DE19958758A1 - Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts - Google Patents
Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalystsInfo
- Publication number
- DE19958758A1 DE19958758A1 DE1999158758 DE19958758A DE19958758A1 DE 19958758 A1 DE19958758 A1 DE 19958758A1 DE 1999158758 DE1999158758 DE 1999158758 DE 19958758 A DE19958758 A DE 19958758A DE 19958758 A1 DE19958758 A1 DE 19958758A1
- Authority
- DE
- Germany
- Prior art keywords
- quaternary ammonium
- benzo
- production
- mol
- reaction
- 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.)
- Withdrawn
Links
- 150000002596 lactones Chemical class 0.000 title claims abstract description 15
- TXZFBHYDQGYOIT-UHFFFAOYSA-N 2-(chloromethyl)benzoyl chloride Chemical class ClCC1=CC=CC=C1C(Cl)=O TXZFBHYDQGYOIT-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 title abstract description 4
- 239000000543 intermediate Substances 0.000 title description 2
- 150000001639 boron compounds Chemical class 0.000 title 1
- 239000000575 pesticide Substances 0.000 title 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- -1 C 1 -C 4 alkyl Chemical class 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 2
- 229910052796 boron Inorganic materials 0.000 abstract 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 abstract 2
- 150000001642 boronic acid derivatives Chemical class 0.000 abstract 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical class C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 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
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YTEUDCIEJDRJTM-UHFFFAOYSA-N 2-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCl YTEUDCIEJDRJTM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001026509 Kata Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung
von o-Chlormethylbenzoesäurechloriden der Formel I,
The present invention relates to a process for the preparation of o-chloromethylbenzoic acid chlorides of the formula I,
in der R1 bis R4 gleich oder verschieden sein können und für Was
serstoff, C1-C4-Alkyl, Halogen oder Trifluormethyl stehen, durch
Umsetzung von benzokondensierten Lactonen der Formel II,
in which R 1 to R 4 can be the same or different and stand for water, C 1 -C 4 alkyl, halogen or trifluoromethyl, by reacting benzocondensed lactones of the formula II,
in der R1 bis R4 die vorgenannte Bedeutung besitzen, mit Thionyl chlorid.in which R 1 to R 4 have the abovementioned meaning, with thionyl chloride.
o-Chlormethyl-substituierte Benzoylchloride sind wichtige Zwi schenprodukte zur Herstellung von beispielsweise pestiziden Wirk stoffen wie sie in den Patentschriften EP-A 460 575, EP-A 463 488, WO-A 95/18789, WO-A 95/21154 und WO-A 97/15552 beschrieben sind.o-Chloromethyl-substituted benzoyl chlorides are important intermediates Products for the production of, for example, pesticidal activity substances as described in the patent specifications EP-A 460 575, EP-A 463 488, WO-A 95/18789, WO-A 95/21154 and WO-A 97/15552 are.
o-Chlormethyl-substituierte Benzoylchloride können zum Beispiel durch Umsetzung von benzokondensierten Lactonen mit Thionylchlo rid oder Phosgen hergestellt werden. Bei der Verwendung von Thio nylchlorid vereinfacht sich die Apparatetechnik und der sicher heitstechnische Aufwand verringert sich.For example, o-chloromethyl substituted benzoyl chlorides by reacting benzocondensed lactones with thionylchlo rid or phosgene can be produced. When using thio nylchloride simplifies the equipment technology and safely technical effort is reduced.
In EP-A 676 389 wird die Herstellung von o-Chlormethylbenzoesäu rechloriden aus benzokondensierten Lactonen mit Thionylchlorid in Gegenwart einer Stickstoff-Verbindung beschrieben. Um einen be friedigenden Umsatz zu erzielen, sind Reaktionstemperaturen von 160 bis 170°C erforderlich, bei denen sich Thionylchlorid bereits teilweise zersetzt und infolgedesssen störende Nebenprodukte ge bildet werden. Weiterhin ist die Zugabe von gasförmiger Salzsäure erforderlich. Schließlich liegen die Ausbeuten zum Teil deutlich unter 90%. EP-A 676 389 describes the preparation of o-chloromethylbenzoic acid rechlorides from benzo-condensed lactones with thionyl chloride in Presence of a nitrogen compound described. To be to achieve peaceful sales, reaction temperatures of 160 to 170 ° C required, at which thionyl chloride is already partially decomposed and consequently disruptive by-products be formed. Furthermore, the addition of gaseous hydrochloric acid required. After all, the yields are partly clear below 90%.
