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WO1999010336A1 - 2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique - Google Patents

2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique Download PDF

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Publication number
WO1999010336A1
WO1999010336A1 PCT/EP1998/005044 EP9805044W WO9910336A1 WO 1999010336 A1 WO1999010336 A1 WO 1999010336A1 EP 9805044 W EP9805044 W EP 9805044W WO 9910336 A1 WO9910336 A1 WO 9910336A1
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WO
WIPO (PCT)
Prior art keywords
compounds
acetic acid
independently
formula
molar ratio
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.)
Ceased
Application number
PCT/EP1998/005044
Other languages
German (de)
English (en)
Inventor
Hans-Joachim Traenckner
Friedrich-Wilhelm Ullrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AU92593/98A priority Critical patent/AU9259398A/en
Publication of WO1999010336A1 publication Critical patent/WO1999010336A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings

Definitions

  • the present invention relates to 2- (1,4-dioxan-2-one-3-yl) acetic acid esters, a process for their preparation, their use and intermediates for the production process.
  • R 2 and R 3 have the meaning given above and
  • R 4 is straight-chain or branched C 1 -C 12 -alkyl
  • R 5 has the meaning given for R 4 independently of R 4 ,
  • the invention further relates to the use of the compounds of the formula (I) as solvents or as formulating agents, for example for the formulation of crop protection agents, pharmaceuticals or similar substances.
  • Alkyl in the formulas mentioned has 1 to 12 carbon atoms and means, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, the isomeric pentyls, hexyls, Octyle, decyle or dodecyle.
  • Alkyl preferably has 1 to 4 carbon atoms and particularly preferably means methyl or ethyl.
  • the maleic acid dialkyl esters to be used according to the invention result from the alkyl substituents mentioned in an obvious manner. Be particularly preferred
  • 1,2-glycols to be used according to the invention also result from the alkyl substituents mentioned in a manner which is obvious to the person skilled in the art.
  • Suitable alkaline compounds are (earth) alkali metal hydrides, amides and alcohols.
  • Amides are derived from NH 3 or from primary or secondary aliphatic amines with 1 to 6 carbon atoms; Amides can also from
  • Alcoholates are derived from C Cg alkanols. However, alcoholates can still be the mono- or bis-alcoholates derived from the 1,2-glycols to be reacted according to the invention. Such glycolates are formed in the reaction mixture by adding the hydrides, amides or alcoholates mentioned. However, they can also be prepared in a separate step before the reaction.
  • (earth) alkali metal hydroxides or carbonates can also be used to prepare the glycolates;
  • water since water is formed when they are used in the formation of glycolate, it is necessary to separate this water of reaction before the start of the reaction according to the invention, for example by an azeotropic distillation, in order to be able to maintain anhydrous conditions during the reaction according to the invention.
  • the substituted acetic acid ester (la) has the restricted scope of R 4 in its alcoholic ester component R 1 .
  • Such a course of the reaction occurs when the lower part of the molar ratio of (II): (III) is 1: 0.5-3, preferably 1: 0.7-2, particularly preferably 1: 0.9-1.1 , very particularly preferably 1: 1. If one chooses molar ratios in the upper part of the range, i.e.
  • the substituted acetic acid ester in its alcoholic component assumes the limited scope that is derived from 1,2-glycol (III).
  • the radicals R 2 and R 3 can be interchanged, as has already been shown in the context of the formula (Vb to e) in the right part of the formula with the ester-like 1,2-glycol.
  • the ethylene glycol is used as the glycol
  • the 2- (1,4-dioxan-2-one-3-yl) acetic acid ester is obtained as a racemate, since an asymmetry center is generated by the addition reaction.
  • substituted glycols which are generally used as a racemic mixture or as a mixture of the diastereomers
  • the diastereomers 2- (1,4-dioxan-2-one-3-yl) -acetic acid ester are accordingly also obtained.
  • R 2 and R 3 are different, two regioisomers are formed their diastereomers. In the manner mentioned, only one of these regioisomers is shown in the formula scheme above; the other results from swapping R 2 and R 3 .
  • the invention further relates to the intermediates (Va to e) produced by the addition reaction and not yet closed to form the 1,4-dioxane ring.
  • the 2- (1,4-dioxan-2-one-3-yl) acetic acid esters of the formula (I) are formed in the process according to the invention, which can also be represented by the sum of the partial formulas (Ia to c).
  • the reaction product is therefore generally a statistical mixture of the various ether esters of the formulas (Va to e), including possible diastereomers and regioisomers.
  • the substituted glycol can form the ether bond with each of the two hydroxyl groups and, independently, can also form the ester bond with each of the two hydroxyl groups. This creates eight regioisomeric compounds, each of which occurs in their diastereomeric species. Five of the possible reaction products (Va to e) are listed here as examples.
  • the other isomers result from exchanging the two substituents R 2 and R 3 on the ether-linked glycol. In the case of symmetrically substituted glycols, only a constitution with their diastereomers and with ethylene glycol a product as a racemic mixture is formed.
  • the desired acetic acid ester (I) is the species with sub-formula (la) in which the alcoholic ester component is from an alkanol
  • Acidic compounds for this are, for example, mineral acids, such as hydrogen chloride, sulfuric acid or phosphoric acid, or organic acids, such as benzenesulfonic acid, toluenesulfonic acid, halogenated alkanesulfonic acids, or acidic ion exchangers;
  • Transesterification catalysts are, for example, titanium or tin tetraalcoholates.
  • the process according to the invention with catalysis by alkaline compounds can be carried out in the presence or in the absence of a solvent.
  • a dipolar aprotic is preferred.
  • cyclic lactams such as N-methyl-pyrrolidone
  • cyclic ureas such as 1,3-dimethyl-imidazolidin-2-one or acetonitrile.
  • the reaction can also be carried out in the absence of solvents if those species of (II) and (III) are used which have a low molecular weight and are therefore liquid or at least one of which is liquid and the other dissolves.
  • non-system solvents which would make work-up more difficult, if a higher molar excess of the 1,2-glycol is used to the extent mentioned and this glycol is liquid.
  • the reaction mixture of (II) and (III) is neutralized after the reaction has ended, for example by adding tartaric acid or another nonvolatile
  • the transesterification to convert the subgroup species (Ib) or (Ic) into the subgroup species (la) can also be carried out in the presence of an anhydrous inert
  • the substances of the formula (I) can be used in a variety of ways as solvents or as formulating agents, for example for crop protection agents and pharmaceuticals. They are characterized by a wide temperature range in which they are in a liquid state under normal pressure. For example, methyl 2- (dioxan-2- on-3-yl) -acetate melts at + 33 ° C, but has a strong tendency to hypothermia and is in the liquid state, especially in the presence of small amounts of residual ethylene glycol, from which it was produced to temperatures of around -5 to + 5 ° C. On the other hand, due to its high
  • Molecular weight has a high boiling point, which is, for example, below 2 mbar at 130 to 132 ° C and cannot be determined exactly under normal pressure due to decomposition phenomena.

