EP0000144B1 - Process for preparing 2-isocyanatoalkyl esters of unsaturated carboxylic acids - Google Patents

Process for preparing 2-isocyanatoalkyl esters of unsaturated carboxylic acids Download PDF

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Publication number
EP0000144B1
EP0000144B1 EP78100156A EP78100156A EP0000144B1 EP 0000144 B1 EP0000144 B1 EP 0000144B1 EP 78100156 A EP78100156 A EP 78100156A EP 78100156 A EP78100156 A EP 78100156A EP 0000144 B1 EP0000144 B1 EP 0000144B1
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EP
European Patent Office
Prior art keywords
oxazoline
alkenyl
water
aqueous solution
alkyl
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.)
Expired
Application number
EP78100156A
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German (de)
English (en)
French (fr)
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EP0000144A1 (en
Inventor
Kenneth Allen Burdett
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Dow Chemical Co
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Dow Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/08—Preparation of derivatives of isocyanic acid from or via heterocyclic compounds, e.g. pyrolysis of furoxans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/12—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms

Definitions

  • This invention is directed to a process for preparing a 2-isocyanatoalkyl ester of an unsaturated carboxylic acid by reacting a water-soluble 2-alkenyl-2-oxazoline with a solution of phosgene in a water-immiscible organic solvent in the presence of an aqueous solution of a hydrochloric acid acceptor characterized by the addition of the 2 - alkenyl - 2 - oxazoline into the reaction mixture as an aqueous solution, the aqueous solution of the 2-alkenyl-2-oxazoline being prepared by (A) reacting a 2-alkyl-2-oxazoline with formaldehyde to form 2-(a-hydroxymethylalkyl)-2-oxazoline, (B) dehydrating the 2 - ( ⁇ - hydroxy - methylalkyl)-2-oxazoline to form the 2 - alkenyl - 2 - oxazoline, and (C) separating a volatile composition
  • the 2 - alkenyl - 2 - oxazolines are treated as a toxic class of compounds.
  • the potential exposure by inhalation is reduced when aqueous solutions of 2 - alkenyl - 2 - oxazolines are employed in comparison with employing solutions in water-immiscible solutions.
  • the process of the present invention requires an aqueous solution of 2 - alkenyl - 2 - oxazolines prepared by (A) reacting a 2 - alkyl - 2 - oxazoline with formaldehyde to form a 2 - (a - hydroxymethylalkyl) - 2 - oxazoline, (B) dehydrating the 2 - (a - hydroxymethylalkyl) - 2 - oxazoline to form the 2 - alkenyl - 2 - oxazoline, and (C) separating a volatile composition comprising water and 2 - alkenyl - 2 - oxazoline which condenses to an aqueous solution of the 2 - alkenyl - 2 - oxazoline.
  • the preferred process for preparing the aqueous solution of the 2 - alkenyl - 2 - oxazoline is described in DE-OS 27 27 824.
  • Suitable 2 - alkyl - 2 - oxazolines are those oxazolines in which the 2-alkyl group contains from 1 to 3 carbon atoms.
  • the oxazoline ring may optionally contain alkyl groups, in the 4- and/or 5-ring positions as long as the resultant 2 - alkenyl - 2 - oxazolines are water-soluble.
  • the most preferred 2 - alkyl - 2 - oxazolines are 2 - methyl - 2 - oxazoline and 2 - ethyl - 2 - oxazoline.
  • the yield of the desired 2 - (a - hydroxymethylalkyl) - 2 - oxazoline is maximized when the molar ratio of oxazoline to formaldehyde is greater than 1:1. Normally, at least 1.5 moles of 2 - alkyl - 2 - oxazoline per mole of formaldehyde is employed.
  • the preferred ratio of reactants is from 2 to 10 moles of oxazoline per mole of formaldehyde. The most preferred ratio is 3 to 5 moles of oxazoline per mole of formaldehyde.