In der WO-A 99/16743 wird die Umsetzung mit Thionylchlorid in Ge genwart von BF3-Etherat und einem quartären Ammoniumsalz bei 90 bis 100°C durchgeführt. Hier erweist sich als nachteilig, daß das BF3-Etherat sehr feuchtigkeitsempfindlich ist und weiterhin im Verlauf der Reaktion Diethylether freisetzten kann. Diethylether ist niedrigsiedend, leicht brennbar und neigt zur Bildung von Peroxiden. Durch Hydrolyse von Bortrifluorid kann weiterhin Flu orwasserstoff (Flußsäure) entstehen, der stark ätzend ist und insbesondere materialtechnische Probleme aufwirft. Für die Durch führung im technischen Maßstab sind daher spezielle Apparaturen erforderlich.In WO-A 99/16743 the reaction with thionyl chloride is carried out in the presence of BF 3 etherate and a quaternary ammonium salt at 90 to 100 ° C. It proves disadvantageous here that the BF 3 etherate is very sensitive to moisture and can continue to release diethyl ether in the course of the reaction. Diethyl ether is low-boiling, highly flammable and tends to form peroxides. Hydrolysis of boron trifluoride can also result in hydrofluoric acid (hydrofluoric acid), which is highly corrosive and in particular poses technical problems. Special equipment is therefore required for implementation on a technical scale.
Aufgabe der vorliegenden Erfindung war es daher ein wirtschaftli ches und prozeßfähiges Verfahren zur Herstellung von o-Chlorme thylbenzoesäurechloriden zu finden, das die oben aufgeführten Nachteile nicht aufweist und dennoch hohe Ausbeuten liefert.The object of the present invention was therefore an economical ches and processable process for the production of o-chlorine to find thylbenzoic acid chlorides that are those listed above Does not have disadvantages and still provides high yields.
Demgemäß wurde das eingangs erwähnte Verfahren gefunden, das da durch gekennzeichnet ist, daß man die Umsetzung in Gegenwart ka talytischer Mengen von Borsäure oder Lewis-saurer Aluminium silikate und katalytischer Mengen eines Ammoniumsalzes durch führt.Accordingly, the above-mentioned method has been found, which is characterized in that the reaction in the presence ka talytic amounts of boric acid or Lewis acidic aluminum silicates and catalytic amounts of an ammonium salt leads.
Zum Einsatz gelangen benzokondensierte Lactone (Phthalide) der
allgemeinen Formel II
Benzo-condensed lactones (phthalides) of the general formula II are used
in der R1 bis R4 gleich oder verschieden sein können und für Was serstoff (H), C1-C4-Alkyl, Halogen (Fluor, Chlor, Brom oder Iod) oder Trifluormethyl stehen. Bevorzugt wird unsubstituiertes Phthalid eingesetztin which R 1 to R 4 can be the same or different and stand for What serstoff (H), C 1 -C 4 alkyl, halogen (fluorine, chlorine, bromine or iodine) or trifluoromethyl. Unsubstituted phthalide is preferably used
Als quartäre Ammoniumsalze kommen insbesondere quartäre Ammonium halogenide wie beispielsweise Tetraalkylammoniumchloride oder Benzyltrialkylammoniumchloride in Frage. Insbesondere geeignet sind: Tetramethylammoniumchlorid, Tetraethylammoniumchlorid, Te trabutylammoniumchlorid, Benzyltrimethylammoniumchlorid, Benzyl triethylammoniumchlorid, Benzyltributylammoniumchlorid, N,N-Dime thylpiperidininumchlorid. Besonders bevorzugt ist Benzyltriethyl ammoniumchlorid. Quaternary ammonium in particular comes as quaternary ammonium salts halides such as tetraalkylammonium chlorides or Benzyltrialkylammoniumchloride in question. Particularly suitable are: tetramethylammonium chloride, tetraethylammonium chloride, Te trabutylammonium chloride, benzyltrimethylammonium chloride, benzyl triethylammonium chloride, benzyltributylammonium chloride, N, N-Dime thylpiperidininum chloride. Benzyltriethyl is particularly preferred ammonium chloride.
