EP3969434A1 - Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol - Google Patents

Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol

Info

Publication number
EP3969434A1
EP3969434A1 EP20724855.0A EP20724855A EP3969434A1 EP 3969434 A1 EP3969434 A1 EP 3969434A1 EP 20724855 A EP20724855 A EP 20724855A EP 3969434 A1 EP3969434 A1 EP 3969434A1
Authority
EP
European Patent Office
Prior art keywords
eugenol
weight
equal
stabilizing compound
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20724855.0A
Other languages
English (en)
French (fr)
Inventor
Valéry DAMBRIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Specialty Operations France SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR1905219A external-priority patent/FR3096050B1/fr
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP3969434A1 publication Critical patent/EP3969434A1/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/46—Use of additives, e.g. for stabilisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a process for the purification of eugenol and to novel compositions comprising Teugenol.
  • Document CN 105294409 indicates a purification process in which eugenol is purified using n-octane and K 2 CO 3 , the mixture is filtered, then washing with water of the K 2 CO 3 is carried out and finally l purified eugenol is distilled from the aqueous phase.
  • the present invention relates to the efficient and selective manufacture of eugenol, in particular a process allowing the separation of eugenol and orthoeugenol, on an industrial scale, efficiently and under good safety conditions.
  • a first object of the present invention relates to a novel process for the purification of eugenol in which a crude eugenol is distilled in the presence of at least one stabilizing compound.
  • the present invention also relates to a process for separating G eugenol and orthoeugenol by distillation in the presence of at least one stabilizing compound.
  • phenol derivative represents a compound comprising a unit corresponding to formula (III):
  • R represents a hydroxyl, a linear or branched alkyl, preferably comprising between 1 and 6 carbon atoms, alkenyl, an alkoxy group, preferably comprising between 1 and 6 carbon atoms, a nitro group, or a nitroso group
  • R2 represents an alkyl linear or branched, preferably comprising between 1 and 6 carbon atoms and n is between 0 and 5, preferably n is equal to 0, 1, 2 or 3.
  • the group R is chosen from the group consisting of hydroxyl , methyl, ethyl, propyl, n-butyl, t-butyl, methoxy, ethoxy, propoxy, iso-propoxy, nitro, nitroso.
  • the group R2 is chosen from methyl, ethyl, propyl, n-butyl, t-butyl.
  • a phenol derivative can be chosen from compounds of the tocopherol family, in particular ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, d-tocopherol.
  • phenothiazine derivative refers to compounds comprising the unit according to formula (V):
  • TEMPO (2,2,6,6-tetramethylpiperidin-l-yl) oxy
  • TEMPO-OH (4-hydroxy-2,2,6,6-tetramethylpiperidin-l-yl) oxy
  • au (4-Oxo-2,2,6,6-tetramethyl-1 -piperidin-1-yl) oxy
  • 4-Amino-2,2,6, 6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO)
  • Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Bishydroxy TEMPO sebacate).
  • stabilizer refers to a compound capable of maintaining the qualities of a product without affecting said product, such as coloring, chemical or thermal stability, in particular during manufacture, storage or. handling of the product.
  • the crude eugenol according to the present invention may contain impurities, in particular linked to the process for synthesizing T eugenol, such as o-eugenol, or product of O-alkylation of guaiacol or of G eugenol, the impurities may also from the starting compounds used in the reaction.
  • the content by weight of each impurity present in the composition relative to the weight of the composition is less than the content of eugenol in the composition.
  • purified eugenol refers to a composition comprising essentially of G eugenol, in particular comprising at least 80% of eugenol, preferably at least 90% by weight of eugenol, even more preferably. at least 95% by weight and even more preferably at least 99% by weight relative to the weight of the composition.
  • eugenol is obtained from guaiacol and allyl halide, preferably allyl chloride as described in document FR 2302991.
  • the alkylation reaction is carried out. in the presence of an aqueous solution of an alkali metal, or of an alkaline earth metal hydroxide, such as NaOH or KOH.
  • the reaction can be carried out in the presence of a catalyst, in particular a copper-based catalyst such as CuCl, CuCl 2 .2I3 ⁇ 4C), Cu (N03) 2, Cu (OAc) 2 .2I3 ⁇ 4C).
  • the reaction can also be carried out in the presence of a composite catalyst as described in patent application CN 105294409.
  • the amount of catalyst is greater than or equal to 0.01% by weight, preferably greater than or equal to 0.02% by weight, more preferably greater than or equal to 0.05% by weight, and very preferably greater than or equal to 0.1% by weight relative to the amount of guaiacol.
  • the amount of catalyst is less than or equal to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 2% by weight, and very preferably greater than or equal to 1% by weight relative to to the amount of guaiacol.
  • the reaction is generally carried out in the presence of an ammonium or ammonia salt as described in document FR 2302991.
  • the ammonia can form with the catalyst a copper-amine type complex.
  • a first object of the present invention relates to a process for purifying a crude eugenol by distillation in the presence of at least one stabilizing compound.
  • the present invention relates to a process for purifying a crude eugenol by distillation in the presence of at least one stabilizing compound and / or an auxiliary compound.
  • the object of the present invention is in particular to:
  • At least one stabilizing compound is chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO derivatives, CB (copper dibutyl dithiocarbamate), para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese (II) acetate, sodium nitrite, sodium or potassium ascorbate or glutathione.
