 title 1
- 229910052698 phosphorus Inorganic materials 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 30
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- NMNKOUVBELKKTR-UHFFFAOYSA-N 2,2-dichloro-1,3-benzodioxole Chemical class C1=CC=C2OC(Cl)(Cl)OC2=C1 NMNKOUVBELKKTR-UHFFFAOYSA-N 0.000 claims abstract description 11
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 abstract description 8
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NZPSDGIEKAQVEZ-UHFFFAOYSA-N 1,3-benzodioxol-2-one Chemical class C1=CC=CC2=C1OC(=O)O2 NZPSDGIEKAQVEZ-UHFFFAOYSA-N 0.000 description 2
- 150000005529 1,3-benzodioxoles Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UHLFKXLHOTZTRU-UHFFFAOYSA-N 2,2-dichloro-4-methyl-1,3-benzodioxole Chemical compound CC1=CC=CC2=C1OC(Cl)(Cl)O2 UHLFKXLHOTZTRU-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229960001701 chloroform Drugs 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LWOLJZRFQMSDAZ-UHFFFAOYSA-N syn-benzene dioxide Chemical compound C1=CC2OC2C2OC21 LWOLJZRFQMSDAZ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Prodn. of 2,2-dichloro-1,3-benzodioxoles of formula (I) comprises reacting unsubstd. cpd. of formula (II) with Cl2 in presence of PCl3. In the formulae, R = H or 1-6C alkyl. Reaction is pref. at 80-180 (esp. 85-120) deg.C, using 0.2-1.2 (esp. 0.8-1) mole PCl5 per mole (II), opt. in presence of inert: solvent, esp. chlorobenzene, 1,2-dichlorobenzene or CCl4. USE/ADVANTAGE - (I) are intermediates for pesticides (see EP 198797 or DE 2819788). This method is better (for technical, economic and ecological reasons) than processes using PCl5 because PCl3 and Cl2 are easy to handle liq. or gas. Aromatic-ring chlorination is almost entirely avoided and where a solvent is used this can be recovered for recycle.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2,2-Dichlor-1,3-benzodioxolen der Formel I
EMI1.1
in welcher R für Wasserstoff oder C1-C6-Alkyl steht.
Die Verbindungen der Formel I sind wichtige Zwischenprodukte bei der Herstellung von pestizid wirksamen Mitteln, wie sie beispielsweise in der Europäischen Patentanmeldung EP-A 198 797 sowie in der Deutschen Offenlegungsschrift DE-OS 2 819 788 beschrieben sind.
Unter Alkyl ist geradkettiges oder verzweigtes Alkyl zu verstehen, z.B.: Methyl, Ethyl, n-Propyl, i-Propyl oder die vier Isomeren Butyl, n-Pentyl oder die isomeren Pentyl sowie Hexyl oder die isomeren Hexyl.
Ausgangs- und Endprodukte des erfindungsgemässen Verfahrens sind bekannt. Es ist ferner bekannt, 2,2-Dichlor-1,3-benzdioxole der Formel I, worin R für Wasserstoff steht, aus entsprechenden 1,3-Benzdioxol-2-onen durch Umsetzung mit Phosphorpentachlorid unter Druck bei einer Temperatur von 200 DEG C herzustellen. Auf diese Weise arbeitende Verfahren sind beispielsweise in den Chem. Ber. (1963), 96, 1382 sowie in den Chem. Ber. (1964), 94, 544 beschrieben.
Weiterhin ist bekannt, 2,2-Dichlor-1,3-benzdioxole durch Chlorierung von 1,3-Benzdioxolen mit Phosphorpentachlorid zu synthetisieren. Verfahren dieses Typs sind zum Beispiel in der Deutschen Offenlegungsschrift DE-OS 2 808 627, im US-Patent 4 043 791 sowie in J. Org. Chem. (1972), 37, 673 beschrieben.
