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WO2017158404A1 - Procédé amélioré pour la préparation de composés de type alkylènedioxybenzène - Google Patents

Procédé amélioré pour la préparation de composés de type alkylènedioxybenzène Download PDF

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Publication number
WO2017158404A1
WO2017158404A1 PCT/IB2016/052563 IB2016052563W WO2017158404A1 WO 2017158404 A1 WO2017158404 A1 WO 2017158404A1 IB 2016052563 W IB2016052563 W IB 2016052563W WO 2017158404 A1 WO2017158404 A1 WO 2017158404A1
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Prior art keywords
formula
compound
alkali
aprotic solvent
iii
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PCT/IB2016/052563
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English (en)
Inventor
Manoj Kumar Mohapatra
Ramamohanrao Bendapudi
Paul Vincent Menacherry
Vincent Paul
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Anthea Aromatics Pvt Ltd
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Anthea Aromatics Pvt Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems

Definitions

  • This invention relates to an improved method for preparing alkylenedioxybenzene compounds of Formula I, from the corresponding ortho-dihydroxy aromatic compound of Formula II,
  • Ri and R 2 independently represent H, linear or branched Ci - Cio alkyl or alkenyl group, cycloalkyl group, halogen selected from CI, Br, I, nitro (-N0 2 ), alkoxy (- OR) or thioether (-SR) wherein R is selected from linear or branched alkyl group comprising Cl- C6 carbon atoms; comprising contacting the said ortho-dihydroxy aromatic compound of Formula II with alkylene dihalide of Formula III in the presence of a base,
  • the present invention relates to an efficient, industrially safe and economically viable process for preparing alkylenedioxybenzene compounds of Formula I from the corresponding compounds of Formula II comprising contacting the said compound of Formula II with alkylene dihalide compound of Formula III and a suitable alkali also referred as base, wherein the alkylene dihalide compound of Formula III is taken in excess of stoichiometric quantity along with a suitable aprotic solvent, and the excess alkylene dihalide compound plus aprotic solvent together constitute a composite solvent, and wherein the said component solvent enables the reaction medium to be maintained in the preferred temperature range of about 60 ° C to about 100 ° C to give the required compound of Formula I in high yield and purity greater than 99%.
  • the present invention is characterized by the use of a composite solvent to enable completion of the reaction at lower temperatures, the addition of ortho-dihydroxy aromatic compound of Formula II and a suitable alkali to the said composite solvent such that the ortho-dihydroxy aromatic compound of Formula II is substantially reacted at a rate faster than the addition rate, an efficient method of separation and recovery of solvents, and improved method for isolation of the alkylenedioxybenzene compounds of Formula I in high purity and yield, thereby providing an economical, industrially viable process for the manufacture of compounds of Formula I.
  • US3436403 discloses a method for the preparation of methylenedioxybenzene comprising reactingortho-dihydroxy aromatic compound of Formula II with methylene dichloride in the presence of aprotic solvent to increase the rate of reaction and to maintain a high dilution of ions derived from dihydroxy aromatic compound thereby increasing yield of product.
  • catechol is added to methylene dichloride in an aprotic solvent such as dimethyl sulfoxide (DMSO) followed by the addition of powdered sodium hydroxide and carrying out reaction in the preferred temperature range of 110 °C to 140 °C and the product of Formula I was collected by steam distillation, followed by extraction in a solvent and purification by distillation in reported yields of 46% to 91% with no mention of purity.
  • aprotic solvent such as dimethyl sulfoxide (DMSO)
  • JP03275683 discloses a process wherein solid caustic alkali is dissolved in an aprotic solvent such as dimethyl sulfoxide under heating, and a mixed solution of catechol dissolved in an aprotic solvent and a methylene halide is dripped into the solution to give the objective compound of Formula I.
  • the ratio in the reaction is preferably 2.1 mol caustic alkali and 1.1 to 1.5 moles of methylene chloride per mole of catechol and the reported yield is 92% without any indication of purity.
  • CN1180073 discloses a process for preparing methylenedioxybenzene product of Formula I comprising using catechol as raw material; wherein dichloromethane and dimethyl sulfoxide are first mixed in a ratio of 1 :4, to which is added catechol dissolved in DMSO at a temperature of 53 ° C to 90 ° C, followed by further heating at 85 ° C to 92 ° C, however the said patent does not mention the purity of the finished product so obtained.