Die quartären Ammoniumsalze werden im allgemeinen in Mengen von 0,1 bis 20 mol-% bezogen auf die eingesetzte Menge an benzokon densiertem Lacton, bevorzugt in Mengen von 0,5 bis 10 mol-%, zu gegeben.The quaternary ammonium salts are generally in amounts of 0.1 to 20 mol% based on the amount of benzokone used densified lactone, preferably in amounts of 0.5 to 10 mol% given.
Die Reaktion wird weiterhin in Gegenwart katalytischer Mengen von Borsäure oder eines Lewis-sauren Aluminiumsilikats vom Zeolith- Typ durchgeführt. Besonders bevorzugt wird Borsäure eingesetzt. Derartige Verfahren liefern hervorragende Ausbeuten und haben den Vorteil, daß die Reaktionsgemische frei von Fluoridionen sind. Damit kann im Verlauf der Reaktion keine Flußsäure (Fluorwasser stoff) enstehen. Im Vergleich zur analogen Reaktion mit BF3-Deri vaten als Lewis-Säure vereinfacht sich die gesamte Apparatetech nik.The reaction is further carried out in the presence of catalytic amounts of boric acid or a Lewis acidic zeolite-type aluminum silicate. Boric acid is particularly preferably used. Such processes provide excellent yields and have the advantage that the reaction mixtures are free from fluoride ions. This means that no hydrofluoric acid (hydrogen fluoride) can arise in the course of the reaction. Compared to the analogous reaction with BF 3 derivatives as Lewis acid, the entire apparatus technology is simplified.
Die Borsäure wird in Mengen von 0,1 bis 20 mol-% bezogen auf die eingesetzte Menge an benzokondensiertem Lacton (Phthalid), bevor zugt in Mengen von 0,5 bis 10 mol-%, zugegeben.The boric acid is present in amounts of 0.1 to 20 mol% based on the amount of benzo-condensed lactone (phthalide) used before added in amounts of 0.5 to 10 mol%, added.
Weiterhin kann es von Vorteil sein heterogene, Lewis-saure Kata lysatoren wie z. B. Zeolithe vom Faujasit-Typ, bei denen aus tauschbare Kationen teilweise oder vollständig durch Protonen er setzt sind, einzusetzen. Eine heterogen katalysierte Reaktion hat den Vorteil, daß sie im Festbett durchgeführt werden kann. Der heterogene Katalysator wird in Mengen von 0,01 bis 10 Gewichts-% und bevorzugt in Mengen von 0,1 bis 1 Gewichts-% bezogen auf die eingesetzte Menge an benzokondensiertem Lacton eingesetzt.It can also be advantageous to have heterogeneous Lewis acidic kata analyzers such as B. faujasite-type zeolites, in which exchangeable cations partly or completely by protons are to be used. Has a heterogeneously catalyzed reaction the advantage that it can be carried out in a fixed bed. The heterogeneous catalyst is used in amounts of 0.01 to 10% by weight and preferably in amounts of 0.1 to 1% by weight based on the amount of benzo-condensed lactone used.
In Bezug auf das Phthalid II werden im allgemeinen 1 bis 1,5 Äquivalente Thionylchlorid eingesetzt.Regarding phthalide II, 1 to 1.5 Equivalent thionyl chloride used.
Das Thionylchlorid kann mit den anderen Reaktionspartnern vorge legt werden (batch-Fahrweise) oder im Verlauf der Reaktion inner halb von vorzugsweise 1 bis 8 Stunden zudosiert werden (semi- batch-Fahrweise). Weiterhin ist es möglich die Reaktion kontinu ierlich durchzuführen.The thionyl chloride can be used with the other reactants be placed (batch mode) or in the course of the reaction half of preferably 1 to 8 hours are added (semi batch mode). It is also possible to continue the reaction to be carried out.
