SU475767A3 - Method for producing olefin oxides - Google Patents

Description

a solution in 50 ml of benzene and 0.0418 g of a catalyst consisting of a molybdenum hydroxy-8 quinoline oxide complex (Compound 1) (molar ratio hydroperoxide catalyst is 100: 1). Heat the reaction mixture to a temperature of 80 ° C. After 120 reaction reactions, the conversion of hydroperoxide is 100% and the selectivity of epoxidation cyclohexium is 90%. Consequently, the yield of eioxyclohexaia is 90%. Example 2. The same reagents, the same catalyst, are used in the same productions as in Example 1, but the catalytic system is activated beforehand. For this purpose, the catalyst (hydroperoxide in solution) is subjected to interaction (previously, before its introduction into the cyclohexea in benzene solution). The activation time is 4 hours (IoOio can be shortened). Then, an actuated cathode catcher is introduced into the solution of cyclohexene. After a 23 mH reaction, the complete conversion of the hydronerexide is observed; the selectivity of enoxyspclohexaia is 100%. The yield is 100%. Example 3. The experiments, identical to examples 1 and 2, are repeated according to the use of a catcher consisting of a complex of molybdenum oxide – acetylacetoacetate (a catalyst not suitable for catalyst 1). With a non-activated catalyst noreobravovine hydroperoxide and a hydrochloride after 40 minutes, 1) eacia, and the selectivity of enoxyhexane is only 70%. Yield 70%. With active catalyst {reversed} {full time after 23 mnn reaction, the epoxpd selectivity is 63%. The output of epoksnda 63%. Example 4. Oioratsionny conditions are the same as in examples 1 and 2. The catalyst is inorganic, molybdenum and MoO3, which is chemically useful in the same modern case as in the previous example. A non-activated kata.ppzator gives traces of results. Reaction time, mii230 Transformation of hydro-eurexisp,% 50 Selectivity of eioxaneplohexane,% 100 Yield of hexagon dioxide, hexane,% 50 Good active catalyst (4 hours activation). B | 1em 1) actions, mi230 Transformation of hydroirrex,% 50 Seq.activity, eioxycychochexia,% 100 Exit of eioxycyclohexaia. These rezu.htyaty orders in tablip, e. It can be stated that the results of Ziachtelio are lower than those that can be achieved with the use of good and rare metallographic catalytic systems. So, with ly.shbdeyovy.m. apgidrpdom, the difference in the selectivity of enoxide is obtained, and the formation of the bad is bad even after a long time of recovery. This distinctive result in the perception of securi- tiveness justifies the choice of molybdea as the metal component of the catalyst used in each example among the various metals V and VI of the periodic system of elements, in association with the organic compound. PRPMER 5. The sametsioynye conditions are the same as those found in Example 1: 1 ml of hydro-peroxide butyl, 10 ml of cyclohexene in solution in 50 ml of benzene. 0.0468 g of a catalyst consisting of an organometallic compound, in which the nitrogenous organic chelating agent is narachlorobenzhydroxamic acid (compound 2), in a solution of 10 ml of cyclohexepa and 1 ml of hydropex) eppsigregl butyl in 50 ml of xyloxype, in a mixture of 50 ml, wasn yyyyyyi in 50 ml of yyo-yyo-yyo-yyo-yseene in a mixture of 50%, y / y; mixture at 80 ° C. The unactivated catalnsagor has the following results. Reaction time, min20 Hydroperoxide conversion,% 100 Selectivity of epoxy cyclohexaa,% 100 Yield of ecsoxylloxohexa,% 100 Hydroxycatalyst (activation of 15 mi). Reaction time, min9 Transformed hydrocereacid,% 100 Selectivity of epoxy (% 100) Eioxycyclohexane yield,% 100 Example 6. U. of the same as in b) e 5, 0.0352 g of catalyst corresponding to MoO2 (Ci3HioO2N) 2 are introduced. (Compound} video 3). The results are as follows. Inactivating catalyst Reactivity time, mpp35 Hydroperoxide conversion,% 100 selec- EXAMPLE 7 Introduced into the reactor were 1 ml of gret-butyl hydronerexis, 4.2 g of ironylene c) and a solution of 50 ml of benzene and 0.0468 g of a catalyst consisting of an organometallic compound used in Example 5 and which gives no result Ata in epoksndnrovaiii tsik.chogeksena. Heat reagion mixture at 80 ° C. After 65 minutes of reaction, the conversion of the perpendicular product reaches 9 (5%, and the selectivity of the epoxpropane composition is 95%. The average yield of irope oxide is 91.2%. Example 8. U11). the same reagents, the same catalyst, in the same reactors, hhO in nrimer 7, but the catalytic system of the reactants is activated. To do this, before it is introduced into the propylene solution in Bepzole, the catalyst is reacted with hydroperoxide in solution for 40 minutes. The activated catalyst is then introduced into the ironllop solution. After 15 minutes of reaction, the hydroperoxide conversion is 98% and the nonionia oxide is obtained with a selectivity of 98%. Therefore, the yield is 96%.

According to the table, it can be stated that the catalysts according to the invention represent the combined advantages of already known organic and inorganic. The organic catalysts of the previous methods result in conversion rates of hydroperoxide to 100%, but 63-70% of eioxide selectivities (example 3), while the already known inorganic catalysts lead to inverse transformations of hydroperoxide, according to the selectivity of enoxide 100%. Only the catalysts used in the proposed method allow the conversion rates and selectivities to be brought to 100%.

Eioxidation of iropileia is easier than CMP Logexia. Trudio to obtain a quantitative yield.

Subject and d on and e and

The method of obtaining olefium oxides by means of olefin oxidation by organic hydroperoxide in an organic solvent solvent medium at an elevated temperature followed by separation of the target product by known methods, characterized in that, in order to trace the process and increase the yield of the final product, a preactivator in the same procedure, a method in the same procedure as the one of the one of the participants of the one of the one of the participants of the one of the one of the participants of the one of the one of them plans to use the one of the one of the one of the one of the one of them in the course of the program, the same as the one of the one), the procedure and the procedure in which the engine is using; based on metal oxide of elements of the V and VI groups of the periodic system emy orgaiicheskogo and nitrogenous compounds, chelate-forming compound with a metal oxide with 1 omoi; Strongly two bonds between the atoms of nitrogen and metal compounds, nairimer, hydroxy-N-hshyulnna PLD compound formuL1) 1

6

ngs-to-l;

about ol

where RI is an alkyl radical or an aromatic nucleus,

R2 is hydrogen, an alkyl radical or an aromatic nucleus.

characterized in that

2. The method according to claim 1, the molar ratio of the process is carried out with hydroperoxide equal to the catalyst and 0.1: 0.005.

3. Method according to paragraphs. 1 and 2, distinguished {ic

topics

that the process is carried out with respect to solvent and hydroperoxide, equal to 1.2-5 volumes per 1 volume of hydroperoxide.

4. Method but nn. 1-3, characterized in that cyclohexep or iropylclad is used as olefip.

Priority featured:

02.04.71. The catalytic system for the enoxidation of olefins is an organometallic complex based on metal oxide of elements V and VI of the periodic table and hydroxide-8 hydroxy;

02.04.71. The catalytic system for the enoxidation of olefnons is an metal-ororganic complex based on metallic oxide of the elements V and VI of the periodic system with a compound of the formula:

 Q - C-S - R2

 g, I about Oil:

where RI is an alkyl radical or aromatic ring,

Ro is hydrogen, alkyl radical or aromatic nucleus.

T a b .4 II c a 1