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WO2015067494A1 - Procédé de production de dérivés d'acide salicylique à double substitution halogène - Google Patents

Procédé de production de dérivés d'acide salicylique à double substitution halogène Download PDF

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Publication number
WO2015067494A1
WO2015067494A1 PCT/EP2014/072990 EP2014072990W WO2015067494A1 WO 2015067494 A1 WO2015067494 A1 WO 2015067494A1 EP 2014072990 W EP2014072990 W EP 2014072990W WO 2015067494 A1 WO2015067494 A1 WO 2015067494A1
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compound
formula
present
molar equivalents
iii
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Inventor
Eric George KLAUBER
Michael Rack
Thomas Zierke
Nicole HOLUB
David Cortes
Gerald SCHMELEBECK
Junmin JI
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form

Definitions

  • the present invention relates to a process for providing dihalogen substituted salicylic acid derivatives.
  • the present invention provides an improved process for the production of the herbicide dicamba (3,6-dichloro-2-methoxybenzoic acid). Background of the invention
  • Dicamba is a selective herbicide currently used for treating e.g. corn, wheat or grassland. It kills broadleaf weeds before and after they sprout.
  • the trivial name dicamba refers to the compound 3,6-dichloro-2-methoxybenzoic acid.
  • the estimated global demand for dicamba in 2012 was about 12.000 million tons per year. However, it is expected that the global demand for dicamba will increase significantly.
  • Dicamba is typically produced on an industrial scale from 2,5-dichlorophenol using carboxyla- tion under Kolbe-Schmitt conditions, methylation and subsequently saponification/acidification.
  • 2,5-Dichorophenol in turn can be obtained from 1 ,4-dichlorobenzene or 1 ,2,4-trichlorobenzene.
  • the synthetic route via 1 ,4-dichlorobenzene involves nitration and subsequent diazotation, and, therefore is undesired for use on an industrial scale.
  • the synthetic route via 1 ,2,4- trichlorobenzene suffers from limited availability of this starting material and from the formation of several byproducts which are formed in the synthesis of 2,5-dichlorophenol.
  • the object of the present invention is to meet the above needs. It is a further object of the present invention to implement the improved process for the synthesis of dicamba on an industrial scale. A further object of the present invention is the provision of a cost effective process for the synthesis of dicamba. Even minor improvements in the yield in reaction sequences for obtaining dicamba would provide a tremendous benefit. For example, an improvement of yield of 1 % would provide an additional annual amount 120 million tons of dicamba.
  • the present invention relates to an improved process for providing dihalogen substituted salicyl- ic acid derivatives using decarboxylative etherification of dihalogenated phtalic acid derivatives.
  • the present invention relates to a process for providing a compound of formula (IV):
  • R 1 is hydrogen or -(Ci-C4)alkyl
  • R 2 is -(Ci-C4)alkyl
  • each Hal is an independently selected halogen.
  • R 1 and Hal are defined as above, and R 3 is an alkali metal, in the presence of a Ag(l) compound, a Cu(ll) compound, and a compound selected from Si(OR 2 ) 4 and B(OR 2 )3.
  • the step of reacting the compound of formula (III) is carried out in the further presence of a co-oxidant.
  • the co-oxidant is preferably selected from molecular oxygen (O2), benzoquinone, K2S2O8, Na2S20s, and a peroxyacetic acid ester. More preferably, the co- oxidant is O2.
  • the Ag(l) compound is in preferred embodiments selected from Ag2C03, Ag(l) acetate (AgOAc), and Ag20. More preferably, the Ag(l) compound is Ag2C03.
  • the Cu(ll) compound is selected from Cu(ll) acetate, and CuBr2. More preferably, the Cu(ll) compound is Cu(ll) acetate (Cu(OAc)2).
  • the compound selected from Si(OR 2 ) 4 and B(OR 2 ) 3 is Si(OR 2 ) 4 .
