IL100531A - Process for the preparation of optically active esters of quinoxalinyloxy-phenoxypropionic acid - Google Patents

Process for the preparation of optically active esters of quinoxalinyloxy-phenoxypropionic acid

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IL100531A
IL100531A IL10053191A IL10053191A IL100531A IL 100531 A IL100531 A IL 100531A IL 10053191 A IL10053191 A IL 10053191A IL 10053191 A IL10053191 A IL 10053191A IL 100531 A IL100531 A IL 100531A
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substituted
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IL10053191A
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Hoechst Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

PROCESS FOR THE PREPARATION OF OPTICALLY ACTIVE ESTERS OF QUINOXALINYLOXYPHENOXYPROPIONIC ACID HOECHST AKTIENGESELLSCHAFT HOE 90/F 391 Dr. WE Process for the preparation of optically active esters of quinoxalinyloxyphenoxypropionic acid The present invention relates to a process for the preparation of optically active esters of D-guinoxalinyl-oxyphenoxypropionic acid of the formula I O in which is H, halogen, preferably chlorine, Cj-C^-haloalkyl, preferably CF3, CN, N02/ preferably CH3 or preferably OCH3, particularly halogen, is H or halogen, preferably H, is C1-C18-alkyl , benzyl, C5-C8-cycloalkyl , C3-C4- alkenyl which is unsubstituted or substituted by one or more halogen atoms, C3-C4-alkynyl which is unsubstituted or substituted by one or more halogen atoms, or (CH2)n(0)mR<, is Ci-Ce-alkyl which is unsubstituted or substituted by Ci-Ce-alkoxy, or is a 5- or 6-membered ring which is saturated or unsaturated, carbocyclic or heterocyclic having 1 to 4 heteroatoms selected from the group comprising oxygen and nitrogen, and unsubstituted or substituted by 1-3 substituents selected from the group comprising oxo, C^-C8-alkyl and Cx-C3-alkoxy, or is a group of the formula N=CR5R6, and R6 are, independently of each other, Ci-Cg-alkyl, C3-C8-cycloalkyl , Ci-Cg-alkylcarbonyloxy- Cj-Cg-alkyl, Cx-Cg-alkoxy, or, together with the carbon atom to which they are bonded, cycloalkyl radical having 3-8 ring members, n is 1 or 2 and m is 0 or 1, which comprises reacting a substituted quinoxaline of the formula II 0 Π III in which Rx and R2 have the same meanings as in formula I and X is a leaving group, such as e.g. halogen, particularly chlorine or bromine, or methanesulfonyl, with a (D) -2-(4-hydroxyphenoxy) propionate of the formula III in which and, if R3 is not identical to R7, transesterifying the resulting lower alkyl ester of the formula IV or of IV completely or substantially without racemization to give the desired compound of the formula I.
Here and hereinafter halogen means fluorine, chlorine, bromine or iodine; alkyl can be straight-chain or branched, the same applying to the unsaturated radicals alkenyl and alkynyl, and the alkyl moieties of the substituted radicals; lower alkyl is Ci-C8-alkyl, herbicides against a great number of weeds of economic significance.
However, in most cases, racemates are employed, although EP-A-2800 discloses that in the class of substituted aryloxy- or heteroaryloxyphenoxypropionic acids, the enantiomers having the D-configuration have considerably higher activity than the L-enantiomers or the racemates . The reduction that this makes in the possible application rate for the same biological effect is highly advant-ageous from both the economic and the ecological viewpoints .
However, the synthesis of optically active compounds of the formula I has hitherto only been described for R3 = H and CH3 (DE-A-3004770 (US-A-4 , 629 , 493 ) ) , R3 = CH2CH3 (J. Pesticide Sci. 1985, 10, 69), R3 = (H3C)2C=N-0-(CH2)n where n = 1 or 2 (EP-A-52798 (US-A-4 , 435 , 207 )) , and R3 = tetrahydrofurfuryl (EP-A-383613) .
Optically active compounds of the formula I have been synthesized hitherto essentially by two processes, that is either by reacting together 2- ( 4-hydroxyphenoxy)quin-oxaline VI and the corresponding L-lactic acid derivatives VII (DE-A-3004770 (US-A-4, 629,493) ; J. Pesticide Sci. 1985, 10, 69; EP-A-52798 (US-A-4 , 435 , 207 )) , or in the case where R3 = tetrahydrofurfuryl (EP-A-383613), by reacting together substituted quinoxalines of the formula II and the specific tetrahydrofurfuryl (D) -2- (4-hydroxyphenoxy)propionate of the formula III in which R7 = tetrahydrofurfuryl.