  • CN1907980 discloses a process for preparing methylenedioxybenzene product of Formula I comprising taking 1.6 kg of sodium hydroxide dissolved in 3.85 kg dimethyl sulfoxidein the reactor, then adding 1.4 kg dichloromethane under stirring and adding; catechol 1.6 kg dissolved in 1.65 kg dimethyl sulfoxide under heating. When the temperature reaches to the 90 ° C, catechol solution is slowly added into the reactor, and temperature in the reactor is controlled at 90 ° C to 110 ° C for about 2.5 hours. The reported yield is 95%, however there is no mention of purityof the finished product and also the method prescribes the use of large excess of DMSO.
  • US2698329 discloses aprocess for the preparation of trimethylenedioxyaryl compounds, particularly trimethylenedioxybenzene, comprising reacting a trimethylene halide such as trimethylene bromide or trimethylene chloride, with the corresponding ortho-dihydroxyaryl compound in the presence of an alkaline material such as sodium methylate.
  • trimethylenedioxybenzene is ⁇ 27% with no mention of purity.
  • US2007/0027184A1 discloses a method for preparation of trimethylenedioxybenzene (3,4- Dihydro-2H-benzo [l,4]dioxepine), comprising adding potassium carbonate and 1,3- dibromopropane to a solution of catechol in DMF.
  • the reported yield of the target compound is 91% with no mention of purity.
  • the ratio of aprotic solvent to catechol used is 15: 1.
  • the inventors of the present invention have disclosed an improved, efficient and economical process for preparation of alkylenedioxybenzenes to overcome the problems mentioned herein above, for the preparation of alkylenedioxybenzene compounds of Formula I in high purity (greater than 99% by Gas Chromatography analysis) and high yield (greater than 95% weight/weight on the corresponding ortho-dihydroxy aromatic compound of Formula II), with reduced usage of aprotic solvent, and improved the process for separation and isolation of the target compound of Formula I, as well as recovery of solvents, thereby making the process industrially safe, efficient and economical.
  • the present invention relates to an improved industrially safe, economical and viable process for preparing aromatic alkylenedioxybenzene compounds of Formula I from corresponding ortho- dihydroxy aromatic compounds of Formula II;
  • a salient feature of the present invention is the use of reduced quantity of suitable aprotic solvent such as DMSO along with stoichiometric excess of alkylene dihalide reactant of Formula III, wherein the stoichiometric excess of alkylene dihalide reactant of Formula III is between about 0.5 to about 3.0, and preferably greater than 0.8.
  • the inventors of the present invention have observed that use of said composite solvent system enables the completion of the desired reactions at lower temperatures resulting in improved safety and energy efficiency of the process, and enables the manufacture of the title compounds of Formula I in high purity (greater than 99% by Gas Chromatographic analysis) and high yield (greater than 95% wt./wt).
  • a second feature of the present invention is the simultaneous and/or sequential and/or lot wise addition of ortho-dihydroxy aromatic compound of Formula II and suitable alkali, also referred as base, to the composite solvent maintained at the desired reaction temperature, and to carry out the addition such that the ortho-dihydroxy aromatic compound of Formula II is substantially reacted at a rate faster than the rate of addition, so as to maintain a high molar ratio of aprotic solvent to the ortho-dihydroxy aromatic compound of Formula II in the reaction medium.
  • the inventors of the present invention have observed that the best results are obtained when the composite solvent system is maintained at a preferred reaction temperature of about 60 ° C to about 100 ° C, and more preferably between about 70 °C to about 90 °C, and when the addition of ortho-dihydroxy aromatic compound of Formula II and suitable alkali, also referred as base, is carried out lot-wise over an extended period, preferably exceeding about 2 hours,
  • a third feature of the present invention is an improved process for separation of target compound of Formula I and recovery of unreacted alkylene dihalide at reduced temperature facilitated by the addition of water to the reaction mass and carrying out azeotropic distillation to separate out the alkylenedioxybenzene compounds of Formula I along with the unreacted alkylene dihalide, the said process being preferably carried out in a Dean-Stark type apparatus.
  • the alkylenedioxybenzene compounds of Formula I is easily isolated from the alkylene dihalide using a conventional process such as distillation.
  • a fourth feature of the present invention is the removal of water from the DMSO after the separation of target compound and unreacted alkylene dihalide, to reduce the solubility of salt and alkali, also referred as base, in DMSO.
  • the salt and excess alkali is removed by conventional techniques such as filtration prior to DMSO recovery which reduces DMSO decomposition and polymerization and improves DMSO recovery.
