DE1111186B - Process for the production of carboxylic acid esters - Google Patents
Process for the production of carboxylic acid estersInfo
- Publication number
- DE1111186B DE1111186B DEB52239A DEB0052239A DE1111186B DE 1111186 B DE1111186 B DE 1111186B DE B52239 A DEB52239 A DE B52239A DE B0052239 A DEB0052239 A DE B0052239A DE 1111186 B DE1111186 B DE 1111186B
- Authority
- DE
- Germany
- Prior art keywords
- carbonyl
- parts
- carboxylic acid
- acid esters
- production
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/60—Maleic acid esters; Fumaric acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Umsetzung von Carbonsäuren mit Alkoholen zu Carbonsäureestern geschieht üblicherweise in Gegenwart starker Säuren als Katalysatoren, durch die die Einstellung des Estergleichgewichtes beschleunigt wird. Gegen starke Säuren empfindliche Carbonsäuren oder Alkohole können daher auf diese Weise nicht oder nur mit schlechter Ausbeute verestert werden.The conversion of carboxylic acids with alcohols to carboxylic acid esters is usually done in The presence of strong acids as catalysts, which accelerate the establishment of the ester equilibrium will. Carboxylic acids or alcohols sensitive to strong acids can therefore be used in this way not be esterified or only with poor yield.
Es wurde gefunden, daß Carbonsäureester leicht hergestellt werden können, ohne daß ein Zusatz von Säuren erforderlich ist, wenn man die Carbonsäure und den Alkohol oder das Phenol zusammen mit Carbonyl-diimidazol, Carbonyl-ditriazol oder Carbonyl-dipyrazol umsetzt. Als Carbonsäuren lassen sich ein- oder mehrwertige gesättigte oder ungesättigte aliphatische oder cycloaliphatische sowie aromatische Carbonsäuren, wie etwa Essigsäure, Propionsäure, Fumarsäure, Sorbinsäure, Benzoesäure oder Zimtsäure, verwenden. Die verwendeten Alkohole können primär, sekundär oder tertiär, ein- oder mehrwertig und gesättigt oder ungesättigt sein. Sie können auch funktioneile Gruppen, wie z. B. Äthyleniminringe, tragen. So lassen sich z. B. Äthanol, Isopropanol, Äthylenglykol oder 3-Hydroxy-4-äthyleniminobuten-l verwenden. Als Phenole können Phenol selbst, Resorein, «-Naphthol oder /3-Naphthol dienen.It has been found that carboxylic acid esters can be easily prepared without the addition of Acids is required when using the carboxylic acid and the alcohol or the phenol together Carbonyl-diimidazole, carbonyl-ditriazole or carbonyl-dipyrazole implements. The carboxylic acids can be mono- or polyvalent, saturated or unsaturated aliphatic or cycloaliphatic and aromatic carboxylic acids, such as acetic acid, propionic acid, Use fumaric acid, sorbic acid, benzoic acid, or cinnamic acid. The alcohols used can primary, secondary or tertiary, mono- or polyvalent and saturated or unsaturated. You can also functional groups, such as. B. Ethylenimine rings wear. So z. B. ethanol, isopropanol, Use ethylene glycol or 3-hydroxy-4-ethyleneiminobutene-1. Phenol itself, resorein, «-Naphthol or / 3-naphthol are used.
Außer Carbonyl-diimidazol, Carbonyl-ditriazol und Carbonyl-dipyrazol sind auch deren Substitutionsprodukte, beispielsweise die Alkylderivate, wie Carbonyl-di-4-methylimidazol oder Carbonyl-di-3,5-dimethylpyrazol, geeignet. Auf jede zu veresternde Carboxylgruppe wird im allgemeinen ein Mol einer heterocyclischen Carbonylverbindung angewandt. In manchen Fällen kann jedoch ein Überschuß des. Alkohols oder der Carbonsäure günstig sein.In addition to carbonyl-diimidazole, carbonyl-ditriazole and carbonyl-dipyrazole, their substitution products are also used, for example the alkyl derivatives, such as carbonyl-di-4-methylimidazole or carbonyl-di-3,5-dimethylpyrazole are suitable. On every carboxyl group to be esterified one mole of a heterocyclic carbonyl compound is generally used. In some In some cases, however, an excess of the alcohol or the carboxylic acid can be advantageous.