Optional kann zur Beschleunigung der Ringöffnung gasförmiger Chlorwasserstoff eingeleitet werden. Bevorzugt wird jedoch auf die Einleitung von Chlorwasserstoff während der Synthese verzich tet.Optionally, to accelerate the ring opening can be gaseous Hydrogen chloride are introduced. However, preference is given to renounce the introduction of hydrogen chloride during the synthesis tet.
Üblicherweise werden Reaktionstemperaturen von 100 bis 180°C und vorzugsweise 110 bis 150°C angewendet. Reaction temperatures of 100 to 180 ° C and preferably 110 to 150 ° C applied.
Das Verfahren wird vorzugsweise ohne Lösungsmittel durchgeführt. Es ist jedoch möglich ein gegen Thionylchlorid inertes Lösungs mittel zuzusetzen. Inerte Lösungsmittel sind z. B. aromatische Kohlenwasserstoffe wie Toluol, o-, m- oder p-Xylol oder deren Ge mische, chlorierte aromatische Kohlenwasserstoffe wie Chlorbenzol oder Dichlorbenzolen oder cyclische Carbonate wie Ethylen- oder Propylencarbonat. Weiterhin ist es möglich, Thionylchlorid selbst als Lösungsmittel einzusetzen, das am Ende der Reaktion destilla tiv abgetrennt und erneut in den Prozeß eingeschleust werden kann.The process is preferably carried out without a solvent. However, a solution which is inert to thionyl chloride is possible add funds. Inert solvents are e.g. B. aromatic Hydrocarbons such as toluene, o-, m- or p-xylene or their Ge mix, chlorinated aromatic hydrocarbons such as chlorobenzene or dichlorobenzenes or cyclic carbonates such as ethylene or Propylene carbonate. It is also possible to use thionyl chloride itself to use as a solvent, which is distilled at the end of the reaction tiv separated and reintroduced into the process can.
Die Reaktion wird im allgemeinen bei Normaldruck oder bei 1 bis 10 bar Druck durchgeführt.The reaction is generally at normal pressure or at 1 to 10 bar pressure carried out.
Die nachfolgenden Beispiele sollen das Verfahren weiter erläu tern.The following examples are intended to explain the process further tern.
In einer Rührapparatur bestehend aus einem 1,6 l Doppelmantel reaktor mit aufgesetzter Intensivkühlungskaskade wurden jeweils X mol Phthalid zusammen mit dem jeweiligen Katalysatorsystem vorge legt. 1,3 Äqivalente Thionylchlorid bezogen aufs Phthalid wurden entweder mit den anderen Komponenten vorgelegt oder während des Zeitraums von 1 bis 8 Stunden zugetropft. Danach ließ man 1 bis 15 Stunden bei Reaktionstemperatur nachrühren. Der Wertgehalt der Rohmischung wurde per GC ermittelt. In ausgewählten Beispielen wurde das Produkt bei 0,5 mbar und 75 bis 85°C durch fraktionierte Destillation isoliert.In an agitator consisting of a 1.6 l double jacket reactors with an attached intensive cooling cascade were each X mole of phthalide together with the respective catalyst system sets. 1.3 equivalents of thionyl chloride based on phthalide were either submitted with the other components or during the Dropped from 1 to 8 hours. Then left 1 to Stir at reaction temperature for 15 hours. The value of the Raw mixture was determined by GC. In selected examples the product was fractionated at 0.5 mbar and 75 to 85 ° C Distillation isolated.
268 g (2 mol) Phthalid, 12,4 g (0,2 mol, 10 mol%) Borsäure und 45,4 g (0,2 mol, 10 mol%) Benzyltriethylammoniumchlorid wurden im Rührbehälter vorgelegt und auf 130°C erwärmt. Zu dieser Schmelze wurden innerhalb von 5 Stunden 310 g (2,6 mol) Thionylchlorid zu getropft. Anschließend wurde noch 5 Stunden bei 130°C nachgerührt. Der Reaktionsaustrag enthielt 97 GC-Flächen-% o-Chlormethylben zoylchlorid. 268 g (2 mol) phthalide, 12.4 g (0.2 mol, 10 mol%) boric acid and 45.4 g (0.2 mol, 10 mol%) of benzyltriethylammonium chloride were added in Stirring vessel submitted and heated to 130 ° C. To this melt 310 g (2.6 mol) of thionyl chloride were added within 5 hours dripped. The mixture was then stirred at 130 ° C for 5 hours. The reaction discharge contained 97 GC area% o-chloromethylbene zoyl chloride.
