AU653376B2 - Process for the preparation of optically active esters of quinoxalinyloxyphenoxypropionic acid - Google Patents
Process for the preparation of optically active esters of quinoxalinyloxyphenoxypropionic acid Download PDFInfo
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- AU653376B2 AU653376B2 AU90080/91A AU9008091A AU653376B2 AU 653376 B2 AU653376 B2 AU 653376B2 AU 90080/91 A AU90080/91 A AU 90080/91A AU 9008091 A AU9008091 A AU 9008091A AU 653376 B2 AU653376 B2 AU 653376B2
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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
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- 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
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- 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
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description
Regulation 3,2(2)
AUSTRALIA
Patents Act 1990 65337 ORIGiNAL COMPLETE SPECIFICATION STANDARD PATENT sea* 00 0 0 Application Number: Lodged: 00 0. 0 Invention Title: PROCESS MOR THE PREPARATION OF OPTICALLY ACTIVE ESTERS OF QUINOXALINYLOXYP-' NOXYPROPIONIC ACID The following statement is a full description of this invention, including the best method of performing it known to Us I 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-quinoxalinyloxyphenoxypropionic acid of the formula I 0 o R, N O
R
3 2 N ECH3 in which I be 0 R, is H, halogen, preferably chlorine, Cl-C 4 -haloalkyl, preferably CF,, CN, NO 2
C
1
-C
4 -alkyl, preferably CH, or C 1
-C
4 -alkoxy, preferably OCH 3 particularly "coo halogen, Rz is H or halogen, preferably H,
R
3 is C 1 -Cl.-alkyl, benzyl, C-C,-cycloalkyl, C 3
-C
4 :alkenyl which is unsubstituted or substituted by one or more halogen atoms, C 3
-C
4 -alkynyl which is unsubstituted or substituted by one or more halogen 0* atoms, or (CH 2 )n(O),R 4 0 0
R
4 is C-C 6 -alkyl which is unsubstituted or substituted by C-C.-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, Cl-C 3 -alkyl and Cl-C 3 -alkoxy, or is a group of the formula
N=CR
5
R
6 R, and R 5 are, independently of each other, Cl-C 6 -alkyl, C 3
-C
8 -cycloalkyl, Cl-C 6 -alkylcarbonyloxy- C,-C.-alkyl, Cl-C 6 -alkoxy, C 1
-C
6 -alkylthio or, together 2 with the carbon atom to which they are bonded, a 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 N
CH
3 II
III
in which RI and R 2 have the same meanings as in formula I and O*L 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
R
7 is Ci-C 4 -alkyl, 5 and, if R 3 is not identical to R 7 transesterifying the resulting lower alkyl ester of the formula IV or of eS formula I in which R 3
=R
7 0 R 1 N 0 )C
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-C 6 -alkyl, -3preferably Cl-C 4 -alkyl.
Of particular interest is the process according to the invention in which, in formula I,
R
3 is Cl-C-alkyl, benzyl, C 5
-C
6 -cycloalkyl, C 3
-C
4 alkenyl, C 3
-C
4 -alkynyl or 4 preferably
C.-C
4 -alkyl, CH 2
CH
2 ON=C (CH 3 2 or tetrahydrofurfuryl,
R
4 is Cl-C-alkyl, (Cj-Cr,-alkoxy)C 1
-C
4 -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 sub- *GSS stituted by 1-3 substituents selected from the group comprising oxo, methyl, ethyl, n- and i-propyl, oose methoxy, ethoxy, n- and i-propoxy and N=CR 5
R.,
R
5 and R. are, independently of each other, Cl-C 4 -alkyl, C 5
-C
6 -cycloalkyl, Cl-C 4 -alkylcarbonyloxy-
C,-C
4 -alkyl, C,-C 4 -alkoxy, C,-C-alkylthio or, together with the carbon atom to which they are bound, a cycloalkyl radical having 5-6 ring members, n isl1or 2and m is 0ori1.
