DE1252687B - Process for the epoxidation of organic compounds which contain one or more olefinic double bonds in the molecule - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .. C07d

German Kl 12 ο-27

Number.
File number filing date:
Display day

1252687
U10652IV b / 12 ο
April 11, 1964
October 26, 1967

The invention relates to a method for Epoxidation of organic compounds that one or contain several olefinic double bonds in the molecule, only lower percarboxylic acids or such containing mixtures of hydrogen peroxide and lower carboxylic acids in the presence of catalysts.

The epoxidation of organic compounds with one or more olefinic double bonds using lower percarboxylic acids or using lower carboxylic acids and Hydrogen peroxide - in the so-called in-situ process - is known There are already numerous catalysts for accelerating epoxidation has been described as sulfuric acid, p-toluenesulfonic acid, Hydroxyalkylsulfonic acids, aluminum oxide or ion exchange resins

The epoxidation is a strongly exothermic reaction, at which slightly em stormier, uncontrollable The course of the reaction occurs With known epoxidation catalysts it is not possible to let the reactants react with each other quickly without that the course of the reaction begins stormy and uncontrollable The strongly exothermic reaction could can only be kept under control despite cooling, that the addition of the per compounds on The beginning of the reaction is extremely gentle, e.g. carried out over the course of 2 or more hours This gentle addition is intended to increase the concentration of the reactants and undesired so that a sudden stormy reaction can be avoided.

The object of the invention is to provide a Process for the catalytic epoxidation of organic compounds containing one or more olefinic Contain double bonds in the molecule, hereinafter referred to as "unsaturated compounds" for short, in which the epoxidation in a much shorter reaction time, than they do with the known epoxidation processes is required with a good degree of epoxidation is made possible, and products are obtained which are largely free of undesired by-products are.

Surprisingly, it has been found that the reaction time in the epoxidation of unsaturated compounds can be reduced quite considerably while still avoiding a stormy, uncontrollable course of the reaction and side reactions such as ζ. Β Cleavage of the oxyran ring, can be suppressed if, during the epoxidation of the unsaturated compounds with percarboxylic acids, ζ. Β arising from H ₂ O ₂ and mederen carboxylic acids, such as methods for augmentation of organic Epoxydi
Compounds, the eme or more olefinic
Contain double bonds in the molecule

Applicant

Dr Angelos N Sagredos,
Hamburg 20, Lenhartzstrasse 6;
Dipl -Chem Themistochs K Katsibas,
Hamburg 33, Tieloh 18

Named as the inventor

Dr Angelos N Sagredos,

Dipl.-Chem. Themistochs K. Katsibas, Hamburg

Formic acid or acetic acid, or anthraquinone certain derivatives thereof or compounds from which these substances can arise through oxidation, used as a catalyst.

According to the invention, therefore, the catalyst used is anthraquinone, 2-ethylanthraquinone, 1,5-dihydroxyanthrachmone, anthraquinone monosulfonic acid or the sodium salt thereof in an amount of 1 to 5 percent by weight, based on the aqueous Medium.

According to a further embodiment of the present Process can use the anthraquinone catalysts also only in the epoxidation mixture of anthracene, 2-ethylanthracene or 1,5-dihydroxyanthracene be formed in a manner known per se. It has been found that using the mentioned catalysts in amounts of 1 to 5 percent by weight, based on the aqueous medium, in comparison with the known processes, the same

Degree of epoxidation in a fraction of the previous one usual response times can be achieved

The inventively applied harbors reaction temperature is generally between about 20 and 100 ⁰ C, preferably 50 to 8O ⁰ C. The carboxylic acid amount should be such that about 0.1 to 1, preferably 0.25 to 0.7 mol per mol of double bond to Application comes. The hydrogen peroxide is expediently in an amount of about 1.0 to 3.0, preferably 1.1 to 2.0 moles per mole of double bond

applied. With a larger excess of hydrogen peroxide, the epoxidation can
can be increased to a certain limit

The invention is illustrated below with reference to Examples explained in more detail

example 1

197 g of soybean oil (iodine number 129.0) with 23 g of formic acid (0.5 mole per mole of double bond) and 1.7 g of anthraquinone (2%, based on the aqueous phase) were placed in a reaction flask equipped with a stirrer, thermometer, reflux cooler and dropping funnel ) mixed the mixture was m a water bath at 60 ⁰ C then warmed wuiden 15 g 6O ° / oiges H ₂ O ₂ was added dropwise, with the temperature increase occurring by the exothermic reaction was einreguhert by cooling to 7O ⁰ C. Then 47.3 g of H ₂ O _{2 were} added dropwise with continued cooling (total amount 1.1 mol per mole of double bond). The _{addition of H 2} O ₂ can be carried out in a total of 10 to at most 20 minutes kept at 70 ^° C. After 80 minutes, the reaction was already over. The resulting ohge product was worked up in the usual way, washed out and dried in vacuo. After standing for a short time, precipitated anthraquinone was filtered off. The filtrate obtained had an end product whose iodine number was 9.7 and which had an epoxy-oxygen content of 5.82, corresponding to an epoxidation yield of 77.3%. exhibited. The anthraquinone filtered off after the reaction has ended can be purified by recrystallization

ίο in turn used as an epoxy catalyst will

Example 2

The starting materials given in Table I below were epoxidized in a corresponding manner as described in Example 1 with 1.1 mol of H ₂ O ₂ per mol of double bond, 0.5 mol of formic acid and 2% of anthraquinone, calculated on the aqueous phase The results obtained were summarized in Table I.