  • Product yields of the 2 - (a - hydroxymethylalkyl) - 2 - oxazoline are also maximized by conducting step A under anhydrous or substantially anhydrous conditions.
  • the oxazoline reactant is preferably predried, employing such drying agents as, for example, molecular sieves or solid sodium hydroxide.
  • Paraformaldehyde having a 95 percent or greater formaldehyde content is the preferred formaldehyde source.
  • Step A is conducted at any suitable temperature that promotes the reaction and is below the decomposition temperature of the desired product. Satisfactory reaction rates have been observed at temperatures of from 90°C to 115°C. Temperatures of from 95°C to 105°C are preferred. At those temperatures, reaction times of from 2 to 8 hours are conventional. Inert organic solvents such as, for example, benzene or toluene may be employed if desired. Preferably the process is conducted without employing a solvent.
  • the 2 - ( ⁇ - hydroxymethylalkyl) - 2 - oxazoline is recovered from the reaction product of step A by conventional techniques. Fractional distillation under reduced pressure at a temperature below the decomposition temperature of the 2 - ( ⁇ - hydroxymethylalkyl) - 2 - oxazoline is preferred. The excess 2 - alkyl - 2 - oxazoline and water co-distill first and are recovered.
  • the 2 - (a - hydroxymethylalkyl) - 2 - oxazolines are higher boiling. They are preferably further purified by such conventional techniques as, for example, distillation employing a falling film still.
  • the 2 - (a - hydroxymethylalkyl) - 2 - oxazolines are dehydrated to form the 2-alkenyl-2-oxazoline by contacting the reactant with an alkali or alkaline earth metal hydroxide.
  • the dehydration reaction is conducted at a temperature of from 95°C to 200°C under reduced pressure such as, for example, 10 to 150 mm of mercury.
  • the efficiency of the alkali or alkaline earth metal hydroxide as a dehydration catalyst tends to correlate with the solubility of the hydroxide in hot water.
  • the more soluble hydroxides are the more efficient catalysts.
  • the preferred catalysts are lithium hydroxide, sodium hydroxide, potassium hydroxide, and barium hydroxide. Most preferred is sodium hydroxide.
  • the dehydration step may be conducted batchwise or continuously, the continuous process being preferred.
  • the 2 - (a - hydroxymethylalkyl) - 2 - oxazoline is added to the dehydration catalyst at the desired reaction temperature.
  • the 2 - alkenyl - 2 - oxazoline product is volatilized at the reaction temperature under reduced pressure and co-distills with water from the reaction vessel.
  • the 2 - (a - hydroxymethylalkyl) - 2 - oxazoline is metered into the reaction vessel at substantially the same rate at which the 2 - alkenyl - 2 - oxazoline/water mixture is removed as overheads.
  • the product is a solution of water and 2 - alkenyl - 2 - oxazoline.
  • Inert solvents which are liquid at the reaction temperature may be employed in the dehydration step.
  • Lower alkyl monoethers of polyalkylene glycols are solvents for alkali and alkaline earth metal hydroxides and are preferred solvents for this step.
  • Suitable compounds include, for example, the methyl, ethyl, propyl and butyl ethers of diethylene glycol and triethylene glycol.
  • the preferred solvent is the monomethyl ether of triethylene glycol when sodium hydroxide is employed as the catalyst.
  • the crude aqueous solution of 2 - alkenyl - 2 - oxazoline is surprisingly useful in the present process.
