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WO2018150230A1 - Procédé de préparation de dérivés alcényle et alkyle d'alkylènedioxybenzène - Google Patents

Procédé de préparation de dérivés alcényle et alkyle d'alkylènedioxybenzène Download PDF

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Publication number
WO2018150230A1
WO2018150230A1 PCT/IB2017/052230 IB2017052230W WO2018150230A1 WO 2018150230 A1 WO2018150230 A1 WO 2018150230A1 IB 2017052230 W IB2017052230 W IB 2017052230W WO 2018150230 A1 WO2018150230 A1 WO 2018150230A1
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WIPO (PCT)
Prior art keywords
formula
compound
linear
acyl halide
alkylenedioxybenzene
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PCT/IB2017/052230
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English (en)
Inventor
Manoj Kumar Mohapatra
Ramamohanrao Bendapudi
Paul Vincent Menacherry
Vincent Paul
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Anthea Aromatics Private Limited
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Publication of WO2018150230A1 publication Critical patent/WO2018150230A1/fr

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    • 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
    • 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

  • the present disclosure generally relates to the method of preparation of compounds of Formula IV.
  • alkylenedioxybenzene derivatives have gained much importance in the pharmaceutical, pesticide, perfumery and food sectors due to their application as an end product or intermediates for the synthesis of wide range of finished products.
  • a large number of processes are available in the prior art for the preparation of alkylenedioxybenzene derivatives, particularly dihydrosafrole.
  • Dauksas et al. disclose a process involving 1,3-benzodioxole and acyl chloride as raw materials and using A1C13 or SnC14 as catalyst to prepare piperonyl ethyl ketone with a yield of -58%.
  • CN1907980 discloses a method comprising Friedel-Crafts acylation of 1,3- benzodioxole using propionic anhydride as the acylating agent in the presence of perchloric acid as the catalyst with a yield of -72% with no data on purity.
  • CN100473650C discloses a 3 step process to prepare dihydrosafrole comprising Friedel-Crafts acylation of catechol, catalytic hydrogenation followed by cyclization to obtain target product.
  • the disclosed process requires Zinc chloride in high stoichiometric quantity (about 1.2 moles per mole of catechol) to complete the acylation.
  • the document discloses that the reported yield of the product obtained is -74% with a purity of 98.2%.
  • CN102070596 discloses a process for the preparation of dihydrosafrole by Friedel- Crafts acylation of 1,3-benzodioxole using propionyl chloride as acylating agent in the presence of Lewis acid catalyst like Zinc chloride to prepare the acyl compound, followed by its reduction by Wolf-Kishner reaction using hydrazine hydrate with a yield of -82% with a purity of 99%.
  • the disclosed process requires Zinc chloride in high stoichiometric quantity (about 1.2 moles per mole of catechol) to complete the acylation.
  • the disclosed reaction requires the use of highly toxic and carcinogenic hydrazine hydrate.
  • EP1048664A2 discloses a process for the preparation of dihydrosafrole that comprises a 5 step reaction comprising the use of 4-hydroxyphenyl acetone as a starting material and the said starting material is subjected to catalytic hydrogenation followed by esterifi cation, rearrangement, hydrolysis and cyclization to give the target product.
  • the disclosed process fails to disclose yield or purity of the title compound so obtained.
  • WO2000040575 discloses a process for the preparation of dihydrosafrole from methylenedioxybenzene and propionic anhydride using perchloric acid as catalyst followed by using 5% Pd/C during the hydrogenation stage to obtain dihydrosafrole with a yield of 79.5% on methylenedioxybenzenewith no disclosure of purity of the product.
  • US2015038465A1 discloses a process for preparation of higher alkyl derivatives (C4 - CIO) of 1,3-benzodioxole, said process comprising use of the corresponding acyl chloride and Zinc chloride as catalyst to obtain the final product with a reported yield of 39.3%.
  • W09639133 discloses that the acylated product of 1,3-benzodioxole is difficult to purify and involved repeated treatments for decolorization.
  • Another object of the present disclosure is to provide a process for the acylation of alkylenedioxybenzene without substantial degradation of alkylenedioxybenzene or acylated product formed therefrom.
  • Yet another object of the present disclosure is to provide a process for the acylation of alkylenedioxybenzene that substantially reduces the amount of Lewis acid, such as Zinc chloride, used as catalyst.
  • Yet another object of the present disclosure is to provide a process for the acylation of alkylenedioxybenzene compounds to prepare the acylated product in high yield.
  • Yet another object of the present disclosure is to provide a process for the acylation of alkylenedioxybenzene compounds to prepare the acylated product with high purity.
  • Yet another object of the present disclosure is to provide an efficient process for preparation of alkyl and alkylene derivatives of alkylenedioxybenzene compounds without substantial degradation of any of the starting compound(s) and the desired product during the course of reaction.
  • the present disclosure generally relates to the method of preparation of compounds of Formula IV.
  • An aspect of the present disclosure relates to a process for preparation of compound of Formula IV, said process comprising the step of reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • the amphoteric oxide is selected from a group consisting of Zinc oxide, Tin oxide, Aluminum oxide, Beryllium oxide, and mixtures thereof, and the amphoteric oxide is used in a quantity ranging from 0.2 to 0.9 moles per mole of acid halide.
  • the amphoteric oxide selected is Zinc oxide, and wherein Zinc oxide is used in a quantity ranging from about 0.4 moles to about 0.6 moles per mole of acyl halide.