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

Abstract

On peut obtenir des 2-(1,4-dioxanne-2-one-3-yle)-esters d'acide acétique de la formule (I), où R<1>, R<2>, et R<3> représentent, indépendamment les uns des autres, C1-C12-alkyle ramifié ou non ramifié; où R<2> et R<3> peuvent également, indépendamment l'un de l'autre, représenter hydrogène, ou bien représenter ensemble -(-CH2-)n pour n = 3, 4 ou 5, tandis que R<1> peut aussi représenter -CH(R<2>)-CH(R<3>)-OH ou bien -CH(R<3>)-CH(R<2>)-OH, en mettant à réagir des esters diéthyle d'acide maléique avec des 1,2-glucols des formules (II) et (III), où R<2> et R<3> ont la signification susnommée et R<4> représente C1-C12-alkyle ramifié ou non ramifié, lors d'une catalyse par des composés alcalins et dans des conditions caractérisées par l'absence d'eau.
PCT/EP1998/005044 1997-08-22 1998-08-08 2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique Ceased WO1999010336A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU92593/98A AU9259398A (en) 1997-08-22 1998-08-08 Acetic acid 2-(1,4-dioxane-2-one-3-yl)-esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19736543.4 1997-08-22
DE1997136543 DE19736543A1 (de) 1997-08-22 1997-08-22 2-(1,4-Dioxan-2-on-3-yl)essigsäureester