  • the aqueous solution of the 2 - alkenyl - 2 - oxazoline can be added per se into the reaction mixture or it can be further diluted with water before adding it to the reaction mixture. It is important that there be sufficient water present in the reaction mixture to create two phases with the water-immiscible solvent.
  • the 2 - alkenyl - 2 - oxazoline is an effective coupling agent. An insufficient amount of water in the reaction mixture would result in a single phase, which is not desirable.
  • Preferably at least 15 moles of water per mole of oxazoline reactant is employed in the reaction mixture. Most preferably the proportion of water is at least 25 moles of water per mole of oxazoline reactant.
  • Phosgene is employed as a solution in an inert water-immiscible organic solvent.
  • suitable solvents include hydrocarbons such as hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, and diisopropylbenzene; and chlorinated hydrocarbons such as methylene chloride, chloroform, chlorobenzene, and ortho-dichlorobenzene. Mixtures of such solvents may also be employed. Methylene chloride is the preferred solvent.
  • Suitable hydrochloric acid acceptors include both inorganic and organic bases such as, for example, sodium and potassium hydroxides, sodium and potassium carbonates, sodium and potassium phosphates, triethylamine and pyridine.
  • inorganic water-soluble bases are preferred due to cost and ease of handling.
  • Sodium hydroxide is the most preferred acid acceptor.
  • the reaction step to produce the 2 - isocyanatoalkyl ester is normally conducted at a temperature of from -30°C to 25°C, preferably from -10°C to 15°C, and more preferably from 0°C to 10°C.
  • This reaction step is preferably conducted by simultaneously introducing a pre-cooled aqueous solution of the 2 - alkenyl - 2 - oxazoline, a pre-cooled organic solution of phosgene and a pre-cooled aqueous solution of the hydrochloric acid acceptor into a reaction vessel with vigorous stirring and cooling.
  • the reaction is essentially instantaneous and is normally complete upon thorough mixing of the reactants. This step can be conducted batchwise or in a continuous fashion.
  • the 2 - isocyanatoalkyl ester of the unsaturated carboxylic acid is recovered from the organic phase of the reaction mixture by conventional techniques such as, for example, distillation. Product yields are maximized by recovering the product from the organic phase as soon as practical to minimize losses due to hydrolysis. Examples 1A to 1 B are illustrative of the feasibility of the individual steps making up the process of claim 1.
  • the mixture contained 2.5 weight percent unreacted 2-ethyl-2-oxazoline; 11.7 weight percent water; and 85.8 weight percent 2 - isopropenyl - 2 - oxazoline. This amounts to a 97.8 percent yield of 2 - isopropenyl - 2 - oxazoline.
  • a 3-liter jacketed reactor vessel was charged with 100 ml of methylene chloride and cooled to approximately 0°C.
  • a solution of 2 - isopropenyl - 2 - oxazoline (100 g) in 177 ml of water, a solution of phosgene (131.5 g) in 400 ml of methylene chloride, and 250 ml of a solution of 35 weight percent sodium hydroxide in water were added simultaneously to the reaction vessel with stirring and cooling.
  • the rates of addition were such that the three reagents were added over approximately a 50 minute time span with the temperature being maintained at 10°C to 18°C. Stirring was continued for two minutes and the layers allowed to separate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100156A 1977-06-15 1978-06-14 Process for preparing 2-isocyanatoalkyl esters of unsaturated carboxylic acids Expired EP0000144B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US806805 1977-06-15
US05/806,805 US4278809A (en) 1977-06-15 1977-06-15 Process for preparing 2-isocyanatoalkyl esters of organic carboxylic acids