: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 *0 R 3 0H
V
in which R 3 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-4,629,493), EP-A-042750 (US-A-4,609,396), EP-A-52798 (US-A-4,435,207), EP-A-288275 (US-A-4,948,421), EP-A-323727 (ZA-A-88/9732) and EP-A-383613, and are used as selectively active -4 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 advantageous 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 R 3 H and CH 3 (DE-A-3004770 (US-A-4,629,493)), R 3
CH
2
CH
3
(J.
15 Pesticide Sci. 1985, 10, 69), R 3
(H
3
C)
2
C=N-O-(CH
2 )n where Sn 1 or 2 (EP-A-52798 (US-A-4,435,207)), and R 3 tetrahydrofurfuryl (EP-A-383613).
Optically active compounds of the formula I have been synthesized hitherto essentially by two processes, that :20 is either by reacting together 2-(4-hydroxyphenoxy)quinoxaline 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 R 3 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 R 7 tetrahydrofurfuryl.
RI N OH 0 O X R3 R 2 0CH 3 VI VII Both processes have major disadvantages.
I
5 Thus, for example, compounds of the formula VI are only obtainable by multiple-step syntheses involving removrl 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% Pesticide Sci. 1985, 69).
The reaction of the compounds of the formula II with compounds of the formula III in which R 7 is tetrahydro- 0 furfuryl does lead to products of higher optical purity, but has the disadvantage that only compounds o.r the formula I where R 3 tetrahydrofuryl can be obtained, so that the range of variation of the ester function is very :15 small. Furthermore, the preparation of compounds of the formula III in which R 7 tetrahydrofuryl is also a complex, multi-step process (EP-A 383613).
Compounds of the formula III where R 7 Ci-C 4 -alkyl are, by contrast, intermediates available in large amounts, *"20 and their preparation is described in e.g.
JP-A-62/178543.
09 Because of the disadvantages of the known processes mentioned, the process according to the invention constitutes a major technical advance. It allows the whole 25 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 0 C. To avoid hydrolytic side reactions, it is therefore advantageous, when using alkali metal hydrogen carbonates above these reaction 0° temperatures, to remove water from the reaction by 4' 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 3) or acyclic cryptands such as TDA-1 (J.
Org. ChemL 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 mol%, particularly in amounts of 0.1 to 0.7 mol%, relative to the compound of the formula II.
7 The process according to the invention is preferably carried out in the temperature range from 30 0 C to 150 0
C,
particularly in the range from 80 0 C to 120 0 C. The order of addition of the reactants is generally not critical.
The process is carri3d 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.
0 C To achieve complete conversion of the component of the formula II, it is advisable to use a slight excess of the .15 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.
0* After the solvent has been distilled off, the end products or intermediates of the formula I where R 3
R
7 or formula IV are generally obtained in yields of over 90% of theory and in optical purities of 90%. They can, 25 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 0
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)isopropylate and titanium(IV)butylate. The amount of catalyst 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. PrI'. r to work-up, the alcohol component of the formula V used in excess can be recovered e.g. by .00 distillation.
0 00 Taking up the reaction mixture after the transesterification 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 .oo* III. The crude prodct obtained in this manner can, if required, be further purified by measures such as recrystallization or chromatography.
o* To avoid side reactions due to atmospheric oxygen or 0 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 corresponding to an approximate 85% enantiomeric excess.
Example 1 Ethyl (D)-2-[4-(6-chloro-2-quinoxalinyloxy)phenoxy]propionate 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 a;e 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-chlo .)-2-quinoxalinyloxy)phenoxy]propionate are obtained as a beige solid.
0*2.
29.430 (c 1.15, CHC1 3 0 Relative to [a]D 20 35.90 (c 1.20, CHC13) for optically o :15 pure material Pesticide Sci. 1985, 10, 75), this corresponds to an optical purity of 82%.
If the optical purity of the ethyl (D)-2-(4-hydroxyphenoxy)propionate used as starting material is taken into account, ethyl (D)-2-[4-(6-chloro-2-quinoinoxalinyloxy)phenoxy]propionate would be obtained in an optical purity of 90.9% from 100% pure ethyl (D)-2-(4-hydroxyphenoxy)propionate.
