SU388550A1 - Method of simultaneous obtaining of carbonyl compounds and epoxy compounds - Google Patents

Description

This invention relates to a process for the simultaneous production of carbonyl compounds and enoxysadinates used as intermediates in the manufacture of synthetic detergents, as well as polyester and polyamide resins.

A known method of producing higher aldehydes and ketones o.xosynthesis (M. Complexity of technical formulations (MEEEI and low selectivity of the main product make it difficult to carry out this method. It is also known to obtain epoxy compounds by reaction of hydroperoxides with olefins, according to which olefins are obtained with a cold yield, but alcohols are formed as a second product.

To eliminate these drawbacks, a demolition was proposed, in which the reaction of the interaction of olefins is carried out with a wide variety of peroxides of various structures, obtained by ozone reaction of olefins, at a temperature of 50-170 ° C, pressure O-40 atm in the presence of epoxidation catalysts.

The carbonyl and epoxy compounds are obtained simultaneously with the chorus yield by the proposed method.

Example 1. Synthesis of hydroperoxide a-tertbutoxidecyl.

Gregbutoxydecyl hydroperoxide is obtained by ozonation reaction 10 g of undecene-1

at 2:00 g g / z-butyl alcohol in a 250 m bubbling type reactor. Ozonized oxygen is passed through the reaction mixture for 15 minutes (concentration

ozone 3-4 vol.%) at a rate of 1.5 l / min until the cessation of ozone absorption. The temperature of the mixture in the reactor does not exceed 25 ° C.

The ozonation product is diluted with a large amount of water; the resulting oil layer is washed several times with water, resulting in 16.5 g of hydroperoxide a-greg-butoxydecyl as a viscous liquid. Product identification and purity determination are carried out using thin layer chromatography, IR spectroscopy and I | MP spectroscopy.

Preparation of the catalyst. 7.2 g of MoO3 (0.05 mol), 6.3 g of oxalic acid (0.05 mol) and 100 ml of water are placed in a flask.

The mixture is heated in a water bath for 12 hours. The next day, water is evaporated and 70 g of abietic acid (0.23 mol) are added to the residue. The mixture is heated for 2 hours at 200 ° C. The dark brown melt is drained.

from the flask and the solidified precipitate is ground in the fringe.

Conducting the reaction of peroxide with olefin. A mixture of 10 ml of cyclohexene, 3 g of a-tert-butoxydecylhydronerekis n 0.07 g of catalyst

(abietta Mo) incubated for 2.5 h

Ave. and energetic unmixing, three 90 ° C in jieaKTope with Reversible fridge.

The reaodionic mixture is cooled and filtered, after which excess cyclohexene is distilled off from the filtrate and then the products are separated by distillation. The degree of decomposition of hydroperoxide is 91.0%. The yield of aldehyde oxide is 88.5% of the theoretical value (all calculated on decomposed hydroperoxide).

L p and m e r 2. Reaggtstsi with a, a-dioxydidecyl peroxide.

The reaction of the preparation of a, a-dioxy-isadiadrenexy 1 is tested as follows.

20.0 g of undecene — 1.56.0 g of water and 300 g of acetone are mixed until a clear, uniform solution is formed. After cooling; g to 0 ° C, ozonized oxygen (concentration 3-4 vol.%) Is passed through the solution at a rate of 1.5 liters and stopped until it is absorbed. The ozoniro | Vani product is diluted with a large amount of water and extracted several times with ether. From the ether extract after the dried sulphate over the sulfate: the ether is distilled off by the ether IB vacuum without heating. As the ether is distilled off, white peroxide crystals are isolated. Yield 21.2 g. For the analysis of the obtained peroxide, a part of the crystals twice 1 × recrystallize from an aqueous alcohol. Characteristics of the obtained a, a-dioxydidecylnerekis: T. nl. 70 ° C, mol. weight. 346, the content of a1 active oxygen is 4.6%. A mixture of 10 ml of d clogaxene, Zg a, adecoidEdecillerexis and 0.07 g of catalyst (Mo abieta), prepared analogously to example 1, is incubated for 2.5 hours with vigorous stirring (with cloves, and a magnetic stirrer) at 91 ° C.

The epoxidation products are separated in the same manner as in Example 1. The degree of decomposition by peekioi is 94.0%. The output of cyclohexene oxide is 97.0%; the yield of capric (decane) aldehyde is 88.6% (on decomposed peroxide).

Example 3. Reaction with ozonide g & xena-. Oeonide hexene-1 was obtained by ozone treatment with 20 g of hexene-1 in 200 g of hexane IB in a 250-cm barbon type reagent. The reaction solution is cooled to -70 ° C (dry ice and acetone) and ozone-treated oxygen (acolo ozone 4 vol.%) At a speed of 1.6 m / min until it stops; ozone is consumed. The reactor with the reaction product is removed from the cooling mixture, the solvent is distilled off in vacuo without heating. The cube residue is a colorless mobile liquid with an active oxygen content of 7% and a boiling point of 42 ° C (.10 mm Hg). The yield of the ozonide hexena-compound is 90% of the theoretical; the purity of the obtained product is determined by thin layer chromatography using an IK-spectrum 01C copy and NMR spectroscopy.