Both processes have major disadvantages. - 3 - preferably Ci-C-alkyl .
Of particular interest is the process according to the invention in which, in formula I, R3 is C1-Ce-alkyl, benzyl, C5-C6-cycloalkyl, C3-C4- alkenyl, C3-C-alkynyl or (CH2)n(0)mR The transesterification to be carried out where needed following the reaction of the compounds of the formulae II and III is preferably carried out using an alcohol of the formula V R3OH V in which R3 has the same meaning as in formula I, in the presence of a catalyst.
Compounds of the formula I are described e.g. in DE-A-3004770 ( US -A- , 629 , 493 ) , EP-A-042750 (US-A-4 , 609 ,396 ) , EP-A-52798 (US-A-4 , 435 , 207 ) , EP-A-288275 (US-A-4 , 948r421 ) , EP-A-323727 ( ZA-A-88/9732 ) and EP-A-383613, arid are used as selectively active - - herbicides against a great number of weeds of economic significance.
However, in most cases, racemates are employed, although EP-A-2800 discloses that in the class of substituted aryloxy- or heteroaryloxyphenoxypropionic acids, the enantiomers having the D-configuration have considerably higher activity than the L-enantiomers or the racemates. The reduction that this makes in the possible application rate for the same biological effect is highly advant-ageous from both! the economic and the ecological viewpoints .
However, the synthesis of optically active compounds of the formula I has hitherto only been described for R3 = H and CH3 (DE-A-3004770 (US-A-4 , 629 , 493 ) ) , R3 = CH2CH3 (J. Pesticide Sci. 1985, 10, 69), R3 = (H3C)2C=N-0-(CH2)n where n = 1 or 2 (EP-A-52798 (US-A-4 , 435 , 207 )) , and R3 = tetrahydrofurfuryl (EP-A-383613) .
Optically active compounds of the formula I have been synthesized hitherto essentially by two processes, that is either by reacting together 2-(4-hydroxyphenoxy)quin-oxaline VI and the corresponding L-lactic acid derivatives VII (DE-A-3004770 (US-A-4 , 629 , 493 ) ; J. Pesticide Sci. 1985, 10, 69; EP-A-52798 (US-A-4 , 435 , 207 )) , or in the case where R3 = tetrahydrofurf ryl (EP-A-383613), by reacting together substituted quinoxalines of the formula II and the specific tetrahydrofurfuryl (D)-2-(4-hydroxyphenoxy)propionate of the formula III in which R7 = tetrahydrofurfuryl.
VII - 4a - Two similar processes are described in US-A-4687849 with respect to the preparation of 2- ( isopropylidenoaminooxyl ) -ethyl D-2- ( 4- ( 6-chloro-chinoxalinyloxy) -phenoxy) -propionate . In one variant 2- ( isopropylidenoaminooxy) -ethyl D-2-halogeno- or D-2-tosyloxy-propionate is reacted with 4-(6-chloroquinoxalinyloxy ) -phenole . In the other variant 2,6-dichloro-quinoxaline is reacted with 2- ( isopropylidenamino-oxy) -ethyl D-2- ( 4 -hydroxyl-phenoxy) -propionate in an aprotic dipolar solvent. Both types of processes have major disadvantages . - 5 - Thus, for example, compounds of the formula VI are only obtainable by multiple-step syntheses involving removal of protecting groups, such as, for example, the benzyl group. Since partial racemization occurs during the reaction of VI with VII, the optical purity of the compounds of the formula I prepared in this manner is usually not higher than 79% (J. Pesticide Sci. 1985, 10, 69) .
The reaction of the compounds of the formula II with compounds of the formula III in which R7 is tetrahydro-furfuryl does lead to products of higher optical purity, but has the disadvantage that only compounds of the formula I where R3 = tetrahydrofuryl can be obtained, so that the range of variation of the ester function is very small. Furthermore, the preparation of compounds of the formula III in which R7 = tetrahydrofuryl is also a complex, multi-step process (EP-A 383613).
Compounds of the formula III where R7 = C1-C4-alkyl are, by contrast, intermediates available in large amounts, and their preparation is described in e.g.
JP-A-62/178543.
