US3557167A - Process for the preparation of 2-aryloxyethyl carboxylates - Google Patents

Process for the preparation of 2-aryloxyethyl carboxylates Download PDF

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Publication number
US3557167A
US3557167A US724630A US3557167DA US3557167A US 3557167 A US3557167 A US 3557167A US 724630 A US724630 A US 724630A US 3557167D A US3557167D A US 3557167DA US 3557167 A US3557167 A US 3557167A
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weight
parts
ester
esters
aryl
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Hans-Leo Hylsmann
Gustav Renckhoff
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DYNAMIT NOBEL AG WERK WITTEN
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DYNAMIT NOBEL AG WERK WITTEN
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    • 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
    • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D267/00—Heterocyclic compounds containing rings of more than six members having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D267/02—Seven-membered rings
    • C07D267/06—Seven-membered rings having the hetero atoms in positions 1 and 3

Definitions

  • the present invention relates to a process for the preparation of uniform Z-aryloxyethyl esters of aliphatic, cycloaliphatic or aromatic carboxylic acids. More particularly, the present invention is concerned with a process for the preparation of 2-aryloxyethyl esters from aryl esters of mono-, aliphatic, cycloaliphatic or aromatic carboxylic acids and the aryl esters of poly-, aliphatic, cycloaliphatic 0r aromatic carboxylic acids. The process of the present invention is also effective and relates to the preparation of mixed alkyl aryl esters of said acids.
  • An object of the present invention is to avoid the prior art disadvantages in the preparation of Z-aryloxyethyl carboxylates.
  • Another object of the present invention is to provide an improved process for the preparation of Z-aryloxyethyl esters of aliphatic, cycloaliphatic or aromatic carboxylic acids which may be carried out in an eflicacious and economical manner.
  • a further object of the present invention is to pro vide a process for preparation of Z-aryloxyethyl carboxylates in high yields.
  • Suitable starting materials for the process of the present invention are the aryl esters of monoaliphatic, cycloaliphatic or aromatic carboxylic acids and the aryl esters of poly-, aliphatic, cycloaliphatic or aromatic carboxylic acids.
  • the aryl esters which are substituted in the aryl residue by one or more than one halogen and/ or alkyl groups such as for example, cresol esters or the isomeric monoor dichlorophenyl esters, can also be used.
  • the preferred aryl esters are the phenyl esters or the phenyl esters which are substituted in the phenyl residue by one or more than one halogen and/or alkyl group.
  • the aliphatic carboxylic acids which can be used to produce the aryl ester starting materials of the present invention include the aliphatic carboxylic acids having about 2 to 18 carbon atoms, such as for example, acetic acid, butyric acid, lauric acid, stearic acid, succinic acid, sebacic acid and other like acids.
  • the cycloaliphatic carboxylic acids include cyclohexane monocarboxylic acid, cyclohexane dicarboxylic acid, hexahydrobenzoic acid and the like.
  • the aromatic carboxylic acids which can be effectively used to produce the aryl esters used in the present process comprises acids such as benzoic acid, isomeric toluic acids, terephthalic acid, hexahydroterephthalic acid, chloroterephthalic acid, dichloroterephthalic acid, isophthalic acid, diphenyl dicarboxylic acids, diphenylmethane dicarboxylic acids, benzophenone dicarboxylic acids, trimesic acid, naphthalene dicarboxylic acids, etc.
  • acids such as benzoic acid, isomeric toluic acids, terephthalic acid, hexahydroterephthalic acid, chloroterephthalic acid, dichloroterephthalic acid, isophthalic acid, diphenyl dicarboxylic acids, diphenylmethane dicarboxylic acids, benzophenone dicarboxylic acids, trimesic acid, naphthalene dicarboxylic acids