Table I.

Epoxidation at 70 ⁰ C with 0.5 moles of formic acid per mol double bond, 1.1 moles hydrogen peroxide per mole of double bond and 2% of anthraquinone as a catalyst, based on the aqueous phase

Starting product JZ after
Wijs Gram Reaction time
Minutes JZ after
Wijs Epoxy-S
calculated
7th oxygen
found
% Epoxidation
yield
Vo Cottonol. .
Safflorol ... .
Oleic acid methyl ester
Oleic acid 109
142.5
86.5
92.0 233
178
294
276 *) 120
80
80
80 4.2
17.2
10.3
14.2 6.43
8.25
5.16
5.48 4.81
5.95
4.11
3.53 74.9
72.0
79.3
64.5

*) In a mixture with 276 g of hexane

Example 3

In a corresponding manner as indicated in Example 1, were the starting products listed in Table II below with the sodium salt the anthraquinone-2-sulfonic acid epoxidized as a catalyst. Table II shows the results.

Table II

Epoxidation at 70 ⁰ C with 0.5 moles of formic acid per mol double bond, 1.1 moles hydrogen peroxide per mole of double bond and 2% of sodium salt of Anthracbinon-2-sulfonic acid, based on the aqueous phase

Table ΙΠ

Epoxidation of soybean oil at 70 "C with 1.1 mol of hydrogen peroxide and 0.5 mol of form sauce per mol of double bond and 2% of catalysts, based on the aqueous phase

40 Without . ... Reak Epoxy Epoxy Catalysts Anthracene .... functional
duration Sour-
material dation
yield 2-ethyl anthraquinone. Minutes 7o V. 1,5 - dioxyanthraquinone 80 5.22 69.2 80 5.75 76.5 80 5.52 73.4 80 5.7 76

Starting
matena! iodine
number Reaction
duration
Minutes Epoxy
Sour-
material
7th Epoxy
dation
yield
7th Soybean oil. .
Fish oil.
Olefins *). 130
198.7
187 80
50
80 5.61
6.1
6.08 74.6
55
57.6

*) Mixture of unsaturated hydrocarbons C ₁ to C ₁₈ , boiling range 170 to 200 ^° C. with a 2 mm Hg column

Example 4

Soybean oil was given in a manner similar to that in Example 1, with those listed in Table III Catalysts epoxidized The results obtained are shown in Table III.

Example 5

Soya oil was epoxidized according to Example 1, the Hydrogen peroxide amount was varied. The results are shown in Table IV.

Table IV

Epoxidation of soya oil (JZ 129.0) with 0.5 mol of formic acid per mol of double bond, varied Amount of water sturdy peroxide (60%) and 2% anthra-

S ₀ quinone (based on the aqueous phase) at 70 ⁰ C

Moles of H, O _{3 per mole}
Double bond Reaction
duration
Minutes JZ
after
Wijs Epoxy
Sour-
material
7o the end
prey
7th 65
1.1
1.5
2.0 80
90
90 13.1
2.7
1.7 5.83
6.22
6.33 77.5
82.7
84.2

As the examples show, the process enables according to the invention, the epoxidation of unsaturated Compounds with a good degree of epoxidation in a comparatively very short time that the known epoxidation process is not achievable

It is surprising that when working with the catalysts provided according to the invention, the reaction can be kept well under control in the usual way by cooling even if the H ₂ O _{2 is} added to the reaction mixture within 10 to 20 minutes. This not only saves time, but also makes a continuous working method considerably easier.

In addition, the method according to FIG the invention has the further advantage that the catalysts provided according to the invention due to poor solubility precipitate in oil and water at room temperature after cooling the reaction mixture and can be recovered by filtration and reused.

With variation of the amounts given in the examples and the choice of other reagents in the frame similar results are obtained according to the invention. So z. B. instead of those mentioned in the examples Formic acid also includes other lower aliphatic carboxylic acids be applied

The in the method according to the invention obtained products are good as plasticizers or stabilizers for plastics, especially for polymeric halogen-containing vinyl compounds are suitable. They are also of particular importance as components in the production of polymers or copolymers.

Claims (2)

Patent claims: 1. Process for the epoxidation of organic compounds, the eme or more olefinic Contain double bonds in the molecule, only lower percarboxylic acids or containing such Mixtures of hydrogen peroxide and lower carboxylic acids in the presence of catalysts, characterized in that the catalyst used is anthraquinone, 2-ethylanthraquinone, 1,5-dihydroxyanthracninone, anthraquinone monosulfonic acid or their sodium salt is used in an amount of 1 to 5 percent by weight, based on the aqueous medium. 2. The method according to claim 1, characterized in that one anthraquinone catalysts used only in the epoxidation mixture of anthracene, 2-ethylanthracene or 1,5-dihydroxyanthracene have been formed in a manner known per se.