  • the Lewis acid is selected from a group consisting of Zinc chloride, Tin chloride, Aluminum Chloride, Beryllium chloride, and mixtures thereof, and the Lewis acid is used in a quantity ranging from 0.0 moles to about 0.5 moles per mole of acyl halide.
  • the Lewis acid selected is Zinc chloride, and wherein Zinc chloride is used in a quantity ranging from about 0.01 moles to about 0.25 moles per mole of acyl halide, and more preferably from about 0.01 moles to about 0.1 moles per mole of acyl halide.
  • the solvent is selected from the group consisting of dichloromethane, ethylene di chloride, 1 ,2-dichloropropane, or mixtures thereof.
  • the solvent selected is dichloromethane.
  • Another aspect of the present disclosure relates to a process for preparation of a compound of Formula IA, said process comprising the steps of: (a) obtaining a compound of Formula IV by reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • Still further aspect of the present disclosure relates to a process for preparation of a compound of Formula IB, said process comprising the steps of: (a) obtaining a compound of Formula IV by reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • the Nickel catalyst is Raney Nickel.
  • the acid catalyst is selected from a group consisting of p-toluene sulfonic acid, anhydrous Sodium bisulphate, anhydrous Potassium bisulphate, Nickel chloride, Ferrous sulphate, Zinc chloride or mixtures thereof.
  • the compound of Formula IB is dihydrosafrole of Formula VII.
  • the present disclosure generally relates to the method of preparation of compounds of Formula IV.
  • An aspect of the present disclosure relates to a process for preparation of compound of Formula IV, said process comprising the step of reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • the amphoteric oxide is selected from a group consisting of Zinc oxide, Tin oxide, Aluminum oxide, Beryllium oxide, and mixtures thereof, and the amphoteric oxide is used in a quantity ranging from about 0.2 moles to about 0.9 moles per mole of the acyl halide.
  • the amphoteric oxide selected is Zinc oxide, and more preferably wherein the Zinc oxide is used in a quantity ranging from about 0.4 moles to about 0.6 moles per mole of the acyl halide.
  • the Lewis acid is selected from a group consisting of Zinc chloride, Tin chloride, Aluminum Chloride, Beryllium chloride, and mixtures thereof, and the Lewis acid is used in a quantity ranging from 0.0 moles to about 0.5 moles per mole of acyl halide.
  • any other Lewis acid can be used to serve its intended purpose as laid down in the present disclosure without departing from the scope and spirit of the invention.
  • the Lewis acid selected is Zinc chloride, and more preferably wherein the Zinc chloride is used in a quantity ranging from about 0.01 moles to about 0.25 moles per mole of acyl halide and most preferably wherein Zinc chloride is used in a quantity ranging from about 0.01 moles to about 0.1 moles per mole of acyl halide.
  • the solvent is selected from the group consisting of dichloromethane, ethylene dichloride, 1 ,2-dichloropropane, other chlorinated hydrocarbons or mixtures thereof.
  • the solvent selected is dichloromethane.
  • Another aspect of the present disclosure relates to a process for preparation of a compound of Formula IA, said process comprising the steps of: (a) obtaining a compound of Formula IV by reacting an alkyl enedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • selective reduction is carried out in presence of a metal catalyst.
  • the metal catalyst is selected from precious metal catalysts such as Palladium, Platinum, Ruthenium and the likes.
  • the metal catalyst is Raney Nickel.
  • any other catalyst as known to or appreciated by a person skilled in the art can be utilized to effect selective reduction without departing from the scope and spirit of the invention.
  • said metal catalyst is supported on conventional supports such as carbon, alumina, silica and the likes.
  • dehydration is carried out in presence of a catalyst selected from p-toluene sulfonic acid, Sodium bisulphate, Potassium bisulphate, sulphuric acid and the likes.
  • a catalyst selected from p-toluene sulfonic acid, Sodium bisulphate, Potassium bisulphate, sulphuric acid and the likes.
  • any other catalyst as known to or appreciated by a person skilled in the art can be utilized to effect dehydration without departing from the scope and spirit of the invention.
  • the compound of Formula IA is isosafrole of Formula V.
  • the compound of Formula IIA is reacted with the acyl chloride of Formula IIIA in the presence of an amphoteric oxide such as Zinc oxide in combination with catalytic quantity of Lewis acid such as Zinc chloride in a suitable solvent to obtain compound of Formula IVA.
  • an amphoteric oxide such as Zinc oxide
  • Lewis acid such as Zinc chloride
  • said compound of Formula IVA is subjected to selective reduction and dehydration to obtain the compound of Formula V in high yield (greater than 100% wt./wt. of the alkylenedioxybenzene consumed) and high purity (more than 99% by GC), as shown in Scheme 1 below.
  • Formula IB said process comprising the steps of: (a) obtaining a compound of Formula ⁇ by reacting an alkylenedioxybenzene compound of Formula II with an acyl halide of Formula III in presence of a solvent,
  • the Nickel catalyst is Raney Nickel.
  • the acid catalyst is selected from a group comprising p-toluene sulfonic acid, anhydrous Sodium bisulphate, anhydrous Potassium bisulphate, Nickel chloride, Ferrous sulphate, Zinc chloride or mixtures thereof.
  • any other acid catalyst as known to or appreciated by a person skilled in the art can be utilized to serve its intended purpose without departing from the scope and spirit of the present invention.
  • the compound of Formula IB is dihydrosafrole of Formula VII.
  • the compound of Formula IIA is reacted with the acyl chloride of Formula IIIA in the presence of an amphoteric oxide such as Zinc oxide in combination with catalytic quantity of Lewis acid such as Zinc chloride in a suitable solvent to obtain compound of Formula IVA.
  • an amphoteric oxide such as Zinc oxide
  • Lewis acid such as Zinc chloride