S
Example 2 (±)-Tetrahydrofurfuryl (D)-2-[4-(6-chloro-2-quinoxalinyloxy)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 onc~ 4th 20 hil of water. After drying over magnesium sulfa,'-,_ and elimination of the solvent in vacuo, 3.8 g (88.6% of theory) of -tetrahydrofurfuryl (6-chloro-2-quinoxalinyloxy)phenoxy)propionate are obtained as a light-brown oil.
IaD0= 27.30 (c 2.34, CHC1 3 'H-NMR (CDC1 3 6 1.41-2.12 (in, 4, CHCH 2
CII
2
CH
2 1.65 (d, 3, J 7 Hz, OCHCH 3 COO), 3.61-4.01 (mn, 2, OCH 2
CHO),
4.01-4.40 (in, 3, OCH 2
CHOCH
2
CH
2
CH
2 4.82 1, J =7 Hz, 0 OCHCH 3 COO), 6.84-7.25 (in, 4, aromatic), 7.48-7.77 (in, 2, *aromatic), 8.02 1, J =2.5 Hz, aromatic), 8.65 1, aromatic).
OS 0 00
Claims (14)
1. A process for the preparation of an optically active ester of D-guinoxalinyloxyphenoxypropionic acid of the formula I 0 RN 0R 3 N CH, R N 0 in which R, is H, halogen, C-C 4 -haloalkyl, CN, NO 2 C3,-C 4 o alkyl or Cl-C 4 -alkoxy, .00R 2 is H or halogen, R, is Cl-C.-alkyl, benzyl, Cs-C 8 -cycloalkyl, C.-C 4 alkenyl which is unsubstituted or substituted by one or more halogen atoms, C,-C 4 -alkynyl which is 0:...:unsubstituted or substituted by one or more halogen atoms, or (CH 2 ).(O)mR 41 R 4 is Cl-C 6 -allvyl which is unsubstituted or sub- stituted by Cl-C 6 -alkoxy, or is a 5- or 6-membered ring which is saturated or unsaturated, car- bocyclic or heterocyclic having 1 t~o 4 hetero- atoms selected from the group G ~'4goxygen 20 and nitrogen, and unsubstituted or substitutdby 001-3 substituents selected from the grouppi OXO, Cl-C 3 -alkyl and Cl-C-alkoxy, or is a group of the formula R 5 and R. are, independently of each other, C 1 -C 6 -alkyl, C 3 -CB-CYCloalkyl, Cl-Cr 5 -alkylcarbonyl- oxy-Cl-Cr,-alkyl, Cl-C 6 -alkoxy, Cl-C-alkylthio or, together with the carbon atom to which they are bonded, a cycloalkyl radical having 3-8 ring members, n is 1or 2and 0in is 0or 1, 12 which comprises reacting a substituted quinoxaline of the formula II 0 R-U I CH 3 II III in which RI and R 2 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- Sphenoxy)propionate of the formula III in which 4 p. ,*10 R 7 is Ci-C 4 -alkyl, and, if R 3 is not identical to transesterifying the resulting lower alkyl ester of the formula IV or of formula I, in which R 3 =R 7 BO a N 1 N SR2 N 0 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 3 is C 1 -C.-alkyl, benzyl, Cs-C-cycloalkyl, C
3 -C 4 alkenyl, C 3 -C 4 -alkynyl or (CH 2 )n(0),R
4 R 4 is C 1 -C 4 -alkyl, (Ci-C-alkoxy)C-C 4 -alkyl, or a 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 selected from the group G\goxo, methyl, ethyl, n- and i-propyl, methoxy, ethoxy, n- and i-propoxy and N=CR 5 R 6 R 5 and Re are, independently of each other, C 1 -C 4 -alkyl, Cs-C-cycloalkyl, Ci-C 4 -alkylcarbonyl- oxy-Ci-C 4 -alkyl, C 1 -C 4 -alkoxy, Ci-C 4 -alkylthio or, 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. S3. The process as claimed in claim 1 or 2, wherein the reaction of compound II with compound III is carried out in a non-polar, organic solvent. :'15 4. The process as claimed in\one er-m4a 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 -e es of claims 1-4, wherein the reaction of compound II with compound III is carried out in the presence of an acid-binder. 4 a
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 inone eg-mes 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 emrcg\ 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 cata- /0 lyst 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 oa-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 0 C to 150°C.