  • the Ag(l) compound is present in an amount of about 0.1 to about 1 .0 molar equivalents per one molar equivalent of the compound of formula (III). More preferably, the Ag(l) compound is present in an amount of about 0.25 to about 1 .0 molar equivalents per one molar equivalent of the compound of formula (III). In a still further preferred em- bodiment, the Ag(l) compound is present in an amount of about 0.25 molar equivalents. It is preferred according to the present invention that the Cu(ll) compound is present in an amount of about 0.1 to about 1.0 molar equivalents per one molar equivalent of the compound of formula (III). More preferably, the Cu(ll) compound is present in an amount of about 0.2 to about 1 .0 molar equivalents per one molar equivalent of the compound of formula (III), still fur- ther preferably in an amount of about 1.0 molar equivalent.
  • the compound selected from Si(OR 2 ) 4 and B(OR 2 )3 is preferably present in an amount of about 1 .0 to about 5.0 molar equivalents per one molar equivalent of the compound of formula (III). More preferably, the compound selected from Si(OR 2 ) 4 and B(OR 2 )3 is present in an amount of about 5.0 molar equivalents.
  • the co-oxidant is present in an amount of about 0.8 to about 1 .2 molar equivalents per one molar equivalent of the compound of formula (III). More preferably, the co-oxidant is present in an amount of about 1.0 molar equivalent per one molar equivalent of the compound of formula (III).
  • the co- oxidant is O2 and is provided is gaseous form.
  • O2 is provided at a pressure of about 100 kPa to about 200 kPa, more preferably about 101.3 kPa.
  • the above step of reacting the compound of formula (III) is carried preferably out at a temperature of about 100°C to about 160°C. More preferably, the step of reacting the compound of formula (III) is carried out at a temperature of about 1 15°C to about 150°C, still more preferably about 120°C to about 145°C.
  • Hal is preferably selected from -F, -CI, -Br and -I, more preferably - CI and -Br, and most preferably -CI.
  • R 1 is selected from hydrogen, methyl and ethyl, more preferably hydrogen.
  • R 1 is -(Ci-C 4 )alkyl, such as methyl or ethyl, in the compound of formula (III), and the resulting compound of formula (IV), in which R 1 is likewise -(Ci-C 4 )alkyl, is preferably converted to a compound of formula (IV), in which R 1 is hydrogen.
  • R 2 is according to the invention preferably selected from methyl and ethyl, more preferably from methyl.
  • R 3 is preferably selected from lithium, sodium and potassium, more preferably from sodium and potassium, and most preferably is potassium.
  • the processes according to the present invention are employed for obtaining dicamba.
  • the compound of formula (IV) finally obtained is
  • Hal or "halogen” when used in the context of the present invention refers to -F, -CI, -Br or -I.
  • the halogen is -CI or -Br, more preferably -CI.
  • OAc refers in the context of the present invention to an acetate ion -0(0)C-CH3.
  • -(Ci-C4)alkyl refers according to the invention to a straight chained or branched aliphatic alkyl residue having one to four carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl.
  • the present invention relates to a process for providing a compound of formula (IV), as defined above, comprising the step of: reacting a compound of formula (III), as defined above in the presence of a Ag(l) compound, a Cu(ll) compound, and a compound selected from Si(OR 2 ) 4 and B(OR 2 ) 3 .
  • Compounds of formula (III), in which R 3 is an alkali metal, can be obtained by neutralizing a corresponding carboxylic acid using a suitable base.
  • the base for neutralizing the correspond- ing carboxylic acid is not specifically limited and is preferably selected from alkali metal alkoxides, such as alkali metal (Ci-C4)alkoxides.
  • An especially preferred base is potassium tert- butoxide.
  • the base is typically used in stoichiometric amounts.
  • the resulting alkali metal car- boxylate salts of formula (III) can be isolated or can be prepared in-situ.
  • the Ag(l) compound is according to the invention preferably selected from Ag2C03, Ag(l) acetate (AgOAc), and Ag20, more preferably Ag2C03.