Publications (1)

Publication Number Publication Date
WO1999010336A1 true WO1999010336A1 (fr) 1999-03-04

Family

ID=7839824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/005044 Ceased WO1999010336A1 (fr) 1997-08-22 1998-08-08 2-(1,4-dioxanne-2-one-3-yle)-ester d'acide acetique

Country Status (3)

Country Link
AU (1) AU9259398A (fr)
DE (1) DE19736543A1 (fr)
WO (1) WO1999010336A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT326365B (de) * 1972-07-14 1975-12-10 Unilever Nv Kunststoffzusammensetzung
EP0023293A1 (fr) * 1979-07-14 1981-02-04 Hoechst Aktiengesellschaft Procédé de préparation de 2.3-perfluoro-1.4-dioxannes et de trifluorométhyl-1,4-dioxaunes
EP0302007A1 (fr) * 1987-07-14 1989-02-01 Ciba-Geigy Ag Acides hydroxy-éther-carboxyliques et leur lactones, procédé pour les produire et leur utilisation comme inhibiteurs de corrosion
WO1997002326A1 (fr) * 1995-06-30 1997-01-23 Bp Chemicals Limited Diluants reactifs
WO1997002229A1 (fr) * 1995-06-30 1997-01-23 Bp Chemicals Limited Diluants reactifs
WO1997025452A1 (fr) * 1996-01-11 1997-07-17 Monsanto Company Processus de preparation de tetraalkyle 1,2,3,4-butanetetracarboxylates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT326365B (de) * 1972-07-14 1975-12-10 Unilever Nv Kunststoffzusammensetzung
EP0023293A1 (fr) * 1979-07-14 1981-02-04 Hoechst Aktiengesellschaft Procédé de préparation de 2.3-perfluoro-1.4-dioxannes et de trifluorométhyl-1,4-dioxaunes
EP0302007A1 (fr) * 1987-07-14 1989-02-01 Ciba-Geigy Ag Acides hydroxy-éther-carboxyliques et leur lactones, procédé pour les produire et leur utilisation comme inhibiteurs de corrosion
WO1997002326A1 (fr) * 1995-06-30 1997-01-23 Bp Chemicals Limited Diluants reactifs
WO1997002229A1 (fr) * 1995-06-30 1997-01-23 Bp Chemicals Limited Diluants reactifs
WO1997002230A1 (fr) * 1995-06-30 1997-01-23 Bp Chemicals Limited Diluants reactifs
WO1997025452A1 (fr) * 1996-01-11 1997-07-17 Monsanto Company Processus de preparation de tetraalkyle 1,2,3,4-butanetetracarboxylates

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEM.PRUM., vol. 20, no. 1, 1970, pages 20 - 22 *
CHEM.PRUMYSL, vol. 16, no. 2, 1966, pages 97 - 100 *
CHEMICAL ABSTRACTS, vol. 66, no. 2, 9 January 1967, Columbus, Ohio, US; abstract no. 2818k, ZDENEK ORDELT: "Addition of 1,2-diols and glycidylethers to double bonds during polymerization with maleic anhydride II. Addition of glycidyl butyl ether and reaction mechanisms." page 328; column 1; XP002088142 *
CHEMICAL ABSTRACTS, vol. 72, no. 23, 8 June 1970, Columbus, Ohio, US; abstract no. 121465a, KRATKY BOHUMIL ET AL.: "preparation of 2-hydroxyethoxysuccinic acids and their ether lactones." page 348; column 2; XP002088141 *

Also Published As

Publication number Publication date
DE19736543A1 (de) 1999-02-25
AU9259398A (en) 1999-03-16

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