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WO2018104208A1 - Procédé de clivage d'acide oléique et/ou de ses dérivés - Google Patents

Procédé de clivage d'acide oléique et/ou de ses dérivés Download PDF

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Publication number
WO2018104208A1
WO2018104208A1 PCT/EP2017/081321 EP2017081321W WO2018104208A1 WO 2018104208 A1 WO2018104208 A1 WO 2018104208A1 EP 2017081321 W EP2017081321 W EP 2017081321W WO 2018104208 A1 WO2018104208 A1 WO 2018104208A1
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WIPO (PCT)
Prior art keywords
oleic acid
acid
hydrogen peroxide
derivatives
cleaving
Prior art date
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Ceased
Application number
PCT/EP2017/081321
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English (en)
Inventor
Uday RAZDAN
Mayuri SHAIWALE
Gururajan Padmanaban
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Solvay SA
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Solvay SA
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Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Publication of WO2018104208A1 publication Critical patent/WO2018104208A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds

Definitions

  • the present disclosure relates to a method of cleaving unsaturated fatty acids, more precisely oleic acid, and/or derivatives thereof.
  • the present disclosure further relates to a method of producing long chain carboxylic acids.
  • Long chain carboxylic acids find a wide range of applications in various chemical industries, such as, pharmaceuticals, and agrochemicals. Preparation of long chain carboxylic acids is a challenging task due to high unpredictability of chemical arts. One of the most common and successful techniques for the preparation of long chain carboxylic acid is by way of oxidative cleavage of unsaturated fatty acids.
  • This method involves the cleavage of the double bond of unsaturated fatty acids by means of a strong oxidant resulting into two saturated fatty acid molecules.
  • this technique such as low selectivity, low yield, and lower than expected level of mass transfer from one medium to another.
  • Selectivity in cleavage is one of the major issues related to the oxidative cleavage technique as all the unsaturated portions of the fatty acids are broken down irrespective of the desired product which in turn reduces the yield of the desired product.
  • C 104447279 discloses a method for synthesizing azelaic acid starting from oleic acid and using a combination of hydrogen peroxide and potassium permanganate.
  • the method comprises the steps of mixing oleic acid, a phosphotungstic acid catalyst, and benzyl triethyl ammonium chloride as phase transfer catalyst, followed by introduction of oxygen and further addition of potassium permanganate, and hydrogen peroxide solution to the reaction mixture.
  • the method described in the aforementioned document uses a combination of potassium permanganate and oxygen as oxidants in addition to hydrogen peroxide.
  • US5939572 teaches a method of contacting an olefinic compound or a vicinal dihydroxy compound with oxygen in the presence of a protic organic solvent, an inorganic oxide catalyst and a peroxidant such as hydrogen peroxide or a peralkanoic acid.
  • the inorganic oxide catalyst is selected from an oxide of tungsten, molybdenum, niobium, vanadium, tantalum, titanium, or yttrium. To achieve the desired product, this prior art method uses a very high amount of protic solvent.
  • salts includes a compound that results from the neutralization reaction of unsaturated fatty acid and a base.
  • the base includes both inorganic base for example alkali metal (e.g. sodium or potassium) and alkali earth metal (e.g. calcium or magnesium) hydroxides and organic bases, for example alkyl amines, arylalkyl amines, and heterocyclic amines.
  • esters includes an organic compound obtained by the replacement of the hydrogen of the unsaturated fatty acid by an alkyl or other organic group for example aryl, cycloalkyl, heteroaryl which can be further substituted.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature range of about 60°C to about 100°C should be interpreted to include not only the explicitly recited limits of about 60°C to about 100°C, but also to include sub-ranges, such as 65°C to 95°C, 80°C to 100°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 65.2°C, 85.6°C, and 96.3°C, for example.
  • reaction media as in the present invention, the decomposition of hydrogen peroxide results in substantial enrichment of oxygen (0 2 ). Bubbles of oxygen bursting at the surface of the reaction medium in turn produce an electrostatic field sufficient to ignite protic solvents/flammable solvents. Each bubble bursting at the surface is oxygen rich and solvent saturated and thus is extremely sensitive to ignition.
  • prior art teaches to include both the hydrogen peroxide as oxidant and the presence of high amount of organic solvent.
  • the present disclosure provides a safe and economical method for cleaving unsaturated fatty acids to obtain long chain carboxylic acids.
  • the present disclosure provides an oxidative cleavage of olefinic group to acid functionality for the synthesis of aliphatic diacids from unsaturated a fatty acid using a stoichiometric amount of hydrogen peroxide.
  • Aliphatic diacids are widely used for making polyamides, polyesters, plasticizers, etc.
  • the catalytic oxidation of the olefin group can be carried out in a single step using oxygen/ hydrogen peroxide in two-phase reaction employing phase-transfer catalyst.
  • oleic acid can be oxidized to azelaic acid and nonanoic acid.
  • the present disclosure thus provides a one step process involving benign reagents.
  • Hydrogen peroxide can be used in stoichiometric amounts, overcoming the issue associated with recycling or disposal of residual hydrogen peroxide.
  • the process can be used for synthesizing diacids from a naturally available fatty acid.