Publications (2)

Publication Number Publication Date
EP0000144A1 EP0000144A1 (en) 1979-01-10
EP0000144B1 true EP0000144B1 (en) 1981-08-05

Family

ID=25194881

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100156A Expired EP0000144B1 (en) 1977-06-15 1978-06-14 Process for preparing 2-isocyanatoalkyl esters of unsaturated carboxylic acids

Country Status (6)

Country Link
US (1) US4278809A (enrdf_load_stackoverflow)
EP (1) EP0000144B1 (enrdf_load_stackoverflow)
JP (1) JPS545921A (enrdf_load_stackoverflow)
AU (1) AU515393B2 (enrdf_load_stackoverflow)
CA (1) CA1099733A (enrdf_load_stackoverflow)
DE (1) DE2860892D1 (enrdf_load_stackoverflow)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5780405A (en) * 1980-11-10 1982-05-20 Dow Chemical Co Addition polymerizable polyethers having ethylenically unsaturated urethane branched group
US4692503A (en) * 1980-12-29 1987-09-08 Ppg Industries, Inc. Coating compositions comprising free radical addition polymers with crosslinkable integral isocyanato groups
US4375546A (en) * 1981-11-16 1983-03-01 The Dow Chemical Company Substituted pyridinyl esters of 2-(1-oxoalkyloxy)ethyl carbamic acid
US4418198A (en) * 1981-11-16 1983-11-29 The Dow Chemical Company Substituted pyridine carbonyl amino ethyl esters of 2-methyl-2-propenoic acid
DE3225247C2 (de) * 1982-07-06 1986-07-10 The Dow Chemical Co., Midland, Mich. Verfahren zur Destillation eines 2-Isocyanatoalkylesters einer α,ß-äthylenisch ungesättigten Carbonsäure
DE3338077A1 (de) * 1983-10-20 1985-05-09 Bayer Ag, 5090 Leverkusen Ungesaettigte esterisocyanate, ein verfahren zu ihrer herstellung und ihre verwendung bei der herstellung von olefinisch ungesaettigten oligourethanen
US4520074A (en) * 1984-07-20 1985-05-28 General Electric Company Polymerizable 3-aroyloxyphenyl carbamates and methods for their preparation and use
JPS61137964A (ja) * 1984-12-10 1986-06-25 株式会社ブリヂストン 床板材
CA1267157A (en) 1985-05-13 1990-03-27 Satoshi Urano Isocyanate compounds and their production
US4650889A (en) * 1985-11-29 1987-03-17 Dow Corning Corporation Silane coupling agents
DE4226805A1 (de) * 1992-08-13 1994-02-17 Henkel Kgaa Bindemittelgemische für Einbrennlacke
EP1660438B1 (en) 2003-07-31 2011-01-26 Showa Denko K.K. Process for preparing high purity (meth)acryloyloxyalkyl isocyanate
US20060229464A1 (en) * 2003-07-31 2006-10-12 Katsutoshi Morinaka Stabilized (meth)acryloyloxyalkyl isocyanate a process for stabilization thereof and a process for preparation of the same
JP5135564B2 (ja) 2007-06-12 2013-02-06 デクセリアルズ株式会社 接着剤組成物
EP2377847A1 (en) 2010-04-14 2011-10-19 3M Innovative Properties Company Process for producing isocyanates
CN102702028B (zh) * 2012-06-12 2013-11-06 江苏快达农化股份有限公司 甲基丙烯酰氧乙基异氰酸酯的合成方法
US9266824B2 (en) 2014-01-13 2016-02-23 Warsaw Orthopedic, Inc. Methods and compositions for making an amino acid triisocyanate
EP4089070A4 (en) 2020-01-06 2024-04-17 Resonac Corporation (meth)acrylic acid ester compound having isocyanate group, and method for producing same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2821544A (en) * 1954-04-26 1958-01-28 Bayer Ag Production of alkylisocyanate esters of 2-alkenoic acids
FR1217276A (fr) * 1957-12-13 1960-05-03 Bayer Ag Procédé de préparation de polyisocyanates aromatiques contenant des groupes ester
US3535332A (en) * 1968-03-11 1970-10-20 Commercial Solvents Corp Production of vinyl oxazoline esters
GB1252099A (enrdf_load_stackoverflow) 1969-05-14 1971-11-03

Also Published As

Publication number Publication date
EP0000144A1 (en) 1979-01-10
US4278809A (en) 1981-07-14
JPS5757021B2 (enrdf_load_stackoverflow) 1982-12-02
AU515393B2 (en) 1981-04-02
CA1099733A (en) 1981-04-21
DE2860892D1 (en) 1981-11-05
JPS545921A (en) 1979-01-17
AU3705978A (en) 1979-12-20

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