  • the monohydric phenols or naphthols can be mentioned including those which are substituted in the aryl residue by one or more than one halogen and/ or alkyl group.
  • Suitable phenolic compounds include for example phenol, the isomeric cresols or xylenols, butylphenols, octylphenols, benzylphenols, chlorophenol, dichlorophenol, chloro-methylphenol, fi-naphthol, etc.
  • pure phenols it is also possible to employ technical isomeric mixtures such as those commercially available on the market. In the latter case, mixed aryl esters are obtained.
  • the reaction is generally conducted at a temperature of about 100 to 200 C. Preferably a temperature of about to C. is maintained, at which temperatures the reaction proceeds rapidly without there being any major deposition of the ethylene carbonate.
  • the reaction is catalyzed by a number of salts. Very effective are the halides or hydroxides of the alkali and alkaline earth metals, particularly lithium chloride or calcium chloride.
  • rhodanides for example potassium rhodanide are also useful.
  • salts of organic basis such as for example, tetramethylammonium chloride or guanidine rhodanide are also suitable catalysts for the process of the present invention.
  • These catalytically active materials are employed in amounts of about 0.5 to 20% by weight, based on the amount of the aryl ester utilized.
  • the reaction time is dependent upon the concentration of the catalysts employed. For example in the presence of 1% by weight of the above-mentioned catalysts, approximately 20 hours of reaction time is utilized. In the presence of about 10% by weight of the above catalyst the reaction can be terminated in most cases within about 2 to 5 hours.
  • the separation of the reaction products from the catalysts is readily accomplished when using inorganic salts, since these salts are present in the solid phase after the reaction is terminated.
  • the aryloxyethyl esters can be separated from catalysts soluble in the reaction mixture, such as for example, the salts of organic basis, in accordance with conventional methods, such as the distillation of the reaction substance under vacuum or recrystallization from solvents, preferabl from hydrocarbons. In this manner the product can be obtained in a substantially pure form.
  • the process of the present invention for the preparation of 2-aryloxyethyl carbonates exhibits substantial advantages when compared to the conventional processes.
  • the esterification of carboxylic acids with 2- aryloxyethanols had to be utilized for the production of aryloxyethyl esters.
  • higher oxyethylated phenols are produced as by-products and these phenols can only be separated from the reaction mixture with great difliculty.
  • the novel way of preparing 2-aryloxyethy1 carboxylates according to the present invention exhibits the advantage that the formation of esters of the general formula wherein n is a number larger than 1 is prevented.
  • equivalent amount of reactants are employed in the reaction of the present invention.
  • equivalent amounts is meant the number of groups on the reactants which take part in the reaction.
  • an equivalent amount of ethylene carbonate is used for each respective reactive group of the ester employed.
  • a small excess, for example a few percent above the equivalent amount of ethylene carbonate can be employed in order to compensate for minor losses of the latter by thermal decomposition.
  • the 2-aryloxyethyl esters prepared in accordance with the process of the present invention are normally obtained in almost quantitative yields. They are very effective as plasticizers for synthetic materials and intermediates for use in organic synthesis.
  • EXAMPLE 1 136 parts by weight of phenyl acetate (1 mol) is mixed with 88 parts by weight of ethylene carbonate (1 mol), and is heated with stirring to 150 C. in the presence of 1.3 6 parts by weight (1% by weight) of tetramethylammonium chloride, based on the acetic acid phenyl ester employed. After about 2.5 hours the evolution of carbon dioxide terminates. 180 parts by weight of phenoxyethyl acetate, obtained in a quantitative yield, is recovered during the vacuum distillation at a temperature of about 131-- 4 132 C. and a pressure of 15 mm. Hg. The saponification number of the ester is 312 (calculated: 311).