Because of the disadvantages of the known processes mentioned, the process according to the invention constitutes a major technical advance. It allows the whole range of variations of compounds of the formula I to be prepared, on the basis of compounds of the formula III, via an easily synthesizable intermediate, in high optical purity.
Reaction of the compounds of the formula II with the compounds of the formula III is preferably carried out in a non-polar, organic solvent in the presence of an acid-binder, and with or without addition of a catalyst.
Non-polar, organic solvents are taken to mean hydrocarbons which are liquid at room temperature, and - 6 - which may also be halogen-containing, such as e.g. heptane, toluene, xylene, cumene, mesitylene, chlorobenzene or the isomeric dichlorobenzenes .
The acid-binders used are generally organic and inorganic bases, but inorganic bases are preferred. Particular preference is given to alkali metal carbonates or alkali metal hydrogen carbonates, particularly those of sodium and those of potassium. Alkali metal hydrogen carbonates eliminate water above about 90 °C. To avoid hydrolytic side reactions, it is therefore advantageous, when using alkali metal hydrogen carbonates above these reaction temperatures , to remove water from the reaction by appropriate measures, such as e.g. azeotropic distillation or addition of a physical drying agent, such as e.g. a molecular sieve. The same measures are recommended when using alkali metal carbonates above about 90 °C, since alkali metal hydrogen carbonates are formed from these by neutralization during the reaction.
To achieve complete conversion in the abovementioned non-polar solvents, it may be useful under certain circumstances to add a catalyst.
Suitable catalysts are quaternary ammonium or phosphonium salts, polyalkylene glycols and their lower alkyl ethers. Catalyst systems of this type are described in detail in EP-A-105494. Other suitable catalysts are crown ethers, such as e.g. 15-crown-5 or 18-crown-6 (Aldrich Chimica Acta 1976 (1), 3) or acyclic cryptands such as TDA-1 (J. Org. Chem. 1985, 50, 3717).
Long-chain polyalkylene glycols having molecular weights between 1000 and 3000 are preferably used because of the better phase separation during the aqueous work-up.
The catalysts are preferably used in amounts of 0.05 to 1.0 mol%, particularly in amounts of 0.1 to 0.7 mol%, relative to the compound of the formula II.
The process according to the invention is preferably carried out in the temperature range from 30 °C to 150 °C, particularly in the range from 80 eC to 120 °C. The order of addition of the reactants is generally not critical.
The process is carried out, for example, by mixing together the reactants of the formulae II and III in the desired solvent, adding the catalyst if required, and heating the whole reaction mixture to the desired reaction temperature. The point in time at which complete conversion is reached may be determined by commonly-used methods, e.g. by thin layer chromatographic (TLC) or gas chromatographic (GC) analysts of the reaction mixture.
To achieve complete conversion of the component of the formula II, it is advisable to use a slight excess of the component of the formula III. The excess of component III relative to component II is preferably 1 to 10 mol%, particularly 1.5 to 5 mol%, and can easily be removed when the reaction is completed by washing with dilute alkali metal hydroxide solution or a phosphate buffer solution.
After the solvent has been distilled off, the end products or intermediates of the formula I where R3 = R7 or formula IV are generally obtained in yields of over 90% of theory and in optical purities of 90%. They can, as required, either be isolated or be directly transesterified without further purification to give other compounds of the formula I . Transesterification as free as possible from racemization is preferably carried out as follows: The intermediate of the formula IV is dissolved in, for example, a 2 to 100-fold excess of the alcohol of the formula V, preferably in a 2 to 50-fold excess, and, after addition of a catalyst, heated to 80 °C to 120 °C. The reaction mixture can optionally be diluted by addition of an inert solvent. - 8 - The catalysts used can be titanium( IV) tetraalkoxides , as described in Synthesis 1982, 138. Particularly suitable for this are titanium( IV) ethylate, titanium( IV) iso-propylate and titanium( IV) butylate. The amount of cata-lyst used is, for example, 2 to 50 mol% relative to the intermediate of the formula IV.