  • the inventors of the present invention have disclosed an improved novel method for the preparation of said compound of Formula I comprising use of a composite solvent, made up by mixing alkylene dihalide of Formula III and an aprotic solvent such as dimethyl sulfoxide as reaction medium, maintaining said composite solvent at preferred reaction temperature of about 60 ° C to about 100 ° C, and more preferably between about 70°C to about 90°C, and into which is added simultaneously and/or sequentially and/or lot wise the ortho-dihydroxy aromatic compound of Formula II and suitable alkali also referred as base over an extended period, preferably exceeding about 2 hours.
  • a composite solvent made up by mixing alkylene dihalide of Formula III and an aprotic solvent such as dimethyl sulfoxide as reaction medium, maintaining said composite solvent at preferred reaction temperature of about 60 ° C to about 100 ° C, and more preferably between about 70°C to about 90°C, and into which is added simultaneously and/or sequentially and/or lot wise the ortho-dihydroxy aromatic compound of Formula II and suitable al
  • the compound of Formula I so formed along with unreacted alkylene dihalide of Formula III is separated from the aprotic solvent by azeotropic distillation, the said process being preferably carried out in a Dean- Stark type apparatus, and title compound of Formula I is further purified by distillation to give high purity product having purity of more than about 99% in yield more than about 95% wt./wt.
  • the present invention also overcomes the problem of recovery of aprotic solvent like DMSO by removing the water present in the solvent and separating the salt and excess alkali, also referred as base, by a method such as filtration prior to recovery of the DMSO solvent avoiding decomposition and polymerization, thereby increasing the recovery of aprotic solvent and making the process economical.
  • contacted and/or contacting used herein refers to reacting, added, refluxing, stirring and the likes.
  • alkali cited herein is also referred as base and both herein relates to same entity.
  • the present invention relates to an efficient, industrially safe and economically viable process for the preparation of alkylenedioxybenzene compounds of Formula I, from the corresponding ortho-dihydroxy aromatic compound of Formula II,
  • R 2 represents H, linear or branched Ci - C 10 alkyl or alkenyl group, cycloalkyl group, halogen selected from CI, Br, I, nitro (-N0 2 ) , alkoxy (-OR) or SR thioether (-SR) where in wherein R is selected from H or linear or branched alkyl group comprising C1-C6 carbon atoms; comprising contacting said compound of Formula II with alkylene dihalide of Formula III in the presence of a base,
  • Ri represents H, linear or branched Ci - Cio alkyl or alkenyl group, cycloalkyl group, halogen selected from CI, Br, I, nitro (-N0 2 ) , alkoxy (-OR) or SR thioether (-SR); and X is halogen CI, Br, I.
  • Ri and R 2 independently represent H, linear or branched Ci - Cio alkyl or alkenyl group, cycloalkyl group, halogen selected from CI, Br, I, nitro (-N0 2 ), alkoxy (-OR) or SR thioether (-SR), wherein R is selected from linear or branched alkyl group comprising Cl- C6 carbon atoms; and comprising; i) preparing a mixture of alkylene dihalide of Formula III and aprotic solvent, wherein the stoichiometric excess of alkylene dihalide reactant of Formula III is between about 0.5 to about 3.0, and preferably greater than 0.8.
  • step iii) simultaneously and/or sequentially, lot wise and/or continuously adding ortho- dihydroxy aromatic compound of Formula II and suitable alkali, also referred as base, to the said mixture of step ii) over a an extended period, preferably exceeding about 2 hours; and
  • alkali also referred as base
  • alkali is selected from the group comprising alkali metal hydroxide or alkali metal carbonate or alkali metal bicarbonate or mixtures thereof and the like that can prepare dialkalimetal salt of ortho-dihydroxy aromatic compound of Formula II.
  • the preferred alkali, also referred as base, is sodium hydroxide.
  • aprotic solvent is a compound that does not contain acidic hydrogen centers and which is able to form hydrogen bonds with an anion.
  • the aprotic solvent is selected from the group comprising N,N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide, acetonitrile, propionitrile and the like, nitrobenzene, benzonitrile, nitrotoluene, dimethylsulfone, tetrahydrofuran, sulfolane, dimethylsulfoxide (DMSO) or mixtures thereof.
  • the preferred aprotic solvent is DMSO.
  • the first aspect of the present invention is to provide an industrially safe and economically viable process for the preparation of alkylenedioxybenzene compound of Formula I in high yield (greater than 95% wt/wt) and high purity (greater than 99% by Gas Chromatographic analysis).
  • the second aspect of the present invention is the reduction in quantity of aprotic solvent required.