  • EXAMPLE 2 138 parts by weight of phenyl laurate (0.5 mol) is mixed with 44 parts by weight of ethylene carbonate (0.5 mol) and heated to 150 C. in the presence of 1.4 parts by weight of tetramethylammonium chloride (1% by weight, based upon the ester employed). The reaction is terminated after about 3.25 hours.
  • the yield of phenoxyethyl laurate is 159 parts by weight, corresponding to 99.5% of the theoretical yield.
  • the saponification number of the ester is 175.5 (calculated: 175.5). The ester melted at 35.5 to 36.0 C.
  • EXAMPLE 3 180 parts by weight of phenyl stearate (0.5 mol) is reacted as in Example 2 with 44.9 parts by Weight of ethylene carbonate (0.51 mol) with the addition of 1.8 parts by weight of lithium chloride.
  • the yield of phenoxyethyl stearate is 200 parts by weight (calculated: 202), corresponding to 99% of the theoretical yield.
  • the saponification number of the ester is 139 (calculated: 139) and the melting point is about 55 C.
  • the saponification number of the ester is 136.
  • EXAMPLE 5 138 parts by weight of di-m-cresyl cyclohexanedicarboxylate (0.31 mol) is reacted with 69 parts by weight of ethylene carbonate (0.78 mol) at about C. with stirring using 1.4 parts by weight of lithium chloride as the catalyst. After 21.5 hours of reaction time the evolution of carbon dioxide is terminated. The product, di-(m-cresyloxyethyl)-cyclohexanedicarboxylate, obtained in a quantitative yield, is recrystallized from petroleum ether. The reaction product melted at 95 C. and exhibited a saponification number of 248 (calculated: 255).
  • Example 7 Example 6 is repeated with the addition of 1% by weight of calcium chloride instead of lithium chloride. Phenoxyethyl benzoate is recovered in an 81% yield. The saponification number of the ester is 235 (calculated: 232). The melting point is 58 C.
  • EXAMPLE 8 212 parts by weight of m-cresyl benzoate (1 mol) is heated with 88 parts by weight of ethylene carbonate (1 mol) with stirring at 150 C. As the catalyst, 1% by weight of lithium chloride, based on the weight of the cresol ester, is employed. After 18.5 hours, the reaction mixture is distilled. Pure m-cresyloxyethyl benzoate is recovered at a temperature of 153 to 154 C. and a pressure of 0.4 mm. Hg. The ester is liquid at room temperature. The yield is 87% of the theoretical yield.
  • EXAMPLE 9 106 parts by weight of phenyl p-toluate is reacted with 44.9 parts by weight of ethylene carbonate.
  • the phenoxyethyl p-toluate is obtained in a pure form by distillation under vacuum at a temperature of about 165 to 170 C. and a pressure of about 0.4 mm. Hg.
  • As the catalyst 1% by weight of lithium chloride, based on the weight of the phenyl ester, is employed. 122 parts by weight of the ester is distilled, giving a yield corresponding to 97% of the theoretical yield.
  • the saponification number is 224 (calculated: 219).
  • the melting point is about 45 to 46 C.
  • Example 9 is repeated, the catalyst used being 1% by weight of tetramethylammonium chloride. The reaction lasted 1.5 hours. The yield of phenoxyethyl l-toluate is 97% of the theoretical yield and the saponification number is 222.5 (calculated: 219). The ester melted at a temperature of about 44 to 45 .5" C.
  • Example 9 is repeated using 1 part by weight of potassium hydroxide as the catalyst in place of lithium chloride. After a reaction time of 2 hours a yield of 125 parts by weight of phenoxyethyl l-toluate is recovered. This represents 99.5% of the theoretical recovery. The saponification number is 223 (calculated: 219).
  • EXAMPLE 12 79.5 parts by weight of diphenyl isophthalate (0.25 mol) is reacted with 44 parts by weight of ethylene carbonate (0.5 mol) at a temperature of 150 C. and in the presence of 7.95 parts by weight of lithium chloride as the catalyst therefor. The reaction is terminated after 2.5 hours resulting in the production of 100 parts by weight of di-(phenoxyethyl)-isophthalate, corresponding to a 98% recovery of the theoretical yield.
