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WO2001038289A1 - Procede d'aceto-acetylation de composes nucleophiles - Google Patents

Procede d'aceto-acetylation de composes nucleophiles Download PDF

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Publication number
WO2001038289A1
WO2001038289A1 PCT/FI2000/001031 FI0001031W WO0138289A1 WO 2001038289 A1 WO2001038289 A1 WO 2001038289A1 FI 0001031 W FI0001031 W FI 0001031W WO 0138289 A1 WO0138289 A1 WO 0138289A1
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Prior art keywords
acid
reaction
alkyl
solvent
amine
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PCT/FI2000/001031
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English (en)
Inventor
Tiina Lilja
Mervi YLÄ-JARKKO
Salme Koskimies
Petri MÄKIPEURA
Nina Heiskanen
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Neste Chemicals Oy
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Neste Chemicals Oy
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Priority to AU18666/01A priority Critical patent/AU1866601A/en
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Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes

Definitions

  • the present invention relates to a method for acetoacetylation of nucleophilic compounds, particularly of hydroxy functional nucleophilic compounds with alkyl ketene dimers (AKD).
  • the nucleophile is contacted with an alkyl ketene dimer either in the presence of a solvent, or without a solvent, optionally in the presence of a catalyst.
  • Asetoacetate functionality is commonly utilized in the coating industry for crosslink- ing reactions. Coating made of acetoacetylated polymers have several improved properties in comparison with coatings obtained from the corresponding non- acetoacetylated polymers. Reactions favourable for the crosslinking of the acetoace- tylated polymers include reactions with activated olefins (the so-called Michael reaction), polyamines, melamines, and isocyanates. These reactions are rapid, they proceed at low temperatures, and are typically used for the curing of coatings, for instance. As disadvantages accompanying these methods may be mentioned the isocya- nate or epoxy type curing systems that are detrimental to health.
  • acetoacetyla- tion methods useful in industrial scale have been developed and one of the best known is described in EP-376859 Al relating to the acetoacetylation of nucleophiles with ⁇ -dicarbonyl compounds, wherein the acetoacetylation runs via transesterifica- tion.
  • the alcohol formed as a by-product must be separated by distillation.
  • a solvent is used for the removal of the alcohol from the reaction mixture.
  • the solvent is usually selected to form an azeotropic mixture with the alcohol cleaved off, thus facilitating the removal of this alcohol by-product by distillation from the reaction mixture.
  • nucleophilic compounds is carried out with alkyl ketene dimers.
  • a nucleophile is contacted with an alkyl ketene dimer or a mixture of alkyl ketene dimers either in the presence of a solvent, or without a solvent, and optionally in the presence of a catalyst.
  • the alkyl ketene dimers used as starting materials may be produced by dehydrohalogenation of fatty acid halides in the presence of a tertiary amine, and an inert solvent.
  • Straight chain or branched, saturated or unsatu- rated fatty acids suitable for such dehydrohalogenation reactions include C -C 20 fatty acids such as isostearic acid, decanoic acid, oleic acid, caprylic acid, palmitic acid, stearic acid, as well as the commercial tall oil fatty acid mixture and commercial vegetable oil fatty acid mixture.
  • alkyl ketene dimers prepared by means of the dimeriza- tion of ketene may be used as the reagents for the asetoacetylation of the nucleophiles.
  • the ⁇ -lactone ring of the alkyl ketene dimer is opened as a result of the nucleophilic attac, and acetoacetate is obtained as the product.
  • Suitable nucleophiles to be acetoacetylated with alkyl ketene dimers include hydroxy functional saturated and unsaturated polyesters, primary and secondary polyols with the structure HO-R-OH and R(OH) n , R representing a straight or branced chain alkyl, alkenyl, alkynyl, or allyl group, and n being more that 2, preferably 2 - 4.