Phosphorpentachlorid ist ein gelblicher, an der Luft rauchender, giftiger Feststoff, welcher besonders leicht hydrolysierbar ist. Wegen diesen nachteiligen Eigenschaften ist die Handhabung und kontinuierliche Dosierung bei Synthesen im technischen Massstab mit erheblichem apparativem Aufwand verbunden.
Da von den im Phosphorpentachlorid vorhandenen Chloratomen naturgemäss nur eines für den Chlorierungsprozess genutzt werden kann, macht der dadurch erforderliche Umsatz grosser Volumina die bekannten Verfahren zusätzlich technisch aufwendig.
Als ökonomisch besonders ungünstig erweisen sich die Verfahren zur Herstellung von Verbindungen der Formel I aus 1,3-Benzdioxol-2-onen. Bei diesen Prozessen entsteht als Nebenprodukt Phosphoroxychlorid, dessen Entsorgung mit zusätzlichem Aufwand verbunden ist. Ferner setzt der Energiebedarf für die Erzeugung der für die Chlorierung benötigten hohen Drücke und Temperaturen die Wirtschaftlichkeit dieser Prozesse herab.
Mit den bekannten Verfahren lassen sich 2,2-Dichlor-1,3-benzdioxole der Formel I nur mit hohem Aufwand und in wirtschaftlich unbefriedigender Weise herstellen. Es ist daher das Ziel der vorliegenden Erfindung, ein vom technischen, wirtschaftlichen und ökologischen Gesichtspunkt aus verbessertes und allgemein brauchbares Verfahren zur Herstellung von 2,2-Dichlor-1,3-benzdioxolen der Formel I bereitzustellen.
Es wurde gefunden, dass dieses Ziel in vorteilhafter Weise erreicht werden kann, wenn man ein 1,3-Benzdioxol der Formel II in Gegenwart von Phosphortrichlorid mit Chlor umsetzt. Entgegen den Erwartungen zeigt sich dabei, dass die bei der Einwirkung von Chlor auf 1,3-Benzdioxole der Formel I auftretende unerwünschte Kernchlorierung des Aromaten durch die Gegenwart von Phosphortrichlorid nahezu vollständig vermieden werden kann.
Gemäss vorliegender Erfindung wird daher vorgeschlagen, 2,2-Dichlor-1,3-benzdioxole der Formel I
EMI3.1
worin R die oben angegebene Bedeutung hat, in der Weise herzustellen, dass man ein 1,3-Benzdioxol der Formel II
EMI3.2
worin R die oben angegebene Bedeutung hat, in Gegenwart von Phosphortrichlorid mit Chlor umsetzt. Die Menge an Phosphortrichlorid ist an sich nicht begrenzt. Aus ökonomischen Gründen ist eine Menge von 0,2 bis 1,2 Mol Phosphortrichlorid pro Mol Benzdioxol der Formel II bevorzugt. Besonders bevorzugt werden 0,8 bis 1 Mol Phosphortrichlorid pro Mol Benzdioxol der Formel II verwendet.
Die erfindungsgemässe Chlorierung wird vorteilhaft bei erhöhter Temperatur durchgeführt, dabei hat sich ein Temperaturbereich von 80 DEG C bis 180 DEG C als geeignet erwiesen. Bevorzugt ist eine Temperatur von 85 DEG C bis 120 DEG C. Das erfindungsgemässe Verfahren kann in Gegenwart oder in Abwesenheit eines Lösungsmittels durchgeführt werden.
Besonders gut geeignet sind chlorhaltige Lösungsmittel wie z.B. Chlorbenzol, 1,2-Dichlorbenzol, Trichlormethan, Tetrachlormethan oder Dichlorethan, ganz besonders aber Chlorbenzol.
Eine der bevorzugten Ausführungsformen des erfindungsgemässen Verfahrens ist jene, bei welcher die Chlorierung von 1,3-Benzdioxol der Formel II, worin R für Wasserstoff oder Methyl steht, in Gegenwart von 0,8 bis 1 Mol Phosphortrichlorid pro Mol Benzdioxol der Formel II bei einer Temperatur von 85 DEG C bis 120 DEG C erfolgt.