  • the saponifi cation number of the ester is 276.5 (calculated: 276).
  • EXAMPLE 13 79.5 parts by weight of diphenyl terephthalate (0.25 mol) is reacted with 66 parts by weight of ethylene carbonate (0.75 mol) at a temperature of 170 C. and in the presence of 1% by weight of lithium chloride, based on the weight of the diphenyl terephthalate. After distilling 01? the excess ethylene carbonate, 100 parts by weight of di-(phenoxyethyl)-terephthalate is recovered. The ester is recrystallized from benzene. The saponification number is 275 (calculated: 276) and the melting point is about 100 to 101 C.
  • EXAMPLE 14 86.5 parts by weight of di-m-cresyl isophthalate (0.25 mol) is reacted with 44.9 parts by weight of ethylene carbonate (0.51 mol) at a temperature of 150 C. and in the presence of 1% by weight of lithium chloride, based on the weight of the di-m-cresyl isophthalate. After 22.5 hours the reaction is terminated. The reaction product is dissolved in xylene, the solution is then treated with activated charcoal and the solvent is again removed. 95 parts by weight of di-(m-cresyloxyethyl)-isophthalate is obtained which represents a recovery of about 88% of the theoretical recovery. The saponification number of the ester which is liquid at room temperature is 261.5 (calculated: 258).
  • EXAMPLE 15 A mixture of 96.8 parts by weight of di-p-chlorophenyl terephthalate (0.25 mol), 44 parts by weight of ethylene carbonate (0.5 mol) and 1 part by weight of lithium chloride is heated for 16 hours with stirring at a temperature of 150 C. After the period of time has elapsed, the carbon dioxide evolution is complete. The reaction product is recrystallized from petroleum ether. 116.7 parts by weight of di-(p-chlorophenoxyethyl)-terephthalate with a melting point of 148 C. is recovered. The yield corresponds to 98.5% of the theoretical yield. The saponification number of the ester is 236 (calculated: 235.5).
  • EXAMPLE 16 128 parts by weight of monomethylmonophenyl terephthalate (0.5 mol) is heated for 1.75 hours at a temperature of 150 C. with 44 parts by weight of ethylene carbonate (0.5 mol) and 12.8 parts by weight of lithium chloride as the catalyst. The monomethylphenoxyethyl terephthalate is obtained in a quantitative yield. The saponification number of the mixed ester is 375 (calculated: 373).
  • a process for the preparation of 2-aryloxyethyl esters from an aryl ester prepared from a phenolic compound and an acid selected from the group consisting of aliphatic, cycloaliphatic and aromatic monoand polycarboxylic acids, and said aryl esters substituted in the aryl residue with at least one halogen and/ or alkyl group which comprises reacting said aryl ester with ethylene carbonate in approximately equivalent amounts at a temperature of about to 200 C. and in the presence of a catalyst selected from the group consisting of the halides, hydroxides and rhodanides of the alkali and alkaline earth metals and salts of 'organic bases.
  • a reaction catalyst selected from the group consisting of the halides, hydroxides and rhodanides of the
  • aryl esters are mixed alkylaryl esters of aromatic dicarboxylic acids.
  • aryl ester is selected from the group consisting of phenyl acetate, phenyl laurate and phenyl stearate.
  • aryl ester is selected from the group consisting of phenyl hexahydrobenzoate, di-m-cresyl cyclohexanedicarboxylate, phenyl benzoate, m-cresol benzoate, and phenyl p-toluate.
  • aryl ester is selected from the group consisting of diphenyl isophthalate, diphenyl terephthalate, di-m-cresyl isophthalate, dip-chlorophenyl terephthalate, and monomethylmonophenyl terephthalate.
  • the catalyst is selected from the group consisting of tetramethylammonium chloride, lithium chloride, and calcium chloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US724630A 1967-03-21 1968-04-26 Process for the preparation of 2-aryloxyethyl carboxylates Expired - Lifetime US3557167A (en)