  • the Ag(l) compound is present in an amount of about 0.1 to about 1 .0 molar equivalents per one molar equivalent of the compound of formula (III), more preferably about 0.25 to about 1 .0 molar equivalents.
  • the Ag(l) compound is present in an amount of about 0.25 molar equivalents.
  • the Cu(ll) compound is according to the invention preferably selected from Cu(ll) acetate, and CuBr2. More preferably the Cu(ll) compound is Cu(ll) acetate (Cu(OAc)2).
  • the Cu(ll) compound is present in an amount of preferably about 0.1 to about 1 .0 molar equivalents per one molar equivalent of the compound of formula (III), more preferably about 0.2 to about 1.0 molar equivalents, still more preferably in an amount of about 1 .0 molar equivalent.
  • the compound selected from Si(OR 2 ) 4 and B(OR 2 ) 3 is Si(OR 2 ) 4 .
  • the compound selected from Si(OR 2 ) 4 and B(OR 2 ) 3 is preferably present in an amount of about 1 .0 to about 5.0 molar equivalents per one molar equivalent of the compound of formula (III), more preferably in an amount of about 5.0 molar equivalents.
  • the step of reacting the compound of formula (III) according to the invention is preferably carried out in the additional presence of a co-oxidant as defined above.
  • a co-oxidant is used, substoichiometric amounts of the Ag(l) compound and/or Cu(ll) compound can be used, which is preferable e.g. from the viewpoint of costs.
  • the co-oxidant is preferably selected from molecular oxygen (O2), benzoquinone, K2S2O8, Na2S20s, and a peroxyacetic acid ester, such as peroxyacetic acid tert-butyl ester.
  • the co-oxidant is 02.
  • the co-oxidant is preferably present in an amount of about 0.8 to about 1 .2 molar equivalents per one molar equivalent of the compound of formula (III), more preferably about 1 .0 molar equivalent.
  • O2 is used as the co-oxidant, which is preferred, it is provided at a pressure of about 100 kPa to about 200 kPa, more preferably about 101.3 kPa.
  • the above step of reacting the compound of formula (III) is carried preferably out at a temperature of about 100°C to about 160°C, more preferably about 1 15°C to about 150°C, still more preferably about 120°C to about 145°C.
  • the step of reacting the compound of formula (I I I) is carried out in solution in an organic solvent.
  • the organic solvent is not particularly limited as long as it does not interfere with the reaction.
  • Preferred solvents include but are not limited to dioxane, 1 ,2-dichloroethane (DCE), acetonitrile, dimethylsulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone (NMP), N,N- dimethylacetamide (DMA), or ⁇ , ⁇ -dimethylpropionamide (DMP), preferably DMF, DMA, or DMP, most preferably DMF.
  • DCE dioxane
  • DCE dimethylsulfoxide
  • DMF dimethylformamide
  • NMP N-methylpyrrolidone
  • DMA N,N- dimethylacetamide
  • DMP ⁇ , ⁇ -dimethylpropionamide
  • alkali metal hydroxides such as NaOH may be employed here.
  • a composition comprising alkali metal salts, such as sodium salts, are obtained.
  • the alkali metal salt of a compound of formula (IV) is then acidified in aqueous solution using a suitable acid, such as H2SO4 or HCI, preferably HCI, to afford the compound of formula (IV), in which R 1 is hydrogen.
  • Carboxylic acids corresponding to compounds of formula (I II), in which R 1 and R 3 are hydrogen can be obtained from readily available materials in reaction steps suitable to be carried out on an industrial scale.
  • compounds of formula (Il ia) can be provided by oxidizing 1 ,4- dihalonaphthalenes of formula (II), wherein Hal is as defined above.
  • the present invention relates to a process as defined above, wherein the compound of formula (I II) is obtained by oxidizing a compound of formula (I I) and the resulting compound of formula (I l ia) is neutralized with about one molar equivalent of a suitable base such as an alkali metal alkoxide. Furthermore, the compound of formula (II) in turn can be obtained by halogenating naphthalene (referred to as a compound of formula (I)).