Durch das erfindungsgemässe Verfahren wird es möglich, 2,2-Dichlor-1,3-benzdioxole der Formel I auf besonders einfache Art und in guten Ausbeuten herzustellen. Das zur erfindungsgemässen Chlorierung der 1,3-Benzdioxole der Formel II eingesetzte Chlor kann im Gegensatz zum kristallinen Phosphorpentachlorid sowohl gasförmig als auch flüssig in technisch einfach auszuführender Weise dem Reaktionsgemisch kontinuierlich zudosiert werden.
Da das eingesetzte Phosphortrichlorid in flüssiger Form vorliegt, ist dessen Dosierung und Handhabung ebenfalls mit nur wenig Aufwand verbunden. Gegebenenfalls zugesetzte Lösungsmittel können nach Abschluss der Chlorierungsreaktion abdestilliert und gemeinsam mit dem auf gleiche Weise zurückgewonnenen Phosphortrichlorid für den nächsten Ansatz wiederverwendet werden. Beim erfindungsgemässen Verfahren entsteht als einziges Nebenprodukt Chlorwasserstoff, der aus dem Reaktionsgemisch laufend entweicht und problemlos entsorgt werden kann.
Das erfindungsgemässe Verfahren wird durch das folgende Beispiel näher erläutert:
Herstellungsbeispiel
Beispiel 1: 2,2-Dichlor-1,3-benzdioxol
Zu einer Lösung von 200 g 1,3-Benzdioxol in 200 g Phosphortrichlorid werden unter Rückfluss bei einer Temperatur von 90 bis 95 DEG C innerhalb von 6 Stunden 248 g Chlor eingeleitet. Der entstandene Chlorwasserstoff entweicht dabei kontinuierlich. Nach beendeter Chlor-Einleitung wird die Reaktionsmischung 15 Minuten unter Rückfluss gerührt. Nach Abdestillieren des Phosphortrichlorids erhält man als Rückstand 313 g 2,2-Dichlor-1,3-benzdioxol (90-95% d. Th.). Nach Reinigung durch Destillation bei 80 bis 85 DEG C und 25 mbar Druck beträgt der Schmelzpunkt 14 bis 16 DEG C.
Entsprechend der vorstehend beschriebenen Arbeitsweise wurde auch die Verbindung 2,2-Dichlor-4-methyl-1,3-benzdioxol (Kp. 96-99 DEG C/20 mbar, Smp. 16-18 DEG C) erhalten.
The present invention relates to a process for the preparation of 2,2-dichloro-1,3-benzodioxoles of the formula I.
EMI1.1
in which R represents hydrogen or C1-C6-alkyl.
The compounds of the formula I are important intermediates in the preparation of pesticidally active agents, as are described, for example, in European patent application EP-A 198 797 and in German Offenlegungsschrift DE-OS 2 819 788.
Alkyl is to be understood as straight-chain or branched alkyl, for example: methyl, ethyl, n-propyl, i-propyl or the four isomers butyl, n-pentyl or the isomeric pentyl and hexyl or the isomeric hexyl.
Starting and end products of the process according to the invention are known. It is also known that 2,2-dichloro-1,3-benzodioxoles of the formula I, in which R is hydrogen, from corresponding 1,3-benzdioxol-2-ones by reaction with phosphorus pentachloride under pressure at a temperature of 200 ° C. to manufacture. Methods that work in this way are described, for example, in Chem. Ber. (1963), 96, 1382 and in Chem. Ber. (1964), 94, 544.
It is also known to synthesize 2,2-dichloro-1,3-benzo dioxoles by chlorinating 1,3-benzo dioxoles with phosphorus pentachloride. Methods of this type are described, for example, in German Offenlegungsschrift DE-OS 2 808 627, in US Pat. No. 4,043,791 and in J. Org. Chem. (1972), 37, 673.