  • the at least one stabilizing compound is selected from the group consisting above further comprising bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the at least one stabilizing compound is chosen from a group according to the first aspect or according to the second aspect or according to the third aspect or a group according to the fourth aspect, said group further comprising bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate.
  • At least one stabilizing compound is chosen from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), tert-butylcatechol (TBC), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , sodium ascorbate, tert-butylhydroquinone (TBHQ), para-methoxyphenol (PMP) or glutathione.
  • the purification process is carried out in the presence of a stabilizer.
  • the inventors have surprisingly discovered that the addition of at least one stabilizing compound during the distillation of crude eugenol makes it possible to move the temperature zone towards which the thermal decomposition takes place. initiates to prevent the distillation process from being unstable or even explosive.
  • the method according to the present invention can be operated under appropriate safety conditions.
  • the purification process is carried out in the presence of at least one stabilizing compound chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate) derivatives, para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese (II) acetate, sodium nitrite, sodium or potassium ascorbate or glutathione and optionally in the presence of at least one auxiliary compound chosen from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
  • at least one stabilizing compound chosen from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate) derivatives, para-benzoquinone, para-phenylenediamine, diethyl
  • the at least one stabilizing compound is chosen from the above group further comprising bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the total amount of stabilizing compound is greater than or equal to 50 ppm, preferably greater than or equal to 100 ppm, more preferably greater than or equal to 500 ppm, and more preferably greater than or equal to 1000 ppm relative to the amount of eugenol.
  • the at least one stabilizing compound is added to the distillation boiler.
  • the at least one stabilizing compound is chosen from stabilizing compounds having a boiling point higher than that of eugenol, preferably the boiling point of the stabilizing compound is greater than or equal to T eu + 1 ° C, preferably greater than or equal to T eu + 5 ° C, more preferably greater than or equal to T eu + 10 ° C.
  • the at least one stabilizing compound is added to the distillation column.
  • the at least one stabilizing compound can be chosen from stabilizing compounds having a boiling point higher than that of eugenol.
  • the at least one stabilizing compound can be chosen from stabilizing compounds having a boiling point less than or equal to that of G eugenol, preferably the boiling point of the stabilizing compound is less than or equal to T eu ⁇ 1 ° C. , preferably less than or equal to T eu -5 ° C, more preferably less than or equal to T eu -10 ° C.
  • the distillation is carried out using TBC and PMP.
  • the TBC is added to the still boiler and the PMP to the still column.
  • TBC and PMP are added to the still boiler.
  • the distillation is carried out at a temperature greater than or equal to 90 ° C, preferably greater than or equal to 100 ° C and very preferably greater than or equal to 110 ° C, and even more preferably greater than or equal to 120 ° C.
  • the distillation is carried out at a temperature less than or equal to 200 ° C, preferably less than or equal to 190 ° C and very preferably less than or equal to 180 ° C, and even more preferably less than or equal to 150 ° vs.
  • the distillation also makes it possible to separate the excess of guaiacol, the products of O-alkylation of eugenol and / or of guaiacol and of ortho-eugenol.
  • the guaiacol used in the preparation of eugenol can also contain certain impurities such as veratrole or 6-methyl guaiacol, the reaction mixture obtained at the end of the allylation reaction can also contain allylation products of said impurities, in particular allyl-veratrole or 4-allyl-6-methylguaiacol.
  • the reaction mixture obtained at the end of the allylation reaction can also contain isomerization products of the allyl group, in particular isoeugenol or meta-eugenol (also known under the name of 2-methoxy-5 - (prop-2-en-1-yl) phenol).
  • the eugenol obtained at the end of the distillation contains an amount greater than or equal to 0.01% by weight, preferably greater than or equal to 0.05% by weight, and even more preferably greater than or equal to 0.1% by weight of ortho-eugenol relative to the total weight of the composition
  • the process according to the present invention allows in particular the separation of G eugenol and guaiacol.
  • the process according to the present invention allows the preparation of eugenol having satisfactory organoleptic properties.
  • eugenol obtained according to the process of the invention exhibits organoleptic properties similar to those of eugenol obtained by extraction of a natural product.
  • the present invention relates to a process for the preparation of eugenol which comprises a purification process as defined above.
  • the process for preparing eugenol generally includes a step of preparing a crude eugenol. This step can in particular be carried out as described in document LR 2302991, in particular by allylation of guaiacol.
  • the process for preparing eugenol comprises a second step in which the crude eugenol is purified by a method of purification by distillation in the presence of at least one stabilizing compound.
  • the present invention relates to the use of a stabilizer compound to stabilize a eugenol purification process.
  • the present invention relates to a composition