  • the above reaction step can be carried out on an industrial scale, e.g. by aromatic free radical chlorination or bromination.
  • the present invention relates to a process as defined above, wherein the compound of formula (II) is obtained by halogenating a compound of formu la (I).
  • compounds of formula (Ilia) can be obtained by reductive dehalogenation from tetrahalophthalic acid anhydride using zinc powder as described in WO 00/05195.
  • the present invention relates to a process as defined above, wherein the compound of formula (III) is obtained by reductive dehalogenation of tetrahalophthalic acid, and the resulting compound of formula (Ilia) is neutralized with about one molar equivalent of a suitable base such as an alkali metal alkoxide.
  • Carboxylic acids corresponding to compounds of formula (III), in which R 1 is -(Ci-C4)alkyl can be obtained by dehydrating the above compounds of formula (Ilia) to obtain 3,6-dihalophthalic acid anhydride.
  • compounds of formula (Ilia) may be combined in a suitable solvent such as toluene with catalytic amounts of acid (e.g. p-toluenesulfonic acid) under azeotropic removal of water to obtain 3,6-dihaolphthalic anhydride.
  • the reaction may be carried out with acid chloride forming reagents such as SOC or POC in an inert solvent such as chlorinated solvents at increased temperature.
  • the reaction may be accomplished in acetic acid at in- creased temperature.
  • 3,6-dihalophthalic acid anhydride is reacted the with an alcohol of the formula HOR 1 , wherein R 1 is -(Ci-C4)alkyl, to obtain a compound of formula (l l lb), wherein Hal is as defined above and R 1 is -(Ci-C4)alkyl.
  • 3,6-dihalophthalic acid anhydride may be dissolved in an alcohol of formula HOR 1 (e.g.
  • a corresponding alkali metal (Ci-C4)alkoxide e.g. NaOCHs
  • 3,6-dihalophthalic acid anhydride may be dissolved in an alcohol of formula HOR 1 (e.g. methanol) together with catalytic amounts of acid (such as H2SO4 or HCI) at increased temperature.
  • the present invention relates to a process as defined above, wherein the compound of formula (II I), in which R 1 is -(Ci-C4)alkyl, is obtained by dehydrating a compound of formula (I l ia), reacting the resulting 3,6-dihalophthalic acid anhydride with an alcohol of the formula HOR 1 , wherein R 1 is -(Ci-C4)alkyl, and neutralizing the resulting compound of formula (l llb) is neutralized with about one molar equivalent of a suitable base such as an alkali metal alkoxide.
  • a suitable base such as an alkali metal alkoxide
  • 3,6-dihalophthalic acid can be obtained by reductive
  • Hal is -CI
  • R 1 is hydrogen in the finally obtained product.
  • the present invention provides in preferred embodiments an improved reaction sequence for obtaining dicamba.
  • naphthalene is chlorinated for obtaining 1 ,4- dichloronaphthalene as described above. Subsequently, 1 ,4-dichloronaphthalene is oxidized using HNO3 as described above to obtain 3,6-dichlorophthalic acid.
  • 1 ,4-Dichloronaphthalene is a compound according to formula (II) of the present invention in which Hal is CI.
  • 3,6-Dichlorophthalic acid is a compound of formula (Ilia) according to the invention in which Hal is CI.
  • 3,6-dichlorophthalic acid may be obtained by reductive dehalogenation of tertachlorophthalic acid.
  • tetrachlorophthalic acid (1 equivalent) is combined in water with an alkali metal hydroxide such as NaOH (about 3.6 molar equivalents) and zinc powder (about 3.0 molar equivalents) at a temperature of about 70 to 80°C to afford trichlorophtahlic acid.
  • Trichlorophthalic acid (1 equivalent) in turn can be converted to 3,6- dichlorophthalic acid by reacting with e.g. NaOH (about 6.0 molar equivalents) and zinc powder (about 5.8 molar equivalents) in water at a temperature of about 95 to 100°C.