Phosphorus pentachloride is a yellowish, air-smoking, toxic solid that is particularly easy to hydrolyze. Because of these disadvantageous properties, handling and continuous metering in syntheses on an industrial scale are associated with considerable outlay on equipment.
Since, of course, only one of the chlorine atoms present in the phosphorus pentachloride can be used for the chlorination process, the conversion of large volumes required thereby also makes the known processes technically complex.
The processes for the preparation of compounds of the formula I from 1,3-benzdioxol-2-ones have proven to be particularly unfavorable economically. These processes produce phosphorus oxychloride as a by-product, the disposal of which involves additional effort. Furthermore, the energy requirement for the generation of the high pressures and temperatures required for the chlorination reduces the economics of these processes.
With the known processes, 2,2-dichloro-1,3-benzodioxoles of the formula I can be prepared only with great effort and in an economically unsatisfactory manner. It is therefore the object of the present invention to provide an improved and generally usable process for the preparation of 2,2-dichloro-1,3-benzodioxoles of the formula I from the technical, economic and ecological point of view.
It has been found that this goal can be achieved in an advantageous manner if a 1,3-benzdioxole of the formula II is reacted with chlorine in the presence of phosphorus trichloride. Contrary to expectations, it can be seen that the undesired core chlorination of the aromatic compound which occurs when chlorine is subjected to 1,3-benzoxioxoles of the formula I can be almost completely avoided by the presence of phosphorus trichloride.
According to the present invention, it is therefore proposed to use 2,2-dichloro-1,3-benzodioxoles of the formula I.
EMI3.1
wherein R has the meaning given above, in such a way that a 1,3-benzdioxole of the formula II
EMI3.2
wherein R has the meaning given above, reacted with chlorine in the presence of phosphorus trichloride. The amount of phosphorus trichloride is not limited per se. For economic reasons, an amount of 0.2 to 1.2 moles of phosphorus trichloride per mole of benzene dioxide of the formula II is preferred. 0.8 to 1 mole of phosphorus trichloride are particularly preferably used per mole of benzodioxole of the formula II.
The chlorination according to the invention is advantageously carried out at elevated temperature, a temperature range from 80 ° C. to 180 ° C. has proven to be suitable. A temperature of 85 ° C. to 120 ° C. is preferred. The process according to the invention can be carried out in the presence or in the absence of a solvent.
Chlorine-containing solvents such as e.g. Chlorobenzene, 1,2-dichlorobenzene, trichloromethane, carbon tetrachloride or dichloroethane, but especially chlorobenzene.
One of the preferred embodiments of the process according to the invention is that in which the chlorination of 1,3-benzdioxole of the formula II, in which R is hydrogen or methyl, in the presence of 0.8 to 1 mol of phosphorus trichloride per mole of benzodioxole of the formula II in a Temperature from 85 ° C to 120 ° C takes place.
The process according to the invention makes it possible to prepare 2,2-dichloro-1,3-benzodioxoles of the formula I in a particularly simple manner and in good yields. In contrast to the crystalline phosphorus pentachloride, the chlorine used for the chlorination of the 1,3-benzodioxoles of the formula II according to the invention can be metered continuously into the reaction mixture both in gaseous and liquid form in a technically simple manner.
Since the phosphorus trichloride used is in liquid form, its metering and handling is also associated with little effort. Any added solvents can be distilled off after completion of the chlorination reaction and reused together with the phosphorus trichloride recovered in the same way for the next batch. In the process according to the invention, the only by-product is hydrogen chloride, which continuously escapes from the reaction mixture and can be disposed of without problems.