Die Umsetzung, die vorzugsweise unter Wasserausschluß erfolgt, kann mit oder ohne Zusatz von Verdünnungsmitteln durchgeführt werden. Als solche können Tetrahydrofuran, Benzol, Chloroform und andere Lösungsmittel dienen, die gegenüber den Reaktionsteilnehmern indifferent sind. Wird die Veresterung in Gegenwart von Verdünnungsmitteln durchgeführt, so beginnt die Reaktion meistens schon bei Raumtemperatur unter starker Entwicklung von Kohlendioxyd. Nach deren Abklingen erwärmt man zweckmäßig noch einige Zeit unter Rückfluß. Aus dem erhaltenen Reaktionsgemisch kann das neben dem Ester gebildete Imidazol, Triazol oder Pyrrazol z. B. durch Waschen des Reaktionsproduktes oder seiner ätherischen Lösung mit Wasser leicht entfernt werden.The reaction, which is preferably carried out with exclusion of water, can be carried out with or without the addition of Diluents are carried out. As such, tetrahydrofuran, benzene, and chloroform can be used other solvents are used, which are indifferent to the reactants. Will the esterification carried out in the presence of diluents, the reaction usually begins at room temperature with strong evolution of carbon dioxide. After they have subsided, one warms up expediently under reflux for some time. From the reaction mixture obtained, in addition to the Ester formed imidazole, triazole or pyrrazole z. B. by washing the reaction product or its essential solution can be easily removed with water.
Das erfindungsgemäße Verfahren gestattet es im Gegensatz zu den herkömmlichen Veresterungsmaß-Verfahren
zur Herstellung
von CarbonsäureesternIn contrast to the conventional degree of esterification processes, the process according to the invention permits production
of carboxylic acid esters
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft,Corporation,
Ludwigshafen/RheinLudwigshafen / Rhine
Dr. Heinz August Staab, Heidelberg,
ist als Erfinder genannt wordenDr. Heinz August Staab, Heidelberg,
has been named as the inventor
nahmen, empfindliche Carbonsäuren oder Alkohole schnell und schonend in vorzüglichen Ausbeuten zu verestern. Darüber hinaus kann man diese Komponenten in einem Zuge verestern, und zwar, ohne daß starke Mineralsäuren abgespalten werden oder zugegen sein müssen. Das erfindungsgemäße Veresterungsverfahren bereichert daher die Technik erheblich und in einer Weise, die nicht vorhersehbar war. Auch die in den Chemischen Berichten, Bd. 89, S. 1927, veröffentlichten Arbeiten und theoretischen Betrachtungen über das Verhalten von Säureazoliden enthalten keinen Hinweis auf das Veresterungsverfahren. Die in den Beispielen genannten Teile sind Gewichtsteile. took on sensitive carboxylic acids or alcohols quickly and gently in excellent yields to esterify. In addition, these components can be esterified in one go, without strong mineral acids are split off or must be present. The esterification process according to the invention therefore enriches technology considerably and in a way that was not foreseeable. Also the Work and theoretical considerations published in Chemischenberichte, Vol. 89, p. 1927 on the behavior of acid azolides contain no reference to the esterification process. The parts mentioned in the examples are parts by weight.
12,2 Teile Benzoesäure, 16,2 Teile N,N'-Carbonyldiimidazol, 23 Teile Äthanol und 50 Teile Tetrahydrofuran werden bei Raumtemperatur zusammengegeben. Es tritt eine Entwicklung von Kohlendioxyd ein, die nach etwa 10 Minuten beendet ist. Danach erwärmt man das Reaktionsgemisch noch 1J2 Stunde unter Rückfluß zum Sieden. Durch fraktionierte Destillation erhält man den Benzoesäureäthylester vom Siedepunkt 100 bis 105 0C bei 15 mm in einer Ausbeute von 80 bis 90°/0 der Theorie.12.2 parts of benzoic acid, 16.2 parts of N, N'-carbonyldiimidazole, 23 parts of ethanol and 50 parts of tetrahydrofuran are combined at room temperature. There is an evolution of carbon dioxide, which ends after about 10 minutes. The reaction mixture is then heated to boiling under reflux for a further 1 J 2 hours. By fractional distillation, the ethyl benzoate of boiling point 100 to 105 0 C at 15 mm in a yield of 80 to 90 ° / 0 of theory.
An Stelle der gemäß Beispiel 1 verwendeten Benzoesäure werden 14,8 Teile Zimtsäure in der dort angegebenen Weise verestert. Der in einer Ausbeute vonInstead of the benzoic acid used according to Example 1, 14.8 parts of cinnamic acid are used in the form given there Esterified way. Which in a yield of
109 648/421109 648/421
90 % der Theorie erhaltene Zimtsäureäthylester siedet bei 165 bis 1700C bei 15 mm.90% of the theoretical ethyl cinnamate obtained boils at 165 to 170 ° C. at 15 mm.