670 g (5 mol) Phthalid, 9,3 g (0,15 mol, 3 mol%) Borsäure und 34,1 g (0,15 mol, 3 mol%) Benzyltriethylammoniumchlorid wurden im Rührbehälter vorgelegt und auf 130°C erwärmt. Zu dieser Schmelze wurden innerhalb von 5 Stunden 774 g (6,5 mol) Thionylchlorid zu getropft. Anschließend wurde noch 5 Stunden bei 130°C nachgerührt. Nach Destillation des Reaktionsaustrags wurden 940 g (99,4% Aus beute) o-Chlormethylbenzoylchlorid in einer Reinheit von 98,1% (GC) erhalten.670 g (5 mol) phthalide, 9.3 g (0.15 mol, 3 mol%) boric acid and 34.1 g (0.15 mol, 3 mol%) of benzyltriethylammonium chloride were added in Stirring vessel submitted and heated to 130 ° C. To this melt 774 g (6.5 mol) of thionyl chloride were added within 5 hours dripped. The mixture was then stirred at 130 ° C for 5 hours. After distillation of the reaction product, 940 g (99.4% Aus loot) o-chloromethylbenzoyl chloride in a purity of 98.1% (GC) received.
Claims (4)
in der R1 bis R4 gleich oder verschieden sein können und für Wasserstoff, C1-C4-Alkyl, Halogen oder Trifluormethyl stehen, durch Umsetzung von benzokondensierten Lactonen der Formel II,
in der R1 bis R4 die vorgenannte Bedeutung besitzen, mit Thio nylchlorid,
dadurch gekennzeichnet, daß man die Umsetzung in Gegenwart katalytischer Mengen von Borsäure oder Lewis-saurer Aluminiumsilikate und katalytischer Mengen eines quartären Ammoniumsalzes durchführt.1. Process for the preparation of o-chloromethylbenzoic acid chlorides of the formula I,
in which R 1 to R 4 can be the same or different and represent hydrogen, C 1 -C 4 alkyl, halogen or trifluoromethyl, by reacting benzofused lactones of the formula II,
in which R 1 to R 4 have the abovementioned meaning, with thio nyl chloride,
characterized in that the reaction is carried out in the presence of catalytic amounts of boric acid or Lewis acidic aluminum silicates and catalytic amounts of a quaternary ammonium salt.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999158758 DE19958758A1 (en) | 1999-12-07 | 1999-12-07 | Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts |
| PCT/EP2000/011810 WO2001042182A2 (en) | 1999-12-07 | 2000-11-27 | Method for producing o-chloromethyl benzoic acid chlorides |
| BR0016216-7A BR0016216A (en) | 1999-12-07 | 2000-11-27 | Process for preparing 0-chloromethylbenzoyl chlorides |
| DK00987303T DK1235780T3 (en) | 1999-12-07 | 2000-11-27 | Process for the preparation of o-chloromethylbenzoic acid chlorides |
| US10/130,825 US6727385B1 (en) | 1999-12-07 | 2000-11-27 | Method for producing o-chloromethyl benzoic acid chlorides |
| ES00987303T ES2215780T3 (en) | 1999-12-07 | 2000-11-27 | PROCEDURE FOR OBTAINING O-CHLOROMETILBENZOIL CHLORIDES. |
| EP00987303A EP1235780B1 (en) | 1999-12-07 | 2000-11-27 | Method for producing o-chloromethyl benzoic acid chlorides |
| AT00987303T ATE259770T1 (en) | 1999-12-07 | 2000-11-27 | METHOD FOR PRODUCING O-CHLOROMETHYLBENZOIC ACID CHLORIDES |
| DE50005355T DE50005355D1 (en) | 1999-12-07 | 2000-11-27 | METHOD FOR THE PRODUCTION OF O-CHLORMETHYLBENZOESOIC ACID CHLORIDES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999158758 DE19958758A1 (en) | 1999-12-07 | 1999-12-07 | Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19958758A1 true DE19958758A1 (en) | 2001-07-05 |
Family