The process according to the invention is explained in more detail by the following example:
Manufacturing example
Example 1: 2,2-dichloro-1,3-benzdioxole
248 g of chlorine are introduced over 6 hours under reflux at a temperature of 90 to 95 ° C. to a solution of 200 g of 1,3-benzdioxole in 200 g of phosphorus trichloride. The resulting hydrogen chloride escapes continuously. After the introduction of chlorine has ended, the reaction mixture is stirred under reflux for 15 minutes. After the phosphorus trichloride has been distilled off, 313 g of 2,2-dichloro-1,3-benzdioxole (90-95% of theory) are obtained as the residue. After purification by distillation at 80 to 85 ° C. and 25 mbar pressure, the melting point is 14 to 16 ° C.
According to the procedure described above, the compound 2,2-dichloro-4-methyl-1,3-benzdioxol (bp. 96-99 ° C / 20 mbar, mp. 16-18 ° C) was obtained.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH239888A CH676119A5 (en) | 1988-06-22 | 1988-06-22 | 2,2-Di:chloro-1,3-benzodioxole derivs. prodn. - by reacting 2-unsubstituted cpd. with chlorine and phosphorus tri:chloride, useful as pesticide intermediates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH239888A CH676119A5 (en) | 1988-06-22 | 1988-06-22 | 2,2-Di:chloro-1,3-benzodioxole derivs. prodn. - by reacting 2-unsubstituted cpd. with chlorine and phosphorus tri:chloride, useful as pesticide intermediates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH676119A5 true CH676119A5 (en) | 1990-12-14 |
Family
ID=4232847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH239888A CH676119A5 (en) | 1988-06-22 | 1988-06-22 | 2,2-Di:chloro-1,3-benzodioxole derivs. prodn. - by reacting 2-unsubstituted cpd. with chlorine and phosphorus tri:chloride, useful as pesticide intermediates |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH676119A5 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567848A1 (en) * | 1992-04-27 | 1993-11-03 | Bayer Ag | Process for the alpha-chlorination of arylethern |
| EP0759433A1 (en) * | 1995-08-21 | 1997-02-26 | Bayer Ag | Process for the preparation of 2,2-difluorobenzo(1.3) dioxolcarbaldehydes |
| EP0786446A1 (en) * | 1996-01-23 | 1997-07-30 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde |
| WO2016038627A1 (en) * | 2014-09-11 | 2016-03-17 | Srf Limited | Process for the preparation of halogenated derivatives of aromatic ethers |
| CN114181186A (en) * | 2021-09-23 | 2022-03-15 | 山东福尔有限公司 | Preparation method of difluoro piperonyl |
-
1988
- 1988-06-22 CH CH239888A patent/CH676119A5/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0567848A1 (en) * | 1992-04-27 | 1993-11-03 | Bayer Ag | Process for the alpha-chlorination of arylethern |
| US5440051A (en) * | 1992-04-27 | 1995-08-08 | Bayer Aktiengesellschaft | Process for the α-chlorination of aryl ethers |
| JP3390992B2 (en) | 1992-04-27 | 2003-03-31 | バイエル アクチェンゲゼルシャフト | Method for α-chlorination of aryl ether |
| EP0759433A1 (en) * | 1995-08-21 | 1997-02-26 | Bayer Ag | Process for the preparation of 2,2-difluorobenzo(1.3) dioxolcarbaldehydes |
| US5637737A (en) * | 1995-08-21 | 1997-06-10 | Bayer Aktiengesellschaft | Process for the preparation of 2,2-difluorobenzo[1.3]dioxolecarbaldehydes |
| EP0786446A1 (en) * | 1996-01-23 | 1997-07-30 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde |
| CN1070835C (en) * | 1996-01-23 | 2001-09-12 | 宇部兴产株式会社 | Method for preparation of protocatechuic aldehyde |
| WO2016038627A1 (en) * | 2014-09-11 | 2016-03-17 | Srf Limited | Process for the preparation of halogenated derivatives of aromatic ethers |
| CN114181186A (en) * | 2021-09-23 | 2022-03-15 | 山东福尔有限公司 | Preparation method of difluoro piperonyl |
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