  • nucleophiles comprising a hydroxy group examples include 1 ,4-butanediol, 2-butyl- 2-ethyl-l,3-propanediol (BEPD), trimethylol propane (TMP), 2,2-dimethyl-l,3- propanediol (NPG), 1 ,6-hexanediol (HD), ethylene glycol (EG), propylene glycol
  • PG ethyl hexanediol
  • PE pentaerythritol
  • Curing reaction may further be intensified by means of a crosslinking reaction by reacting a polyfunctional primary or secondary alkylamine having the structure H 2 N-R- NH 2 or H 2 N-R(R2NH 2 )-NH 2 , where the groups R and R 2 are identical or different alkenyl or alkyl groups, R and R 2 being suitably methyl, ethyl, octyl or a butyl group, with an acetylation product of a ketene dimer.
  • Compounds with the above structures may be exemplified with 1 ,2-diaminopropane and 4-aminomethyl-l,8-octane diamide. Post-curing with a crosslinking reaction is particularly advantageous in coating applications.
  • Scheme 2 generally shows the reaction between a hydroxy functional nucleophile (I) and an alkyl ketene dimer (AKD) resulting in alkyl acetoacetate ester (II) as the reaction product.
  • the group R is now a branched or straight chain saturated or unsaturated alkyl side chain having 1 - 8 carbons and the group Ri of the hydroxy functional nucleophile is a primary or secondary alkyl group.
  • alkyl ketene dimers and nucleophiles depends on the length of the alkyl side chains in the AKD used, and on the nucleophile used.
  • AKDs with shorter chains such as a AKD made from caprylic acid chloride, acetoacetylate the hydroxy functional nucleophiles more quickly than alkyl ketene dimers having longer alkyl side chains.
  • the reaction between alkyl ketene dimers having longer chains and nucleophiles may be accelerated by using catalysts such as tertiary amine catalysts, DMAP or 4-dimethyl amino pyridine.
  • catalysts accelerating the acetoacetylation include tetramethyl ganide, triethyl amine, trimethyl amine, triethanol amine, N,N'-tetramethyl diamino compounds such as trans-N,N' -tetramethyl diamino-2-butene and cis-N, -tetramethyl diamino-2-butene, sulphonic acids, alkali metal salts such as alkali metal halides and alkali metal sulfates, ⁇ -chlorinated car- boxylic acids, sulphonic acid salts, tertiary phosphines, carboxylic acid betaines and sulphonic acid betaines.
  • the increased reaction rate brought about by the catalyst also improves the selectivity of the reaction by reducing the amount of the reaction byproducts that are formed via hydrolysis and decarboxylation.
  • the method according to the invention for acetoacetylation of nucleophiles based on the acetoacetylating ability of alkyl ketene dimers may be carried out at a wide tem- perature range.
  • the reaction is typically carried out at a temperature from 25 to 150
  • reaction temperature may be controlled with the rate of addition of the nucleophile or AKD. Reaction times vary between 0.5 and 24 hours, depending on the acetoacetylating reagent and nucleophile used. An exothermal acetoacetylation reaction between the nucleophile and AKD will start immediately as the starting materials are contacted with one another.
  • the use of a solvent in the acetoacetylation method carried out with AKD is optional.
  • a solvent is, however, preferable when hydroxy functional unsaturated or saturated polyesters, or nu- cleophiles with a very high melting point are acetoacetylated.
  • acetoacetates nearly any inert polar and non-polar organic solvent is a suitable optional solvent, including butyl acetate, ethyl acetate, methyl ethyl ketone and cyclo- hexanol.
  • a catalyst is not necessary for the successive acetoacetylation, the use thereof is favourable for the selectivity and rate of the reaction when nucleophiles are acetoacetylated by means of alkyl ketene dimers having longer, branched or straight chain saturated or unsaturated alkyl side chains.