The point in time at which complete conversion is reached may be determined by commonly-used methods, e.g. TLC or GC. Prior to work-up, the alcohol component of the formula V used in excess can be recovered e.g. by distillation.
Taking up the reaction mixture after the transesterifi-cation into dilute hydrochloric acid destroys the titanium( IV) alkoxides , and the product of the formula I can subsequently be isolated by extraction into an organic solvent, e.g. from the group of solvents that may be used in the reaction of the compounds of the formulae II and III. The crude product obtained in this manner can, if required, be further purified by measures such as recrystallization or chromatography.
To avoid side reactions due to atmospheric oxygen or moisture, the process according to the invention is preferably carried out under a protective gas atmosphere. Protective gases that may be used are nitrogen or argon.
The optical yields of the compounds of the formula I obtained by the process according to the invention, including transesterification, are in general over 85%, corresponding to an approximate 85% enantiomeric excess.
Example 1 Ethyl (D)-2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]propio-nate 5.00 g (25 mmol) of 2,6-dichloroquinoxaline, 5.40 g - 9 - (25.8 mmol) of ethyl (D)-2-(4-hydroxyphenoxy)propionate (optical purity: 90.2%) and 3.50 g (25 mmol) of potassium carbonate are suspended in 15 ml of xylene, and, after addition of 0.3 g (0.15 mmol) of polyethylene glycol (mean molecular weight 2000), are heated for 6 hours under nitrogen to 95 °C over a water separator. After this time, no remaining 2 , 6-dichloroquinoxaline is detectable in the thin layer chromatogram. The reaction mixture is cooled to room temperature and filtered, and the filtrate is concentrated in vacuo. 8.49 g (91.1% of theory) of ethyl ( D) -2- [ 4- ( 6-chloro-2-quinoxalinyloxy)phenoxy]propionate are obtained as a beige solid.
[Q]d20 5 = 29.43° (c = 1.15, CHC13) Relative to [ ]D20 = 35.9° (c = 1.20, CHC13) for optically pure material (J. Pesticide Sci. 1985, 10, 75), this corresponds to an optical purity of 82%.
If the optical purity of the ethyl (D)-2-(4-hydroxyphen-oxy) propionate used as starting material (90.2%) is taken into account, ethyl (D)-2-[4-(6-chloro-2-quinoxaliny-loxy) phenoxy]propionate would be obtained in an optical purity of 90.9% from 100% pure ethyl (D) -2- ( 4-hydroxy-phenoxy) propionate .
Example 2 ( + ) -Tetrahydrofurfuryl ( D) -2- [ 4- ( 6-chloro-2-quinoxaliny-loxy)phenoxy]propionate 3.73 g (10 mmol) of ethyl (D)-2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]propionate (from example 1) and 1.14 g (4 mmol) of titanium( IV) isopropylate are dissolved in 50 g (48.9 mmol) of (±) -tetrahydrofurfuryl alcohol and heated for 11 hours to 105 °C. After this time no remaining starting material can be detected by thin layer chromatography. After cooling to room temperature, 20 ml of 1 N HC1 are added to the reaction mixture, and the - 10 - product is extracted by shaking with 100 ml of toluene. The toluene phase is washed once with 20 ml of saturated sodium hydrogen carbonate solution and once with 20 ml of water. After drying over magnesium sulfate and elimina-tion of the solvent in vacuo, 3.8 g (88.6% of theory) of ( ± ) -tetrahydrofurfuryl (D) -2- [4- ( 6-chloro-2-quinoxalinyl-oxy)phenoxy]propionate are obtained as a light-brown oil.
[Q]d20 = 27.3° (c = 2.34, CHC13) ^-NMR (CDC13) 6 1.41-2.12 (m, 4, CHCH2CH2CH20) , 1.65 (d, 3, J = 7 Hz, OCHCH3COO), 3.61-4.01 (m, 2, 0CH2CH0) , 4.01-4.40 (m, 3, 0CH2CH0CH2CH2CH2) , 4.82 (q, 1, J = 7 Hz, OCHCH3COO), 6.84-7.25 (m, 4, aromatic), 7.48-7.77 (m, 2, aromatic), 8.02 (d, 1, J = 2.5 Hz, aromatic), 8.65 (s, 1, aromatic ) .