11. The process as claimed in one e-m\sa of claims 6 10 1-10, wherein the intermediate of the formula IV mentioned is transesterified using a 2- to 100-fold e0 t excess of the alcohol of the formula R30H in which R 3 has the meaning mentioned. -00) oo*
12. The process as claimed in claim 11, wherein the transesterification is carried out in the .presence of a catalyst selected from the group omp6R e the titanium(IV)tetraalkoxides. S"
13. The process as claimed in claim 12, wherein the catalyst is used in an amount of 2 to 50 mol% ,20 relative to the component of the formula IV.
14. The process as claimed in one .e--moe- of claims 11-13, wherein the transesterification is carried S out at 80 0 C to 120"C. DATED this 23rd day of December 1991. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS "THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122. HOE 90/F 391 Abstract Process for the preparation of optically active esters of quinoxalinyloxyphenoxypropionic acid The invention relates to a process for the preparation of optically active esters of (D)-2-[4-(quinoxalinyloxy)phenoxy]propionic acid of the formula I (selective herbicides) 0 R 1 N O R 3 R2 NX CH 3 (I) 6* in which R, is H, halogen, haloalkyl, CN, NO 2 alkyl or Be,. alkoxy, R 2 is H or halogen, R 3 is Ci-C 8 ,-alkyl, benzyl, cycloalkyl, optionally halogenated alkenyl, optionally halogenated alkynyl or (CH 2 )n(O)mR 4 R 4 is C 1 -C 6 -alkyl which may be substituted by alkoxy, or a 5- or 6-membered o carbocyclic or heterocyclic compound or N=CRsR 6 Rs and R 6 are alkyl, cycloalkyl, alkylcarbonyloxyalkyl, alkoxy, alkylthio or, together with the carbon atom to which they are bonded, a cycloalkyl radical, n is 1 or 2 and m is 0 or 1, which comprises reacting a substituted quinoxaline of the formula II 0 N 0 R 7 R 2 X HO II II in which X is a leaving group, with a compouit.i of the formula III in which R 7 is Ci-C 4 -alkyl, and, where R3 is not identical to R 7 transesterifying the este'.' so obtained, of the formula I (R 3 to give another ester of the formula I substantially without racemization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4042098A DE4042098C2 (en) | 1990-12-28 | 1990-12-28 | Process for the preparation of optically active quinoxalinyloxy-phenoxypropionic acid esters |
| DE4042098 | 1990-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU9008091A AU9008091A (en) | 1992-07-02 |
| AU653376B2 true AU653376B2 (en) | 1994-09-29 |
Family
ID=6421615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU90080/91A Ceased AU653376B2 (en) | 1990-12-28 | 1991-12-24 | Process for the preparation of optically active esters of quinoxalinyloxyphenoxypropionic acid |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0492629B1 (en) |
| JP (1) | JPH04295469A (en) |
| KR (1) | KR920012048A (en) |
| AU (1) | AU653376B2 (en) |
| BR (1) | BR9105529A (en) |
| CA (1) | CA2058320A1 (en) |
| DE (2) | DE4042098C2 (en) |
| HU (1) | HU208682B (en) |
| IL (1) | IL100531A (en) |
| ZA (1) | ZA9110055B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU228113B1 (en) * | 1996-06-03 | 2012-11-28 | Nissan Chemical Ind Ltd | Processes for producing phenoxy propionic acid derivatives |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6540490A (en) * | 1989-10-05 | 1991-04-28 | Hoechst Aktiengesellschaft | Herbicidal, heterocyclically substituted phenoxyalkane carboxylic acid derivatives and process for preparing them |