  • the present disclosure relates to a method of cleaving oleic acid, and/or derivatives thereof, the method comprising oxidatively cleaving oleic acid, and/or derivatives thereof with oxygen, hydrogen peroxide, tungstic acid as catalyst, methyltrioctylammonium chloride as phase transfer catalyst, and a solvent in an amount from 0 to 30 wt % with respect to the oleic acid, and/or derivatives thereof resulting in the oxidative cleavage of the oleic acid, and/or derivatives thereof.
  • the Applicant has namely found out that working in these conditions allows reaching high yields of azealic and nonanoic acid without using potassium permanganate or an organic solvent and using low amounts of hydrogen peroxide (about the stoichiometric amount).
  • the derivatives of oleic acid are salts, and/or esters thereof.
  • the tungstic acid catalyst is used in an amount from 1 to 5 mole % with respect to the oleic acid.
  • the hydrogen peroxide to oleic acid molar ratio is in the range from 2: 1 to 8 : 1. In a preferred implementation, the molar ratio of the peroxide compound to oleic acid is about 2: 1.
  • the solvent may be chosen from polar or non-polar solvents.
  • Non-polar solvents may be chosen in the group constituted by 1 ,4 dioxane and chloroform.
  • Polar solvents may be chosen from protic solvents like t-butanol, acetic acid, propionic acid and aprotic solvents like acetone, dichloromethane and diglyme.
  • the solvent is t-butanol.
  • a solvent is used in an amount from 0 to 10 wt % with respect to the oleic acid.
  • the present disclosure relates to a method oxidatively cleaving oleic acid, and/or derivatives thereof with oxygen, hydrogen peroxide, tungstic acid, methyltrioctylammonium chloride, and t-butanol in an amount from 0 to 10 wt % with respect to oleic acid resulting in the oxidative cleavage of the oleic acid, and/or derivatives thereof.
  • the present disclosure relates to a method oxidatively cleaving oleic acid, and/or derivatives thereof with hydrogen peroxide, tungstic acid, methyltrioctylammonium chloride, and t-butanol in an amount from 0 to 10 wt % with respect to oleic acid with of bubbling of oxygen resulting in the oxidative cleavage of the oleic acid, and/or derivatives thereof.
  • Example 1 (according to the invention):
  • Example 2 (according to the invention):
  • Example 3 (according to the invention): The apparatus described in Example 1 was loaded with the same quantities of reagents except that 30wt % of solvent (t-BuOH) was added. A yield of 72 % for Azelaic acid and a yield of 61 % for nonanoic acid were obtained.
  • solvent t-BuOH
  • Example 1 The apparatus described in Example 1 was loaded with the same quantities of reagents except that no methyltrioctyl ammonium chloride is added. Reaction did not take place and azelaic acid and nonanoic acid were not obtained.
  • Example 1 The apparatus described in Example 1 was loaded with the same quantities of reagents except that 7.0 wt % of solvent (t-BuOH) was added. Yields of 80 % Azelaic acid and 62 % nonanoic acid were obtained.
  • solvent t-BuOH
  • Example 6 (Comparative Example):
  • Example 2 Set-up was made same as in Example 1. To 5.0 g oleic acid were added tungstic acid (2.5 mole % w.r.t oleic acid) and methyltrioctylammonium chloride (brand name Aliquat®336; 2.0 mole % w.r.t oleic acid). To this hydrogen peroxide 5.0 mole/mole w.r.t oleic acid was added drop-wise. Yields of 91 % Azelaic acid and 72 % nonanoic acid were obtained.
  • tungstic acid 2.5 mole % w.r.t oleic acid
  • methyltrioctylammonium chloride brand name Aliquat®336; 2.0 mole % w.r.t oleic acid
  • Example 6 which is a comparative Example not using oxygen excess hydrogen peroxide as oxidant is required along with phase transfer catalyst.
  • Example 6 The apparatus described in Example 6 was loaded with the same quantities of reagents except that the catalyst tungstic acid was replaced with phosphotungstic acid and 2.0 mole % methyltrioctylammonium chloride was replaced by 6.0 mole % methyltrioctylammonium chloride. Yields of 66.8 % Azelaic acid and 67.4 % nonanoic acid were obtained.
  • Example 8 (Comparative Example) Set-up was made same as in Example 1. To 5.0 g oleic acid were added tungstic acid (8.58 mole % w.r.t oleic acid) and 8 ml/g (625 wt %) solvent (t-BuOH). Oxygen was bubbled through the reaction mass and temperature was raised to 60°C. To this hydrogen peroxide 2.0 mole/mole w.r.t oleic acid was added drop-wise. Yields of 93.2 % Azelaic acid and 4.9 % nonanoic acid were obtained.
  • This process was using the combination of hydrogen peroxide and oxygen as oxidant, thus reducing the amount of hydrogen peroxide. It was however performed in absence of a phase transfer catalyst, thereby requiring an increased amount the catalyst. This yielded azelaic acid in good yield but the yield of nonanoic acid dropped. Further, this process involved usage of high amount of protic solvent, i.e., 625 wt %, which has an inherent disadvantage in that above 75°C the mixture of t-butanol/oxygen vapours enter explosive regime. Therefore, this process, though reducing the amount of hydrogen peroxide required, was still not viable and economical.
  • the present disclosure thus provides an economical method which is a one-step 5 process involving benign reagents. Hydrogen peroxide is used in equivalent (stoichiometric) proportion, overcoming the issue of recycling or disposal of residual hydrogen peroxide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de clivage de l'acide oléique et/ou de ses dérivés, le procédé comprenant le clivage par oxydation de l'acide oléique et/ou de ses dérivés avec de l'oxygène, du peroxyde d'hydrogène, un catalyseur, un catalyseur de transfert de phase et un solvant en une quantité de 0 à 30 % en poids par rapport à l'acide oléique, et/ou des dérivés de celui-ci.
PCT/EP2017/081321 2016-12-07 2017-12-04 Procédé de clivage d'acide oléique et/ou de ses dérivés Ceased WO2018104208A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201621041887 2016-12-07
IN201621041887 2016-12-07