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DED0052590 1967-03-21
DED0052935 1967-04-27

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US (1) US3557167A (xx)
BE (2) BE712499A (xx)
CH (1) CH494205A (xx)
DE (2) DE1670557A1 (xx)
FR (2) FR95494E (xx)
GB (2) GB1150620A (xx)
LU (1) LU55760A1 (xx)
NL (1) NL6803999A (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478754A (en) * 1982-11-01 1984-10-23 The Procter & Gamble Company Preparation of phenyl esters in the presence of boric anhydride
US20050232881A1 (en) * 2004-04-14 2005-10-20 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Antiperspirant compositions
US20120100323A1 (en) * 2010-10-26 2012-04-26 Tanner James T Novel bis(ARYLOXYALKYL) esters of aromatic polycarboxylic acids and method of preparation
US8344172B2 (en) 2011-03-25 2013-01-01 Stepan Company Preparation of antiplasticizers for thermoplastic polyesters

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR204705A1 (es) * 1972-10-13 1976-02-27 Stauffer Chemical Co Nuevo compuesto antidoto derivado de 3-acil oxazolidinas y tiazolidinas sustituidas util para composiciones herbicidas y la composicion herbicida que lo contiene
CA1014563A (en) * 1972-10-13 1977-07-26 Stauffer Chemical Company Substituted oxazolidines and thiazolidines
EP0002329A1 (en) * 1977-11-30 1979-06-13 Imperial Chemical Industries Plc Plasticized polyvinylchloride compositions
DE3814781A1 (de) * 1988-04-30 1989-11-09 Basf Ag Verfahren zur herstellung von 2-hydroxy-4-(2'-hydroxyethoxy)-benzophenonen
US5560872A (en) * 1995-05-18 1996-10-01 Lever Brothers Company Compositions comprising oxazolidine and tetrahydrooxazine amide surfactants

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478754A (en) * 1982-11-01 1984-10-23 The Procter & Gamble Company Preparation of phenyl esters in the presence of boric anhydride
US20050232881A1 (en) * 2004-04-14 2005-10-20 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Antiperspirant compositions
US7504091B2 (en) 2004-04-14 2009-03-17 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Antiperspirant compositions
US20120100323A1 (en) * 2010-10-26 2012-04-26 Tanner James T Novel bis(ARYLOXYALKYL) esters of aromatic polycarboxylic acids and method of preparation
US20140031578A1 (en) * 2010-10-26 2014-01-30 James T. Tanner Novel bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US9409852B2 (en) * 2010-10-26 2016-08-09 Ethox Chemicals, Llc Bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US20180037535A1 (en) * 2010-10-26 2018-02-08 James T. Tanner Novel bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US9957223B2 (en) * 2010-10-26 2018-05-01 Ethox Chemicals Llc Bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US10899698B2 (en) * 2010-10-26 2021-01-26 Ethox Chemicals, Llc Bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US8344172B2 (en) 2011-03-25 2013-01-01 Stepan Company Preparation of antiplasticizers for thermoplastic polyesters
US8692013B2 (en) 2011-03-25 2014-04-08 Stepan Company Preparation of antiplasticizers for thermoplastic polyesters
US9056964B2 (en) 2011-03-25 2015-06-16 Stepan Company Preparation of antiplasticizers for thermoplastic polyesters

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NL6803999A (xx) 1968-09-23
FR1560184A (xx) 1969-02-03
BE713738A (xx) 1968-10-16
GB1150620A (en) 1969-04-30
FR95494E (fr) 1971-01-15
CH494205A (de) 1970-07-31
LU55760A1 (xx) 1968-03-25
DE1593824A1 (de) 1970-12-10
GB1182081A (en) 1970-02-25
BE712499A (xx) 1968-09-28
DE1670557A1 (de) 1971-07-01

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