12,2 Teile Benzoesäure, 16,2 Teile N,N'-Carbonyldiimidazol und 9,4 Teile Phenol werden bei Raumtemperatur zu 50 Teilen Tetrahydrofuran gegeben. Die einsetzende Entwicklung von Kohlendioxyd ist nach etwa 10 Minuten beendet. Danach erwärmt man noch V2 Stunde unter Rückfluß zum Sieden. Anschließend entfernt man das Tetrahydrofuran durch Verdampfen, wäscht den Rückstand mit 100 Teilen Wasser und kristallisiert schließlich aus einem Gemisch von Alkohol und Äther um. Man erhält den Benzoesäurephenylester in Prismen vom Schmelzpunkt 70° C in einer Ausbeute von 85% der Theorie.12.2 parts of benzoic acid, 16.2 parts of N, N'-carbonyldiimidazole and 9.4 parts of phenol are added to 50 parts of tetrahydrofuran at room temperature. The onset of carbon dioxide evolution ends after about 10 minutes. Thereafter, the mixture is heated to boiling under reflux for a further 2 hours. The tetrahydrofuran is then removed by evaporation, the residue is washed with 100 parts of water and finally recrystallized from a mixture of alcohol and ether. The phenyl benzoate is obtained in prisms with a melting point of 70 ° C. in a yield of 85% of theory.
Zu einer Aufschlämmung von 20 Teilen N,N'-Carbonyl-di-l,2-triazol in 100 Teilen Tetrahydrofuran gibt man 14,2 Teile Benzoesäure, rührt 2 Stunden bei Raumtemperatur und versetzt dieses Reaktionsgemisch danach mit einer Lösung von 15,7 Teilen Zimtalkohol in 30 Teilen Tetrahydrofuran. Man kocht das Gemisch 1 Stunde am Rückfluß, dampft das Tetrahydrofuran ab, versetzt den Rückstand mit Wasser, extrahiert das Reaktionsprodukt mit Äther und reinigt den Benzoesäurecinnamylester durch Destillation. Siedepunkt: 160°C bei 2 mm Hg. Die Ausbeute beträgt 75% der Theorie.To a slurry of 20 parts of N, N'-carbonyl-di-1,2-triazole in 100 parts of tetrahydrofuran 14.2 parts of benzoic acid are stirred for 2 hours at room temperature and this reaction mixture is then treated with a solution of 15.7 parts Cinnamon alcohol in 30 parts of tetrahydrofuran. The mixture is refluxed for 1 hour and then evaporated Tetrahydrofuran from, the residue is treated with water, the reaction product is extracted with ether and purifies the cinnamyl benzoate by distillation. Boiling point: 160 ° C at 2 mm Hg. The yield is 75% of theory.
Claims (1)
Angewandte Chemie, Bd. 68, 1956, S. 754;
Chemische Berichte, Bd. 89, 1956, S. 1934.Considered publications:
Angewandte Chemie, Vol. 68, 1956, p. 754;
Chemical Reports, Vol. 89, 1956, p. 1934.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB52239A DE1111186B (en) | 1959-02-25 | 1959-02-25 | Process for the production of carboxylic acid esters |
BE587720A BE587720A (en) | 1959-02-25 | 1960-02-17 | Process for the production of esters of carboxylic acids. |
FR819408A FR1249104A (en) | 1959-02-25 | 1960-02-24 | Process for the production of esters of carboxylic acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB52239A DE1111186B (en) | 1959-02-25 | 1959-02-25 | Process for the production of carboxylic acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1111186B true DE1111186B (en) | 1961-07-20 |
Family
ID=6969826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEB52239A Pending DE1111186B (en) | 1959-02-25 | 1959-02-25 | Process for the production of carboxylic acid esters |
Country Status (3)
Country | Link |
---|---|
BE (1) | BE587720A (en) |
DE (1) | DE1111186B (en) |
FR (1) | FR1249104A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1186463B (en) * | 1962-09-19 | 1965-02-04 | Jur Heinz Bauer Dr | Process for the preparation of aliphatic carboxylic acid esters of tertiary alcohols |
DE1239682B (en) * | 1962-11-14 | 1967-05-03 | Hoffmann La Roche | Process for the preparation of 6-O-ascorbic acid and isoascorbic acid monooleate |
DE1298521B (en) * | 1963-02-16 | 1969-07-03 | Hoechst Ag | Process for the production of cyanomethyl esters of acrylic acid, methacrylic acid or crotonic acid |
-
1959
- 1959-02-25 DE DEB52239A patent/DE1111186B/en active Pending
-
1960
- 1960-02-17 BE BE587720A patent/BE587720A/en unknown
- 1960-02-24 FR FR819408A patent/FR1249104A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1186463B (en) * | 1962-09-19 | 1965-02-04 | Jur Heinz Bauer Dr | Process for the preparation of aliphatic carboxylic acid esters of tertiary alcohols |
DE1239682B (en) * | 1962-11-14 | 1967-05-03 | Hoffmann La Roche | Process for the preparation of 6-O-ascorbic acid and isoascorbic acid monooleate |
DE1298521B (en) * | 1963-02-16 | 1969-07-03 | Hoechst Ag | Process for the production of cyanomethyl esters of acrylic acid, methacrylic acid or crotonic acid |
Also Published As
Publication number | Publication date |
---|---|
FR1249104A (en) | 1960-12-23 |
BE587720A (en) | 1960-06-16 |
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