  • the third aspect of the present invention is carrying out the reaction in acomposite solvent maintained at preferred reaction temperature between about 60 ° C to about 100 ° C, and more preferably between about 70 °C to about 90 °C.
  • a fourth aspect of the present invention is the simultaneous and/or sequential, lot wise and/or continuous addition of ortho-dihydroxy aromatic compound of Formula II and suitable alkali, also referred as base, to the reaction medium over an extended period,preferably exceeding 2 hours.
  • the fifth aspect of the present invention is the separation of the title compound of Formula I formed along with unreacted alkylene dihalide of Formula III from the aprotic solvent by azeotropic distillation, said title compound of Formula I being further purified by distillation to give high purity product having purity of more than about 99% in yield more than about 95% wt/wt.
  • the sixth aspect of the present invention is the substantial removal of water, salt and/or excess alkali from the aprotic solvent prior to recovery of the aprotic solvent.
  • DMSO Dimethylsulfoxide
  • 1,2-dichloroethane 280g
  • the mixture was heated to 80°C under stirring.
  • 110 g of Catechol (in 5 g lots) and 148 g of sodium hydroxide (in 6.7 g lots) were simultaneously added in 22 lots each at intervals of 7 minutes maintaining the temperature of the reaction medium between 80°C and 85°C under stirring.
  • the reaction medium was stirred for 3 hrs till the catechol content was less than 0.1% by HPLC analysis.
  • DMSO Dimethylsulfoxide
  • 260g 1, 3-dichloropropane
  • the mixture was heated to 80°C under stirring.
  • 110 g of Catechol (in 5 g lots) and 88 g of sodium hydroxide (in 4.0 g lots) were simultaneously added in 22 lots each at intervals of 7 minutes maintaining the temperature of the reaction medium between 80°C and 85°C under stirring.
  • the reaction medium was stirred for 2 hrs till the catechol content was less than 0.1% by HPLC analysis.
  • Example 4 Preparation of 6-Methyl-l, 3 -methyl enedioxybenzene (compound of Formula ID)
  • Dimethylsulfoxide (DMSO, 360g) and dichloromethane (200g) were charged into a 2 liter reaction flask.
  • the mixture was heated to 80°C under stirring.
  • 124 g of 4-methylcatechol (in 5.6 g lots) and 88g of sodium hydroxide (in 4g lots) were simultaneously added in 22 lots each at intervals of 10 minutes maintaining the temperature of the reaction medium between 80°C and 85°C under stirring.
  • the reaction medium was stirred for lhrs till the unreacted 4-methylcatechol was less than 0.1% by HPLC analysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé amélioré pour la préparation de composés de type alkylènedioxybenzène de formule I, à partir du composé aromatique ortho-dihydroxy correspondant de formule II, dans lesquelles n vaut 0, 1, 2 ou 3 ; et R1 et R2 représentent, indépendamment, H, un groupe alkyle ou alcényle en C1–C10 linéaire ou ramifié, un groupe cycloalkyle, halogène choisi parmi Cl, Br, I, nitro (-NO2), alcoxy (-OR) ou SR thioéther (-SR), R représentant un groupe alkyle linéaire ou ramifié comprenant 1 à 6 atomes de carbone.
PCT/IB2016/052563 2016-03-12 2016-05-05 Procédé amélioré pour la préparation de composés de type alkylènedioxybenzène Ceased WO2017158404A1 (fr)

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IN201621008700 2016-03-12
IN201621008700 2016-03-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110563693A (zh) * 2019-09-30 2019-12-13 苏州弘森药业股份有限公司 一种胡椒环制备方法
CN111004205A (zh) * 2019-12-30 2020-04-14 江西兄弟医药有限公司 一种复合碱催化制备胡椒环的合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3436403A (en) * 1965-10-13 1969-04-01 Shell Oil Co Methylenation method
US4082774A (en) * 1974-07-11 1978-04-04 Eli Lilly And Company Methylenedioxybenzene -- improved method of preparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3436403A (en) * 1965-10-13 1969-04-01 Shell Oil Co Methylenation method
US4082774A (en) * 1974-07-11 1978-04-04 Eli Lilly And Company Methylenedioxybenzene -- improved method of preparation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110563693A (zh) * 2019-09-30 2019-12-13 苏州弘森药业股份有限公司 一种胡椒环制备方法
CN110563693B (zh) * 2019-09-30 2022-10-21 苏州弘森药业股份有限公司 一种胡椒环制备方法
CN111004205A (zh) * 2019-12-30 2020-04-14 江西兄弟医药有限公司 一种复合碱催化制备胡椒环的合成方法

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