A mixture of 1-0 ml of cyclohexene, 2.5 g of ovide gwxen, 1.05; . Patriot hydroxide and 0.07 g of catalyst (Mo abieta) are kept in

for 2.5 hours with vigorous stirring at a temperature of 87 ° C. The reaction products are separated by distillation. The degree of decomposition of ozonide is 90.0%. The yield of cyclohexene oxide is 5 72.5% of the theoretical, the yield of valeric aldehyde is 67.5% of the theoretical (on the decomposed ozonide).

PRI: measure 4. 20 g of cyclohexene is ozonated in 200 mm of ethanol at -70 ° C with an ozone-oxygen mixture containing 3-4% ozone before ozone leakage. The content of active oxygen is 2.3 wt. %

A solution containing 12-17% peroxides (mono-dimensional and polymeric ethoxydronerex cis hexanal) is fed to the epoxidation. Epoxidation is carried out in a sealed glass ampoule or in a flask with an agitator at 98-1: 00 ° C for 3 hours.

The catalyst is abiett Mo in the amount of 0.2 wt. % of the loaded hydroperoxide.

The output of the oxide. Cyclohexene 80%. The degree of peroxide decomposition is about 1-00%.

The yield of adinic aldehyde 50%, adipi5 new aldehydic acid 24.5%.

PRI: measure 5. From hydroperoxide obtained by ozonation of cyclohexepa in ethyl alcohol according to Example 4, ethyl alcohol is distilled to a content of 12-15% hydroperoxide. The resulting solution was placed in an epoxidized flask and cyclohexene. The reaction of epo | ksndirovi wires. T analogous to example 4, but with the addition of 0.2 g of crystalline KOH. The output of epoxycyclohexane 86,5%; adinic aldehyde 62.5%, adipic aldehydic acid 11.8%.

Example 6. Wg of cyclopentene in 100 ml of ethyl debris is ozonized at –70 ° C with oxygen-containing oxygen containing 8–10 0 weight. % ozone to ozone breakthrough. Ethanol was distilled off from the resulting reaction mixture containing monomeric and polymeric tidro.peroxides. A solution containing II– 15% hydroperoxide is fed to epoxy. Epoxide is carried out in a manner analogous to Example 4. Peroxide decomposition is close to quantitative. Output of epoxycyclohexane 85%, glutaraldehyde 25%, glutaric aldehyde acid 10%. In the reaction mixture 0, polymeric substances are present - glutaraldehyde condensation products. Product separation is carried out as in Example 1.

Approx. 7. Joint production of capri5 aldehyde and propylene oxide.

Claims (2)

Hydroperoxide a-greg-butoxvdecyl is obtained by ozonization of undecene-1 (obtained by distillation of the products of thermal cracking of soft petroleum steam.phine) in t / et-butyl alcohol in analogy to example 1. 4.5 ml of a stainless steel autoclave are loaded g of the hydroxyperoxide obtained in this way, 20 ml of trimethylcarbonyl, 0.05 g of Mo abietat and 40 g of liquefied polyethylene propylene. The autoclave is heated to 15 ° C for 15 minutes and maintained at this temperature for 1 to 2 hours. The pressure during the reaction is E5-25 atm. Then the autoclave is rapidly cooled and the excess propylene is gradually released. The reaction products are removed from the autoclave and analyzed iodometric method: m on the residual content of peroxide. According to the analysis, the degree of decomposition of hydroperoxide is 99.0%. The reaction products are then separated by rectification. The yrolylene oxide (m.p. 32-35 ° C) yields 82.7% (decomposed hydroperoxide). The yield of kairin aldegia, 2% (ida (t., Ki1P. C / 5 mmHg) decomposed hydroperoxide). Example 8. CoBiMecTHoe production of capric aldehyde and propylene oxide. a, a-Diaxidecyl peres-cis. are obtained by ozonization of undecene-1 (obtained by distillation of products of thermal cracking of soft oil paraffin) in a water-acetone solution in a similar manner to 2. In a stainless steel autoclave with a capacity of 200 ml, 5.05 g of the a, a-diO | Xididecyl pervicis obtained by the above method, 20 ml of trimethyl carbonyl binol, 0.05 g of Mo abietat and 40 g of liquefied prolylene are loaded. The autoclave is heated to 130 ° C for 12 minutes and maintained at this temperature for 1 hour and 45 minutes. The pressure during the reaction is 35-20 atm. The autoclave is cooled and gradually reduces the pressure to atmospheric, releasing an excess of propylene. The reaction products are analyzed by iodometric method for the residual content of nerexis. According to the analysis, the degree of peroxide decomposition is 98.0%. The reaction products are separated by rectification. The yield of oxide-proline 79.0% (on the decomposed hydroxyl), -calin aldehyde (on the decomposed peroxide) 85.0%. DETAILED DESCRIPTION OF THE INVENTION Method for simultaneous production of carbonyl compounds and eioxys compounds, characterized in that olefins are reacted with ethylene oxide compounds — the product of ozonization of ir olefins at a temperature of 50-170 ° C and a pressure of 0-40 atm in the presence of epoxidized catalysts.