Claims (14)

1. - 11 - HOE 90/F 391 Patent claims: A process for the preparation of an optically active ester of D-quinoxalinyloxyphenoxypropionic acid of the formula I 0 in which is H, halogen, CN, N02, Ci-C*,- alkyl or C1-C4-alkoxy, is H or halogen, is Ci-Cie- lkyl, benzyl, C5-Ce-cycloalkyl, C3-C4- alkenyl which is unsubstituted or substituted by one or more halogen atoms, C3-C4-alkynyl which is unsubstituted or substituted by one or more halogen atoms, or (CH2)n(0)mR4, is Ci-Ce-alkyl which is unsubstituted or substituted by Ci-Cg-alkoxy, or is a 5- or 6-membered ring which is saturated or unsaturated, car- bocyclic or heterocyclic having 1 to 4 hetero- atoms selected from the group comprising oxygen and nitrogen, and unsubstituted or substituted by 1-3 substituents selected from the group comprising oxo, Ci-Ca-alkyl and Ci-Cg-alkoxy, or is a group of the formula N=CR5R6, and R6 are, independently of each other, Ci-Cg-alkyl, C3-C8-cycloalkyl, Cj-Ce-alkylcarbonyl- oxy-Ci-Cg-alkyl , C^-Ce-alkoxy, C^-Ce-alkylthio or, together with the carbon atom to which they are bonded, a cycloalkyl radical having 3-8 ring members , is 1 or 2 and is 0 or 1, - 12 - 100531/2 which comprises reacting a substituted quinoxaline of the formula II O in which Rx and R2 have the same meanings as in formula I and X is a leaving group, such as e.g. halogen, particularly chlorine or bromine, or methanesulfonyl, with a (D)-2-(4-hydroxy- phenoxy) ropionate of the formula III in which R7 is C^-C^-alkyl, in a non-polar organic solvent, and, if R3 is not identical to R7, transesterifying the resulting lower alkyl ester of the formula IV or IV completely or substantially without racemization to give the desired compound of the formula I.
2. The process as claimed in claim 1, wherein R, is C^-Ce-alkyl, benzyl, C5-C6-cycloalkyl , C3-C4- alkenyl, C3-C«-alkynyl or (CH2)n(0)mR4, R. is Ci-C-alkyl, or a 5- or 6-membered saturated or unsaturated ring which is carbocyclic or heterocyclic having 0 to 3 oxygen atoms and 0 to 2 nitrogen atoms as ring atoms and at most 3 ring heteroatoms and is unsubstituted or substituted by 1-3 substituents - 13 - 100531/2 selected from the group comprising oxo, methyl, ethyl, n- and i-propyl, methoxy, ethoxy, n- and i-propoxy and N=CR5R6, R5 and R6 are, independently of each other, together with the carbon atom to which they are bound, a cycloalkyl radical having 5-6 ring members , n is 1 or 2 and m is 0 or 1.
3. The process as claimed in claim 1 or 2 , wherein the non-polar organic solvent is selected from the group consisting of hydrocarbons which are liquid at room temperature and which may also be halogen-containing.
4. The process as claimed in one or more of claims 1-3, wherein the solvent used is heptane, toluene, xylene, cumene, mesitylene, chlorobenzene or an isomeric dichlorobenzene .
5. The process as claimed in one or more of claims 1-4, wherein the reaction of compound II with compound III is carried out in the presence of an acid-binder.
6. The process as claimed in claim 5, wherein the acid-binder used is an alkali metal carbonate or alkali metal hydrogen carbonate.
7. The process as claimed in one or more of claims 1-6, wherein the reaction of compound II with compound III is carried out in the presence of a catalyst selected from the group comprising quaternary ammonium or phosphonium salts, polyalkylene glycols and their lower alkyl ethers, crown ethers and acyclic cryptands .
8. The process as claimed in claim 7, wherein the catalyst used is a long-chain polyalkylene glycol having - 14 - a mean molecular weight between 1000 and 3000.
9. The process as claimed in claim 7 or 8, wherein the catalyst is used in an amount of 0.05 to 1.0 mol%, relative to the compound of the formula II.
10. The process as claimed in one or more of claims 1-9, wherein the reaction of the compound of the formula II with the compound of the formula III is carried out at 30°C to 150°C.
11. The process as claimed in one or more of claims I-10 wherein the intermediate of the formula IV mentioned is transesterified using a 2- to 100-fold excess of the alcohol of the formula R3OH in which R3 has the meaning mentioned.
12. The process as claimed in claim 11, wherein the transesterification is carried out in the presence of a catalyst selected from the group comprising the titanium( IV) tetraalkoxides .
13. The process as claimed in claim 12, wherein the catalyst is used in an amount of 2 to 50 mol% relative to the component of the formula IV.
14. The process as claimed in one or more of claims II-13, wherein the transesterification is carried out at 80°C to 120°C.
IL10053191A 1990-12-28 1991-12-26 Process for the preparation of optically active esters of quinoxalinyloxy-phenoxypropionic acid IL100531A (en)