  • the amount of the catalyst to be added depends on the catalyst used. Preferably, the catalyst is added in an amount from 0.01 to 0.10 mmol per millimole of the nucleophile. More prefera- bly, the catalyst is used in an amount of 1 % by weight or less, relative to the total amount of the reaction mixture.
  • the functionalization process of the invention is very simple and reactive. By con- trolling the structure of the AKD carbon chains (saturated/unsaturated), the solubility, viscosity and hardness properties of the product may be modified. It should especially be appreciated that no alcohol that should be removed separately is produced as a byproduct.
  • a catalyst is not necessarily needed in the process, but it may be carried out directly owing to the acetoacetylating ability of the alkyl ketene dimers. Since the acetoacetylation is based on the reaction between the nucleophile and AKD, the reaction mixture will not contain any alcohol that would be produced as a by-product in transacetoacetylation.
  • the acetoacetylation of the nucleophiles may be carried out without any need to distil alcohol off at the end of the synthesis.
  • the method of the invention for the acetoacetylation of nucleophiles may be carried out both without a solvent and in the presence thereof. Since the acetoacetylation by using an AKD does not produce any alcohol that would be cleaved off, the selection of the solvent for the acetoacetylation method of the invention is more simple. With the method of the invention, isocyanate and epoxy type curing systems detrimental to health may be replaced. Accordingly, the invention is directed to an alternative method to carry out rapid reactions at low temperatures, these reactions being typically used for instance for curing of coatings.
  • the solubility, viscosity and hardness properties of the product may be modified as desired.
  • post-curing may be intensified with crosslinking by means of polyfunctional amines.
  • the octanoic acid chloride was separated from the phosphrous acid precipitated on the bottom of the flask by decantation. Based on the NMR analysis of the reaction mixture, the yield of the octanoic acid chloride was 97.8 %.
  • the condenser comprised thereon a drying tube containing silica.
  • the reaction temperature was 45 °C.
  • the triethyl ammoniumhydrogenchloride salt formed therein was filtered off.
  • the solvent and any excess of triethyl amine were evaporated with a rotary evaporator. Based on the NMR analysis of the reaction mixture, the yield of the octyl ketene dimer was 97.3 %.
  • the oleic acid chloride was separated from the phosphrous acid precipitated on the bottom of the flask by decantation. Based on the NMR analysis of the reaction mixture, the yield of the oleic acid chloride was 95.0 %.
  • the condenser comprised thereon a drying tube containing silica.
  • the reaction temperature was 45 °C.
  • the triethyl ammoniumhydrogenchlo- ride salt formed therein was filtered off with suction.
  • the solvent and any excess of triethyl amine were evaporated with a rotary evaporator. Based on the NMR analysis of the reaction mixture, the yield of the oleyl ketene dimer was 97.2 %.
  • the isostearic acid chloride was separated from the phosphrous acid precipitated on the bottom of the flask by decantation. Based on the NMR analysis of the reaction mixture, the yield of the isostearic acid chloride was 93.3 %.
  • R being either -(CH 2 ) ] 5 CH 3 or -(CH 2 ) 13 CH 3
  • the mixture was boiled at about 116 °C under stirring with the magnetic stirrer for 18.0 h.
  • the mixture of alkyl ketene dimers prepared from 75 % of stearyl acid chloride and 25 % of pal- mityl acid chloride acetoacetylates 85.4 % of the 1,4-butanediol to form the aceto- acetate ester having the structural formula (9).
  • acetoacetate (12) (5.0 g; 75 % by weight) synthesized with an acetoacetylation reaction between an alkyl ketene dimer prepared from caprylic acid chloride and 2-butyl-2-ethyl-l,3-propanediol (BEPD), and 4-aminomethyl-l,8- octanediamide (13) (0.65 g) were mixed together. From this mixture of compounds, a thin film was formed on a primed sheet with an applicator, and thereafter, the film was treated in an oven at 150 °C for 4.0 hours. A curing reaction was clearly seen.