ID=7931594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1999158758 Withdrawn DE19958758A1 (en) | 1999-12-07 | 1999-12-07 | Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19958758A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120310010A1 (en) * | 2005-12-01 | 2012-12-06 | Basf Se | Method for producing sulfonamides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999016743A1 (en) * | 1997-09-30 | 1999-04-08 | Korea Research Institute Of Chemical Technology | A PROCESS FOR PREPARING o-(CARBOALKOXY) PHENYLMETHANESULFONYL CHLORIDE DERIVATIVES |
-
1999
- 1999-12-07 DE DE1999158758 patent/DE19958758A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999016743A1 (en) * | 1997-09-30 | 1999-04-08 | Korea Research Institute Of Chemical Technology | A PROCESS FOR PREPARING o-(CARBOALKOXY) PHENYLMETHANESULFONYL CHLORIDE DERIVATIVES |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120310010A1 (en) * | 2005-12-01 | 2012-12-06 | Basf Se | Method for producing sulfonamides |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0543249B1 (en) | Method for the preparation of alkylene carbonates | |
| EP0124002B1 (en) | Process for the preparation of aromatic compounds containing perfluorinated side chains linked by a heteroatom | |
| EP1235780B1 (en) | Method for producing o-chloromethyl benzoic acid chlorides | |
| EP0676389B1 (en) | Process for preparing O-chloromethyl benzoic acid chloride | |
| DE19959066C1 (en) | Preparation of ortho-chloromethyl-benzoyl chloride derivatives from phthalide and thionyl chloride, for use as pesticide intermediate, using boron trifluoride dihydrate and quaternary ammonium catalysts | |
| EP1265837B1 (en) | Method for producing o-chloromethyl benzoic acid chlorides | |
| DE19958758A1 (en) | Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts | |
| EP0505874B1 (en) | Process for the preparation of para-dichlorobenzene | |
| DE10007695A1 (en) | Production of o-chloromethylbenzoyl chlorides from benzo-condensed lactone, useful as intermediates for e.g. pesticides, uses boron compound and quaternary ammonium compound as catalysts | |
| EP1068168B1 (en) | Continuous method for producing propargyl chloride | |
| EP2097366B1 (en) | Method for producing o-chloromethyl benzenecarbonyl chlorides | |
| EP0474074B1 (en) | Process for preparing dichlorobenzene with high content of the p-isomer | |
| DE68922353T2 (en) | Nuclear fluorinated aromatic carboxylates and their manufacturing processes. | |
| EP0388870B1 (en) | Process for preparing aliphatic substituted fluorobenzenes | |
| EP0590259B1 (en) | Process for the preparation of halogenated aromatic compounds | |
| EP0136566A2 (en) | Process for the preparation fo 3,4-dichlorobenzene trihalides | |
| EP0023647B1 (en) | Process for the preparation of halogenated benzoyl fluorides | |
| EP0302331B1 (en) | Esters of arylbisperfluoralkylcarbinols, method for the preparation of the same and of the arylbisperfluoralkylcarbinols in question | |
| DE3712610C2 (en) | ||
| DE2743144B2 (en) | Process for the preparation of m-halobenzoyl halides | |
| DE3930839A1 (en) | METHOD FOR PRODUCING P-CHLORTOLUOL | |
| DE19940861C1 (en) | Process for the preparation of 2-chloro-4-nitroalkylbenzene | |
| EP0732316A1 (en) | Process for the catalytic dehydrohalogenation of halogenated hydrocarbons | |
| DE2558522B2 (en) | Process for the continuous production of di-tert-butyl cresols | |
| DE3720391A1 (en) | METHOD FOR THE PRODUCTION OF HALOGENATED BENZOL DERIVATIVES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| 8130 | Withdrawal | ||
| R082 | Change of representative |