  • NaOH about 6.0 molar equivalents
  • zinc powder about 5.8 molar equivalents
  • 3,6-Dichlorophthalic acid can be partly neutralized using one molar equivalent of potassium tert- butoxide to provide potassium 2-carboxy-3,6-dichlorobenzoate which then is reacted according to the present invention using Ag2C03, Cu(OAc)2, Si(OCHs) 4 and O2 as described above to obtain after acidification dicamba.
  • Potassium 2-carboxy-3,6-dichlorobenzoate is a compound of formula (III) according to the present invention in which R 1 is hydrogen, R 3 is potassium and Hal is CI.
  • Dicamba is a compound of formula (IV) of the invention.
  • 3,6-dichlorophthalic acid can be dehydrated and the resulting 3,6-dichlorophthalic acid anhydride can be reacted with methanol to provide 3,6-dichloro-2- (methoxycarbonyl)benzoic acid.
  • 3,6-Dichloro-2-(methoxycarbonyl)benzoic acid is a compound of formula (1Mb) according to the present invention wherein R 1 is methyl.
  • 3,6-dichlorophthalic acid anhydride can be prepared by reductive dehalogenation from trichlorophthalic acid (which may be obtained as outlined above) under azeotropic removal of water, and subsequently can be reacted with methanol to provide 3,6-dichloro-2- (methoxycarbonyl)benzoic acid.
  • reacting trichlorophthalic acid to provide 3,6- dichlorophthalic acid anhydride can be accomplished with NaOH (about 6 molar equivalents), zinc powder (about 5.8 molar equivalents) in water at about 95 to 100°C, and subsequently add- ing HCI and azeotropic removal of water using toluene at about 1 10°C.
  • 3,6-dichloro-2-(methoxycarbonyl)benzoic acid is converted to potassium 3,6- dichloro-2-(methoxycarbonyl)benzoate using potassium tert-butoxide, and the resulting product is in turn is reacted according to the present invention using Ag2C03, Cu(OAc)2, Si(OCH3)4 and O2 as described above to obtain after acidification methyl 3,6-dichloro-2-methoxybenzoate.
  • Methyl 3,6-dichloro-2-methoxybenzoate is hydrolyzed as described above to obtain dicamba.
  • Potassium 3,6-dichloro-2-(methoxycarbonyl)benzoate is a compound of formula (III) according to the present invention in which Hal is CI, R 1 is methyl and R 3 is potassium.
  • Methyl 3,6- dichloro-2-methoxybenzoate is a compound of formula (IV) according to the invention in which Hal is CI, R 1 is methyl and R 2 is methyl.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé visant à produire un composé de formule (IV), dans laquelle R1 est l'hydrogène ou un alkyle en C1 à C4, R2 est un alkyle en C1 à C4 et chaque Hal représente un halogène choisi de manière indépendante, le procédé comprenant l'étape consistant à : faire réagir un composé de formule (III), dans laquelle R1 et Hal sont tels que définis plus haut, et R3 est un métal alcalin, en présence d'un composé Ag(l), d'un composé Cu(ll) et d'un composé choisi parmi Si(OR2)4 et B(OR2)3.