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

Abstract

Procédé d'acéto-acétylation de composés nucléophiles avec des dimères d'alkylcétènes. Selon le procédé, on met le nucléophile en contact avec un dimère d'alkylcétène soit en présence d'un solvant soit sans solvant, éventuellement en présence d'un catalyseur.
PCT/FI2000/001031 1999-11-25 2000-11-27 Procede d'aceto-acetylation de composes nucleophiles Ceased WO2001038289A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18666/01A AU1866601A (en) 1999-11-25 2000-11-27 Method for acetoacetylation of nucleophilic compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI19992519 1999-11-25
FI19992519A FI19992519A7 (fi) 1999-11-25 1999-11-25 Menetelmä nukleofiilisten yhdisteiden asetoasetyloimiseksi

Publications (1)

Publication Number Publication Date
WO2001038289A1 true WO2001038289A1 (fr) 2001-05-31

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FI (1) FI19992519A7 (fr)
WO (1) WO2001038289A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861060A (zh) * 2021-11-05 2021-12-31 江苏弘和药物研发有限公司 一种鞘氨醇激酶激动剂的合成方法
CN114096509A (zh) * 2019-04-03 2022-02-25 阿尔萨达股份公司 用于制备乙酰乙酰化多元醇的方法
CN116947638A (zh) * 2023-07-24 2023-10-27 淄博飞源化工有限公司 一锅法制备西格列汀中间体的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992014694A1 (fr) * 1991-02-14 1992-09-03 Eastman Kodak Company Compositions d'enduction solidifiables a la chaleur
EP0619289A1 (fr) * 1993-03-26 1994-10-12 Hercules Incorporated Procédé de préparation des cétènes d'alkyle dimères par dimérization avec des amines tertiaires
EP0698598A2 (fr) * 1994-08-22 1996-02-28 Basf Aktiengesellschaft Procédé pour la fabrication d'amides
WO1998045245A1 (fr) * 1997-04-10 1998-10-15 The Procter & Gamble Company Compositions de beta ceto-esters et procede de fabrication
WO1999061479A1 (fr) * 1998-05-25 1999-12-02 Metsa Specialty Chemicals Oy Ethers de cellulose modifies

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992014694A1 (fr) * 1991-02-14 1992-09-03 Eastman Kodak Company Compositions d'enduction solidifiables a la chaleur
EP0619289A1 (fr) * 1993-03-26 1994-10-12 Hercules Incorporated Procédé de préparation des cétènes d'alkyle dimères par dimérization avec des amines tertiaires
EP0698598A2 (fr) * 1994-08-22 1996-02-28 Basf Aktiengesellschaft Procédé pour la fabrication d'amides
WO1998045245A1 (fr) * 1997-04-10 1998-10-15 The Procter & Gamble Company Compositions de beta ceto-esters et procede de fabrication
WO1999061479A1 (fr) * 1998-05-25 1999-12-02 Metsa Specialty Chemicals Oy Ethers de cellulose modifies

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114096509A (zh) * 2019-04-03 2022-02-25 阿尔萨达股份公司 用于制备乙酰乙酰化多元醇的方法
US11802104B2 (en) 2019-04-03 2023-10-31 Arxada Ag Method for preparation of acetoacetylated polyols
CN113861060A (zh) * 2021-11-05 2021-12-31 江苏弘和药物研发有限公司 一种鞘氨醇激酶激动剂的合成方法
CN113861060B (zh) * 2021-11-05 2023-12-08 江苏弘和药物研发有限公司 一种鞘氨醇激酶激动剂的合成方法
CN116947638A (zh) * 2023-07-24 2023-10-27 淄博飞源化工有限公司 一锅法制备西格列汀中间体的方法

Also Published As

Publication number Publication date
AU1866601A (en) 2001-06-04
FI19992519L (fi) 2001-05-26
FI19992519A7 (fi) 2001-05-26

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