  • the compound of Formula IVA is directly converted to the target compound of Formula VII by reacting the compound of Formula IVA with hydrogen in presence of a composite catalyst system, wherein the composite catalyst system comprises of a Nickel catalyst, such as Raney Nickel, in combination with an acid catalyst such as p-toluene sulfonic acid, anhydrous Sodium bisulphate, anhydrous Potassium bisulphate, Nickel chloride, Ferrous sulphate, Zinc chloride and the like, and in a suitable solvent such as methanol, ethanol, n- propanol, isopropyl alcohol, sec-butanol, t-butyl alcohol and the like.
  • the reaction is carried out in a single step.
  • the reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid, and the organic layer was separated and distilled to recover 250 g of unreacted 1,3-benzodioxole, and 310 g of methylenedioxybenzene propiophenone with GC purity > 99%.
  • the methylenedioxybenzene propiophenone was charged into a 2 litre autoclave along with 500 g of isopropyl alcohol, 15g of Raney Nickel catalyst and 0.5 g of anhydrous sodium hydrogen sulphate. The mixture was maintained at 110°C under hydrogen at 100 psi pressure till unreacted methylenedioxybenzene propiophenone reduced to less than 0.5% as observed by GC analysis.
  • the reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid, and the organic layer was separated and distilled to recover 64 g of unreacted 1,3-benzodioxole and 71 g of methyl enedioxybenzene propiophenone with a GC purity of > 99%.
  • the methylenedioxybenzene propiophenone was charged into a 1 liter autoclave along with 125 g of isopropyl alcohol, 4 g of Raney Nickel catalyst and 0.1 g of anhydrous sodium hydrogen sulphate.
  • the mixture was maintained at 110°C under hydrogen at 100 psi pressure till unreacted methylenedioxybenzene propiophenone was reduced to less than 0.5% by GC analysis.
  • the catalyst was separated, and the crude was distilled to give 61 g of dihydrosafrole with a yield of 105.2% (wt./wt. on 1,3-benzodioxole consumed) and purity of > 99% by GC analysis.
  • reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid and the organic layer was separated and distilled to recover 39 g of unreacted 1,3-benzodioxole and 56 g of methylenedioxybenzene propiophenone with a yield of 58.7% (wt./wt. on 1,3-benzodioxole consumed).
  • this reaction approximately 30 g of high boiling distillation residue was obtained.
  • Example 6 The reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid and the organic layer was separated and distilled to recover 245 g of unreacted 1,3-benzodioxole, and 311 g of methylenedioxybenzene propiophenone with a GC purity of >99%.
  • the methylenedioxybenzene propiophenone was subjected to selective reduction and dehydration as discussed in Example 1 to obtain 271 g of dihydrosafrole with a yield of 111.5% (wt./wt. on 1,3-benzodioxole consumed) and purity of > 99% by GC analysis.
  • Example 6 Example 6
  • the reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid and the organic layer was separated and distilled to recover 60 g of unreacted 1,3-benzodioxole, and 80 g of methylenedioxybenzene propiophenone with a GC purity of > 99%.
  • the methylenedioxybenzene propiophenone along with 125 g of isopropyl alcohol, 0. lg of sodium bicarbonate and 4.0 g of Raney Nickel catalyst were charged in a 1 liter autoclave.
  • the mixture was hydrogenated under 100 p.s.i. hydrogen pressure at 110°C till the unreacted MDP was reduced to less than 0.5% by GC analysis.
  • the catalyst was separated by filtration and the crude was distilled to obtain 75 g of a-ethyl-l,3-benzodioxole-5-methanol with purity of >99% by GC analysis.
  • the a-ethyl-l,3-benzodioxole-5-methanol along with 200 g of toluene and 0.5g of 4-methyl benzenesulfonic acid (PTSA) was refluxed at 95°C in a Dean-Stark apparatus for 2 hrs.
  • the organic layer was subjected to aqueous workup to remove PTSA, and distilled to obtain 65 g of isosafrole with a yield of 105% (wt./wt. on 1,3-benzodioxole consumed) and purity of > 99% by GC analysis.
  • the reaction mass was subjected to aqueous workup to remove Zinc chloride and butanoic acid and the organic layer was separated and distilled to recover 65 g of unreacted 1,3-benzodioxole and 75 g of l-(l,3-benzodioxol-5-yl)-l-butanone with a GC purity of > 99%.
  • the l-(l,3-benzodioxol-5-yl)-l-butanone was subjected to selective reduction and dehydration as discussed in Example 2 to obtain 66 g of 5-butyl-l,3-benzodioxole with a yield of 115.8% (wt./wt. on 1,3-benzodioxole consumed) and purity of > 99% by GC analysis.
  • reaction mass was subjected to aqueous workup to remove Zinc chloride and propionic acid and the organic layer was separated and distilled to recover 85 g of unreacted 1 ,4-benzodioxane and 62 g of ethyl enedioxybenzene propiophenone with a GC purity of > 99%.
  • the ethyl enedioxybenzene propiophenone was subjected to selective reduction and dehydration as discussed in example 2 to obtain 53 g of 6-propyl-l,4-benzodioxane with a yield of 104% (wt./wt. on 1 ,4-benzodioxane consumed) and purity of > 99% by GC analysis.
  • the present disclosure provides process(es) to overcome the problems associated with conventional process(es) for the acylation of alkylenedioxybenzene compound(s). [0083] The present disclosure provides a process for the acylation of alkylenedioxybenzene compounds without substantial degradation of the alkylenedioxybenzene or acylated products formed therefrom.
  • the present disclosure provides a process for the acylation of alkylenedioxybenzene compounds that substantially reduces the amount of Lewis acid, such as Zinc chloride, required as catalyst.
  • the present disclosure provides a process for the acylation of alkylenedioxybenzene compounds to obtain the acyl compound of Formula IV in high yield (greater than 100% wt./wt. on the alkylenedioxybenzene consumed).
  • the present disclosure provides a process for the acylation of alkylenedioxybenzene compounds to obtain the acylated product of Formula IV with high purity (greater than 99% by GC analysis).
  • the present disclosure provides an efficient process for preparation of alkyl and alkylene derivatives of alkylenedioxybenzene compounds without substantial degradation of any of the starting compound(s) and the desired product during the course of reaction.

