US2803644A - Condensation of dialkyl succinates - Google Patents

Condensation of dialkyl succinates Download PDF

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Publication number
US2803644A
US2803644A US491207A US49120755A US2803644A US 2803644 A US2803644 A US 2803644A US 491207 A US491207 A US 491207A US 49120755 A US49120755 A US 49120755A US 2803644 A US2803644 A US 2803644A
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US
United States
Prior art keywords
diol
dialkyl
diene
cyclohexa
sodium
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 - Lifetime
Application number
US491207A
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English (en)
Inventor
Lenel Paul-Otto
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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

Definitions

  • the product has, in general, been obtained, in the form of a solid cake, which is ditficult to use in subsequent reactions.
  • the process of the present invention yields a product which is finely divided, and which is thus in a form eminently suitable for use in subsequent reactions.
  • di-alkali metal derivatives of the present invention are well-known in the art and have many and varied wellknown uses. They are in addition suitable for use as intermediates in the production of terephthalic acid and esters thereof by the procedures described in copending applications, Serial Nos. 419,576 and 419,578, filed March 29, 1954.
  • the present invention provides an improved process in which the product is not only in an eminently suitable form for use in subsequent reactions, but in which the yield of product is higher than in the processes previously disclosed.
  • a process for the production of di-alkali metal derivatives of dialkyl cyclohexa-l,4-diene-2,5-diol-1,4-dicarboxylates which comprises contacting a lower aliphatic di-ester of succinic acid with an alkali metal alkoxide in the presence of an organic diluent, which is a liquid under the reaction conditions, the said diluent being an ether having a boiling point of at least 90 C.
  • the alkoxide may be employed alone, or dissolved in a lower aliphatic alcohol, which is conveniently the alcohol corresponding to the alkoxide. If an alcohol is employed together with the alkoxide, this alcohol should be removed after the succinate and alkoxide have been contacted.
  • Di-esters which are specially suitable for use in the process of the present invention are dimethyl and diethyl succinates.
  • alkali-metal alkoxides which are specially suitable are methoxides and ethoxides, sodium methoxide and sodium ethoxide being particularly suitable.
  • a lower aliphatic alcohol is used as a solvent for the alkoxide, it is convenientfor this alcohol to correspond to the alkoxide employed.
  • sodium methoxide it is desirable for methanol to be employed as solvent; similarly, if sodium ethoxide is used, ethanol is a suitable solvent.
  • Ethers suitable for use in the present invention are, for example, di-n-propyl ether, di-n-butyl ether, di-isobutyl ether, di-sec. butyl ether and higher ethers. It is also possible to use ethers containing two oxygen atoms, such as ethylene-glycol dimethyl ether. However, the preferred ether for use in the process of the present invention is 1,4-dioxan (diethylene dioxide).
  • a volume of ether which is greater than the volume of succinate employed.
  • the reaction is carried out by heating together the dialkyl succinate, the alkoxide and the ether diluent.
  • sodium methoxide in the presence of methanol as the condensing agent, and dimethyl succinate as the ester thereaction is initially carried out at about 65 C., i. e., the boiling point of methanol. At this temperature, the
  • the product from the reaction is a dispersion of the di-sodium derivative of the dimethyl ester of cyclohexa-1,4-diene-2,5-diol-1,4- dicarboxylic acid in a single liquid phase, providing that the preferred ratio of reactants and diluents is employed, the said liquid phase comprising dioxan and unchanged dimethyl succinate.
  • the di-sodium derivative may be separated by filtration; the filtrate comprises dioxan and unchanged ester; these may be recycled to the condensation stage, or they may be separated by distillation.
  • Example I 46 grams of sodium metal were dissolved in 500 m1.
  • dry methanol contained in a 3 litre flask. 292 gm. (260 of dimethyl succinate and 900 ml. of dry dioxan were now added.
  • the mixture was heated on a bath maintained at a temperature of 80 to 100 C., and a stream of dry nitrogen was passed through the flask.
  • the methanol was completely removed via the distillation column attached to the flask. In efiecting the complete removal of methanol, some. 30 ml. of dioxan were also distilled over.
  • the reaction mixture was now refluxed under nitrogen for one hour.
  • Example 2 46 grams of sodium metal were dissolved in 600 ml. of ethanol, and a mixture of 348 gm. of di-ethyl succinate and 1000 ml. of dioxan were added. The mixture was heated as described above; dioxan removed at the same time as the ethanol was replaced from time to time. The reaction product was worked up as described above. 219 grams of di-ethyl cyclohexa-1,4-diene-2,5-diol-1,4- dicarboxylate, m. pt. 127 to 129 C., were isolated, this corresponding to a yield of 86% based on the amount of sodium ethoxide employed. From the dioxan filtrate, 5.4 gm.
  • a process for the production of di-alkali metal derivatives of dialkyl cyclohexa-1,4-diene-2,5-diol-1,4- dicarboxylates which comprises the step of contacting a lower aliphatic di-ester of succinic acid with a solution of an alkali metal alkoxide in an alcohol, in the presence of an amount of dioxane such that the dioxanezdi-ester volume ratio is within the limits 2.5 :1 to 10:1 and at a temperature which is initially of the order of the boiling point of the alcohol.
  • a process for the production of the di-sodium derivative of dimethyl cyclohexa-1,4-diene-2,5-diol-1,4- dicarboxylate which comprises the step of contacting dimethyl succinate with a solution of sodium methoxide in methanol, in the presence of an amount of dioxane such that the dioxanezdi-ester volume ratio is within the limits 3:1 to 5:1 and at a temperature which is initially C. and finally of the order of 100 C.
  • A' process for the production of the di-sodium derivative of di-ethyl cyclohexa-1,4-diene-2,5-diol-1,4-dicarboxylate which comprises the step of contacting di-ethyl succinate with a solution of sodium ethoxide in ethanol, in the presence of an amount of dioxane such that the dioxanefdi-ester volume ratio is within the limits 3:1 to 5:1 and at a temperature which is initially C. and finally of the order of C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US491207A 1954-03-19 1955-02-28 Condensation of dialkyl succinates Expired - Lifetime US2803644A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8066/54A GB751035A (en) 1954-03-19 1954-03-19 Improvements in and relating to the condensation of dialkyl succinates