PCT/EP2014/072990 2013-11-08 2014-10-27 Procédé de production de dérivés d'acide salicylique à double substitution halogène Ceased WO2015067494A1 (fr)

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US201361901462P 2013-11-08 2013-11-08
US61/901,462 2013-11-08
EP13195214 2013-11-30
EP13195214.5 2013-11-30

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9988333B2 (en) 2014-05-19 2018-06-05 Basf Se Process for making 2,5-dihalogenated phenol
US10023590B2 (en) 2014-04-17 2018-07-17 Basf Se Substituted pyridine compounds having herbicidal activity
US10087133B2 (en) 2013-12-11 2018-10-02 Basf Se Process for providing dihalogen substituted salicylic acid derivatives
US10093607B2 (en) 2013-10-04 2018-10-09 Basf Se Selective hydrolysis and alcoholysis of chlorinated benzenes
US10093634B2 (en) 2013-12-18 2018-10-09 BASF Agro B.V. Process for the preparation of substituted phenoxyphenyl ketones
US10167297B2 (en) 2014-10-24 2019-01-01 Basf Se Substituted pyridine compounds having herbicidal activity
US10344008B2 (en) 2015-05-08 2019-07-09 BASF Agro B.V. Process for the preparation of terpinolene epoxide
US10538470B2 (en) 2015-05-08 2020-01-21 BASF Agro B.V. Process for the preparation of limonene-4-ol
US10640477B2 (en) 2016-06-15 2020-05-05 BASF Agro B.V. Process for the epoxidation of a tetrasubstituted alkene
US11072593B2 (en) 2016-06-15 2021-07-27 BASF Agro B.V. Process for the epoxidation of a tetrasubstituted alkene
CN114573535A (zh) * 2022-03-18 2022-06-03 常州大学 化工中间体3-羟基邻苯二甲酸酐的制备方法
CN116354928A (zh) * 2023-04-03 2023-06-30 南京优氟医药科技有限公司 一种4-溴-2-（2,6-二氧代哌啶-3-基）7-氟代异吲哚啉-1,3-二酮的制备方法
CN116354929A (zh) * 2023-04-03 2023-06-30 南京优氟医药科技有限公司 一种6-溴-2-（2,6-二氧代哌啶-3-基）4-氟代异吲哚啉-1,3-二酮的制备方法

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10093607B2 (en) 2013-10-04 2018-10-09 Basf Se Selective hydrolysis and alcoholysis of chlorinated benzenes
US10087133B2 (en) 2013-12-11 2018-10-02 Basf Se Process for providing dihalogen substituted salicylic acid derivatives
US10093634B2 (en) 2013-12-18 2018-10-09 BASF Agro B.V. Process for the preparation of substituted phenoxyphenyl ketones
US10023590B2 (en) 2014-04-17 2018-07-17 Basf Se Substituted pyridine compounds having herbicidal activity
US9988333B2 (en) 2014-05-19 2018-06-05 Basf Se Process for making 2,5-dihalogenated phenol
US10167297B2 (en) 2014-10-24 2019-01-01 Basf Se Substituted pyridine compounds having herbicidal activity
US10344008B2 (en) 2015-05-08 2019-07-09 BASF Agro B.V. Process for the preparation of terpinolene epoxide
US10538470B2 (en) 2015-05-08 2020-01-21 BASF Agro B.V. Process for the preparation of limonene-4-ol
US10640477B2 (en) 2016-06-15 2020-05-05 BASF Agro B.V. Process for the epoxidation of a tetrasubstituted alkene
US11072593B2 (en) 2016-06-15 2021-07-27 BASF Agro B.V. Process for the epoxidation of a tetrasubstituted alkene
CN114573535A (zh) * 2022-03-18 2022-06-03 常州大学 化工中间体3-羟基邻苯二甲酸酐的制备方法
CN114573535B (zh) * 2022-03-18 2024-01-23 常州大学 化工中间体3-羟基邻苯二甲酸酐的制备方法
CN116354928A (zh) * 2023-04-03 2023-06-30 南京优氟医药科技有限公司 一种4-溴-2-（2,6-二氧代哌啶-3-基）7-氟代异吲哚啉-1,3-二酮的制备方法
CN116354929A (zh) * 2023-04-03 2023-06-30 南京优氟医药科技有限公司 一种6-溴-2-（2,6-二氧代哌啶-3-基）4-氟代异吲哚啉-1,3-二酮的制备方法
CN116354929B (zh) * 2023-04-03 2025-05-13 南京优氟医药科技有限公司 一种6-溴-2-（2,6-二氧代哌啶-3-基）4-氟代异吲哚啉-1,3-二酮的制备方法

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