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DE4042098A DE4042098C2 (en) 1990-12-28 1990-12-28 Process for the preparation of optically active quinoxalinyloxy-phenoxypropionic acid esters

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IL100531A0 IL100531A0 (en) 1992-09-06
IL100531A true IL100531A (en) 1996-03-31

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CN102584803B (en) * 2012-01-19 2014-12-10 江苏丰山集团有限公司 Preparation method of high-content quizalofop-P-tefuryl
CN105461643A (en) * 2015-12-18 2016-04-06 京博农化科技股份有限公司 Preparing method of quizalofop-p-ethyl preparation

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AU6540490A (en) * 1989-10-05 1991-04-28 Hoechst Aktiengesellschaft Herbicidal, heterocyclically substituted phenoxyalkane carboxylic acid derivatives and process for preparing them

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CA2058320A1 (en) 1992-06-29
AU653376B2 (en) 1994-09-29
EP0492629A3 (en) 1993-01-13
DE4042098C2 (en) 1993-10-07
HU914124D0 (en) 1992-03-30
DE4042098A1 (en) 1992-07-02
DE59106542D1 (en) 1995-10-26
ZA9110055B (en) 1992-09-30
HU208682B (en) 1993-12-28
AU9008091A (en) 1992-07-02
KR920012048A (en) 1992-07-25
EP0492629A2 (en) 1992-07-01
HUT61291A (en) 1992-12-28
JPH04295469A (en) 1992-10-20
EP0492629B1 (en) 1995-09-20
IL100531A0 (en) 1992-09-06
BR9105529A (en) 1992-09-01

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