| AU614620B2 (en) * | 1988-05-31 | 1991-09-05 | Dow Chemical Company, The | An improved process for the minimization of racemization in the preparation of optically active ((ar yloxy) phenoxy) propionates herbicides |
| AU615503B2 (en) * | 1988-01-06 | 1991-10-03 | Uniroyal Chemical Company, Inc. | Heterocyclic-alkylene quinoxalinyloxyphenoxypropanoate herbicides |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033389B2 (en) * | 1979-02-22 | 1985-08-02 | 日産化学工業株式会社 | Heterocyclic ether phenoxy fatty acid derivative, its production method, and herbicide containing the derivative |
| CA1317299C (en) * | 1980-06-23 | 1993-05-04 | Maged Mohamed Fawzi | Quinoxalinyloxy ethers as selective weed control agents |
| ZA818027B (en) * | 1980-11-26 | 1982-10-27 | Hoffmann La Roche | Oxime esters |
| NZ199342A (en) * | 1981-01-12 | 1985-08-16 | Ici Australia Ltd | Quinoxaline derivatives and herbicides |
| JPS6183144A (en) * | 1984-09-28 | 1986-04-26 | Nissan Chem Ind Ltd | Optical resolution of 2-(4-hydroxyphenoxy)propionic acid |
| JPH0610154B2 (en) * | 1984-12-28 | 1994-02-09 | 日産化学工業株式会社 | Process for producing optically active 2- (4-hydroxyphenoxy) propionic acid |
| US4687849A (en) * | 1985-10-04 | 1987-08-18 | Hoffmann-La Roche Inc. | [(Isopropylideneamino)oxy]-ethyl-2-[[6-chloroquinoxalinyl)oxy]phenoxy]propionate postemergent herbicide |
-
1990
- 1990-12-28 DE DE4042098A patent/DE4042098C2/en not_active Expired - Fee Related
-
1991
- 1991-12-19 BR BR919105529A patent/BR9105529A/en unknown
- 1991-12-20 ZA ZA9110055A patent/ZA9110055B/en unknown
- 1991-12-23 CA CA002058320A patent/CA2058320A1/en not_active Abandoned
- 1991-12-24 EP EP91122231A patent/EP0492629B1/en not_active Expired - Lifetime
- 1991-12-24 AU AU90080/91A patent/AU653376B2/en not_active Ceased
- 1991-12-24 DE DE59106542T patent/DE59106542D1/en not_active Expired - Fee Related
- 1991-12-26 IL IL10053191A patent/IL100531A/en not_active IP Right Cessation
- 1991-12-26 JP JP3345246A patent/JPH04295469A/en active Pending
- 1991-12-27 HU HU914124A patent/HU208682B/en not_active IP Right Cessation
- 1991-12-27 KR KR1019910024633A patent/KR920012048A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU615503B2 (en) * | 1988-01-06 | 1991-10-03 | Uniroyal Chemical Company, Inc. | Heterocyclic-alkylene quinoxalinyloxyphenoxypropanoate herbicides |
| AU614620B2 (en) * | 1988-05-31 | 1991-09-05 | Dow Chemical Company, The | An improved process for the minimization of racemization in the preparation of optically active ((ar yloxy) phenoxy) propionates herbicides |
| AU6540490A (en) * | 1989-10-05 | 1991-04-28 | Hoechst Aktiengesellschaft | Herbicidal, heterocyclically substituted phenoxyalkane carboxylic acid derivatives and process for preparing them |
Also Published As
| Publication number | Publication date |
|---|---|
| HU208682B (en) | 1993-12-28 |
| DE4042098A1 (en) | 1992-07-02 |
| BR9105529A (en) | 1992-09-01 |
| CA2058320A1 (en) | 1992-06-29 |
| JPH04295469A (en) | 1992-10-20 |
| AU9008091A (en) | 1992-07-02 |
| EP0492629B1 (en) | 1995-09-20 |
| EP0492629A3 (en) | 1993-01-13 |
| KR920012048A (en) | 1992-07-25 |
| ZA9110055B (en) | 1992-09-30 |
| DE59106542D1 (en) | 1995-10-26 |
| DE4042098C2 (en) | 1993-10-07 |
| IL100531A (en) | 1996-03-31 |
| HUT61291A (en) | 1992-12-28 |
| HU914124D0 (en) | 1992-03-30 |
| EP0492629A2 (en) | 1992-07-01 |
| IL100531A0 (en) | 1992-09-06 |
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