  • a composition comprising eugenol and between 0.1 and 10,000 ppm of at least one stabilizing compound or at least one stabilizing compound and at least one auxiliary compound, in which the stabilizing compound is selected from the group consisting of phenol derivatives, phenothiazine derivatives, TEMPO, CB (copper dibutyl dithiocarbamate), para-benzoquinone, para-phenylenediamine, diethylhydroxylamine, manganese acetate (II ), sodium nitrite, sodium or potassium ascorbate or glutathione and the auxiliary compound is selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
  • the above composition further comprises bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the total amount of stabilizing compound in the composition is greater than or equal to 0.1 ppm, preferably greater than or equal to 1 ppm, more preferably greater than or equal to 10 ppm, and more preferably greater than or equal to 100 ppm relative to the amount of eugenol.
  • the total amount of stabilizing compound is less than or equal to 10,000 ppm, preferably less than or equal to 5000 ppm, more preferably less than or equal to 2000 ppm, more preferably less than or equal to 1000 ppm, and even more preferably less than or equal to 500 ppm relative to the amount of eugenol.
  • the total amount of auxiliary compound is greater than or equal to 0 ppm, preferably greater than or equal to 0.1 ppm, more preferably greater than or equal to 1 ppm, and more preferably greater than or equal to 10 ppm relative to to the amount of eugenol.
  • the total amount of auxiliary compound is less than or equal to 5000 ppm, preferably less than or equal to 2500 ppm, more preferably less than or equal to 2000 ppm, and more preferably less than or equal to 1000 ppm relative to the amount of eugenol.
  • At least one stabilizing compound is a compound of formula (IV) or phenothiazine (PTZ) in particular chosen from the group as constituted above additionally comprising bis (2,2,6,6-tetramethyl- 4-piperidyl) sebacate.
  • the composition according to the invention comprises a stabilizing compound. According to another particular aspect, the composition according to the invention comprises two stabilizing compounds.
  • the composition according to the invention comprises at least one stabilizing compound chosen from the group consisting of T hydroquinone (HQ), para-methoxyphenol (PMP), tert-butylcatechol (TBC), phenothiazine (PTZ ) and at least one auxiliary compound, selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
  • HQ T hydroquinone
  • PMP para-methoxyphenol
  • TBC tert-butylcatechol
  • PTZ phenothiazine
  • at least one auxiliary compound selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).
  • the composition according to the invention comprises at least one stabilizing compound chosen from the group consisting of 2,4-dimethyl-6-tert-butylphenol (Topanol A), 2,4-dinitro-6-sec- butylphenol, 2-methyl-4,6-dinitrophenol, para-nitrosophenol, 2-methyl-4-nitrophenol and at least one auxiliary compound, selected from the group consisting of vitamin E, butyl-hydroxyanisole (BHA), dibutylhydroxytoluene (BHT) , tert-butylhydroquinone (TBHQ).
  • BHA butyl-hydroxyanisole
  • BHT dibutylhydroxytoluene
  • TBHQ tert-butylhydroquinone
  • the composition according to the present invention comprises at least 90% by weight of eugenol, preferably at least 95% by weight of eugenol, more preferably at least 99% by weight, even more preferably at least 99.5 % and even more preferably at least 99.95% by weight of eugenol relative to the total weight of the composition.
  • the content of ortho-eugenol in the composition is less than or equal to 10% by weight, preferably less than or equal to 8% by weight, very preferably less than or equal to 5% by weight and even more preferably less than or equal to 1% by weight relative to the weight of the composition.
  • the iso-eugenol content in the composition is less than or equal to 5% by weight, preferably less than or equal to 2% by weight, very preferably less than or equal to 1% by weight and even more preferably less than or equal to 0.5% by weight relative to the weight of the composition.
  • the present invention finally relates to a composition
  • a composition comprising at least 90% by weight of eugenol and up to 10% by weight of ortho-eugenol relative to the total weight of the composition.
  • the composition comprises at least at least 95% by weight of eugenol, more preferably at least 99% by weight and even more preferably at least 99.5% by weight of eugenol relative to the total weight of the composition.
  • the orthoeugenol content in the composition is less than or equal to 10% by weight, preferably less than or equal to 8% by weight, very preferably less than or equal to 5% by weight and even more preferably less than or equal to 1% by weight relative to the weight of the composition.
  • the inventors have discovered that the compositions according to the present invention exhibit satisfactory organoleptic properties.
  • the compositions according to present invention have organoleptic properties similar or at least equivalent to those of eugenol obtained by extraction of a natural product.
  • compositions according to the present invention can be used in perfumery or in aromatic, analgesic, antibacterial or antioxidant compositions.
  • the compositions according to the present invention exhibit properties suitable for their use in perfumery or in aromatic, analgesic, antibacterial or antioxidant compositions, in particular in terms of organoleptic properties.
  • Table 2 indicates that in the absence of a stabilizing compound, the thermal decomposition of eugenol begins at 275 ° C releasing 398J / g.
  • Examples 2 to 9 indicate that in the presence of a stabilizing compound, the thermal decomposition of eugenol is initiated above 285 ° C and releases a significantly lower amount of energy, thus making it possible to operate. distillation process under suitable safety conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP20724855.0A 2019-05-17 2020-05-14 Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol Pending EP3969434A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1905219A FR3096050B1 (fr) 2019-05-17 2019-05-17 Procede de purification d’eugenol et nouvelles compositions comprenant de l’eugenol
EP19200216 2019-09-27
PCT/EP2020/063521 WO2020234123A1 (fr) 2019-05-17 2020-05-14 Procede de purification d'eugenol et nouvelles compositions comprenant de l'eugenol