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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 d'une manière générale, un procédé de préparation des composés de formule (IV). Un aspect de la présente invention concerne un procédé de préparation d'un composé de formule IV, ledit procédé comprenant l'étape consistant à faire réagir un composé alkylènedioxybenzène de formule II avec un halogénure d'acyle de formule III en présence d'un solvant, caractérisée en ce que l'étape de réaction du composé alkylènedioxybenzène de formule II avec l'halogénure d'acyle de formule III est effectuée en présence d'un oxyde amphotère de manière à tremper in situ le composé de formule H-X formé au cours de la réaction, ce qui permet d'éliminer sensiblement la dégradation des composés de formule IV et de formule II.
PCT/IB2017/052230 2017-02-14 2017-04-19 Procédé de préparation de dérivés alcényle et alkyle d'alkylènedioxybenzène WO2018150230A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021161083A1 (fr) * 2020-02-13 2021-08-19 Anthea Aromatics Private Limited Procédé efficace pour la préparation de dérivés acyle d'alkylènedioxybenzènes
WO2022162223A1 (fr) 2021-01-29 2022-08-04 Endura S.P.A. Procédé de préparation de 3,4-méthylènedioxypropiophénone

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021161083A1 (fr) * 2020-02-13 2021-08-19 Anthea Aromatics Private Limited Procédé efficace pour la préparation de dérivés acyle d'alkylènedioxybenzènes
WO2022162223A1 (fr) 2021-01-29 2022-08-04 Endura S.P.A. Procédé de préparation de 3,4-méthylènedioxypropiophénone

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