Publications (1)

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WO2018104208A1 true WO2018104208A1 (fr) 2018-06-14

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711523A (en) * 1970-09-04 1973-01-16 Procter & Gamble Oxidation of vicinal glycols in the presence of organic peroxides and cobaltous compounds
US5939572A (en) 1995-06-05 1999-08-17 North Dakota State University Research Foundation Method for preparation of carboxylic acids
CN1680253A (zh) * 2005-02-03 2005-10-12 中国科学院新疆理化技术研究所 一种催化氧化体系制备壬二酸的方法
WO2013092353A1 (fr) * 2011-12-20 2013-06-27 Dsm Ip Assets B.V. Procédé de préparation de l'acide azéléique à partir de l'acide 9-octadécènedioïque
CN104447279A (zh) 2014-12-05 2015-03-25 辽宁石油化工大学 一种过氧化氢和高锰酸钾联合氧化合成壬二酸的方法
US9035079B2 (en) 2011-12-01 2015-05-19 Arkema France Method for cleaving unsaturated fatty chains

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711523A (en) * 1970-09-04 1973-01-16 Procter & Gamble Oxidation of vicinal glycols in the presence of organic peroxides and cobaltous compounds
US5939572A (en) 1995-06-05 1999-08-17 North Dakota State University Research Foundation Method for preparation of carboxylic acids
CN1680253A (zh) * 2005-02-03 2005-10-12 中国科学院新疆理化技术研究所 一种催化氧化体系制备壬二酸的方法
US9035079B2 (en) 2011-12-01 2015-05-19 Arkema France Method for cleaving unsaturated fatty chains
WO2013092353A1 (fr) * 2011-12-20 2013-06-27 Dsm Ip Assets B.V. Procédé de préparation de l'acide azéléique à partir de l'acide 9-octadécènedioïque
CN104447279A (zh) 2014-12-05 2015-03-25 辽宁石油化工大学 一种过氧化氢和高锰酸钾联合氧化合成壬二酸的方法
CN104447279B (zh) * 2014-12-05 2016-05-18 辽宁石油化工大学 一种过氧化氢和高锰酸钾联合氧化合成壬二酸的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Practical dihydroxylation and C-C cleavage of unsaturated fatty acid", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 150, - 1999, pages 105 - 111
ANTONELLI ERMANNO ET AL: "Efficient Oxidative Cleavage of Olefins to Carboxylic Acids with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phospate(3-9 under Two-Phase Conditions. Synthetic Aspects and Investigation of the Reaction Course", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 63, 1 January 1998 (1998-01-01), pages 7190 - 7206, XP002142961, ISSN: 0022-3263, DOI: 10.1021/JO980481T *

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