Publications (1)

Publication Number Publication Date
EP3969434A1 true EP3969434A1 (de) 2022-03-23

Family

ID=70617138

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20724855.0A Pending EP3969434A1 (de) 2019-05-17 2020-05-14 Verfahren zur reinigung von eugenol und neuartige zusammensetzungen mit eugenol

Country Status (5)

Country Link
US (1) US20220234979A1 (de)
EP (1) EP3969434A1 (de)
JP (1) JP2022532779A (de)
CN (1) CN113840819A (de)
WO (1) WO2020234123A1 (de)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1030558A (en) 1974-08-16 1978-05-02 Robert S. Desimone Process for the selective allylation of ortho alkoxy phenols
FR2302991A1 (fr) 1975-03-07 1976-10-01 Ube Industries Procede pour la preparation d'ortho-alcoxy-para-allylphenols
WO2007015260A2 (en) * 2005-04-19 2007-02-08 Camlin Fine Chemicals Ltd. Improvement in synthesis of butylated hydroxyanisole from tertiary butyl hydroquinone
JP6027718B2 (ja) * 2005-11-30 2016-11-16 エーデン リサーチ ピーエルシー チモール、オイゲノール、ゲラニオール、シトラール、及びｌ−カルボンから選択されたテルペン又はテルペン混合物を含む組成物及び方法
EP2709977B1 (de) * 2009-10-06 2018-09-05 Basf Se Verwendung von benzotropolonderivaten als photostabile antioxidantien zur stabilisierung von körperpflege- und haushaltsprodukten
CN104326885A (zh) 2014-10-09 2015-02-04 广西壮族自治区林业科学研究院 一种从丁香罗勒油中提取高纯丁香酚的方法
CN105294409B (zh) 2015-09-15 2019-11-05 重庆欣欣向荣精细化工有限公司 一种丁香酚合成方法
CN105709140A (zh) * 2016-01-20 2016-06-29 吕红风 一种治疗过敏性肺炎的药物组合物及其制备方法
CN108383695B (zh) 2018-06-01 2021-03-05 重庆欣欣向荣精细化工有限公司 丁香酚的制备方法及其应用和制备得到的丁香酚

Also Published As

Publication number Publication date
WO2020234123A1 (fr) 2020-11-26
CN113840819A (zh) 2021-12-24
US20220234979A1 (en) 2022-07-28
JP2022532779A (ja) 2022-07-19

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