Publications (1)

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US2803644A true US2803644A (en) 1957-08-20

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US491207A Expired - Lifetime US2803644A (en) 1954-03-19 1955-02-28 Condensation of dialkyl succinates

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US (1) US2803644A (is")
BE (1) BE536624A (is")
DE (1) DE965403C (is")
FR (1) FR1126443A (is")
GB (1) GB751035A (is")

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046817A (en) * 1974-07-19 1977-09-06 Imc Chemical Group, Inc. Method of synthesis of pyrogallol
US4092351A (en) * 1976-02-17 1978-05-30 Imc Chemical Group, Inc. Method of synthesis of 4,5,6-trihydroxyisophthalic acid
EP0057873A1 (de) * 1981-02-10 1982-08-18 Bayer Ag Verfahren zur Herstellung von Dimethylsuccinylosuccinat, dessen Dinatriumsalz, Dianilinodihydroterephthalsäuren, deren Dimethylestern und Salzen sowie von Dianilinoterephthalsäuren, deren Dimethylestern und Salzen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1082907B (de) * 1958-09-10 1960-06-09 Basf Ag Verfahren zur Herstellung von 2, 5-diarylamino-3, 6-dihydro-terephthalsaeureestern

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046817A (en) * 1974-07-19 1977-09-06 Imc Chemical Group, Inc. Method of synthesis of pyrogallol
US4092351A (en) * 1976-02-17 1978-05-30 Imc Chemical Group, Inc. Method of synthesis of 4,5,6-trihydroxyisophthalic acid
EP0057873A1 (de) * 1981-02-10 1982-08-18 Bayer Ag Verfahren zur Herstellung von Dimethylsuccinylosuccinat, dessen Dinatriumsalz, Dianilinodihydroterephthalsäuren, deren Dimethylestern und Salzen sowie von Dianilinoterephthalsäuren, deren Dimethylestern und Salzen
US4435589A (en) 1981-02-10 1984-03-06 Bayer Aktiengesellschaft Process for the preparation of dimethyl succinylosuccinate, the disodium salt thereof, dianilinodihydroterephthalic acids, the dimethyl esters and salts thereof, and dianilinoterephthalic acids, and the dimethyl esters and salts thereof

Also Published As

Publication number Publication date
BE536624A (is")
GB751035A (en) 1956-06-27
DE965403C (de) 1957-06-06
FR1126443A (fr) 1956-11-22

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