DE1768530A1 - Process for the preparation of monoepoxy compounds - Google Patents

Description

PATENT ANWXLTE DR. E. WIEGAND DIPL-ING. W. NIEMANN 1768530 DR. M. KÖHLER DIPL-ING. C. GERNHARDT MÖNCHEN HAMBURG

TELEPHONE: 55547 «8000 MUNICH 15, 24. Times I968

TELEGRAMMEt KARPATENT NUSSBAUMSTRA5SE 10

w. 13 705/68 13 / never

Toa Gosei Chemical Industry Co., Ltd. Tokyo (Japan)

Process for the preparation of monoepoxy compounds

Summary:

line Honoepoxy compound of a cycloolefin with more than 8 carbon atoms, for example i> a-epoxy-5,9-cyclododeg | tdiene or 1,2-epoxycyclododecane, is used in an advantageous manner by oxidizing the corresponding cycloolefin, e.g. 1,5 * 9-cyclod9decfctriene or cyclododecene, with a hydrogen peroxide solution using an oxygen compound of selenium as a catalyst.

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The invention relates to a process for the preparation of a monoepoxy compound using a Cycloolefins with more than 8 carbon atoms as a starting material, and in particular to a process for the preparation of a monoepoxy compound, for example 1,2-epoxy-5,9-cyclododecadiene, 1,2-epoxycyclododecane, 1,2-epoxycyclooctane, 1,2-epoxy-5-cyclooetene and 1,2-epoxy-3-cyclooctene Oxidation of the corresponding cyeloolefin, for example of 1,5,9-cyclododecatriene, cyclododecene, cyclooctene, 1,5-cyclooctadiene and!, ^ - cyclooctadiene.

These monoepoxy compounds prepared by the process according to the invention can be used widely as intermediates for synthetic fibers, for paints and varnishes, plasticizers or the like. be used.

The above-mentioned monoepoxy compounds of Cycloolefins having more than 8 carbon atoms or at least 8 carbon atoms, for example 1,2-epo3ty-5,9-cyclododecadiene or 1,2-epoxycyclododecane, have been hitherto produced by oxidation of 1,5,9-cyclododecatriene or cyclododecene with a organic peroxide, for example performic acid, peracetic acid, perbenaoic acid or the like., Manufactured. However, since In general, such organic peroxides are expensive oxidizing agents and are also very unstable, so that their transport and handling are difficult or dangerous

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be borrowed, and there is also one of these common ones Operation with a considerable amount of the formation of formic acid, acetic acid or the like. as a by-product the practical implementation of such a process on an industrial scale, these difficulties must should always be considered as important problems.

Studies have therefore been made on a method for producing epoxy compounds with a high selectivity or high yield from the above starting materials, making this process practical should be easily feasible on an industrial scale, and it was found that these purposes can thereby can achieve that the cycloolefin with more than 8 or at least 8 carbon atoms, for example 1,5,9-cyclo- «Todecatriene, cyclododecene or the like, with water to ff peroxide in is oxidized in a solvent using an oxygen compound of selenium as a catalyst.

The object of the invention is therefore to provide an improved process for producing the above-mentioned ones Äonoepoxyverbindungen from the corresponding cycloolefins »it more than 8 or at least 8 carbon atoms, that of is free from the difficulties of the customary procedure outlined above.

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ORIGlNAL BATHROOM

A further object of the invention is to provide a process for the preparation of the above-mentioned monoepoxy compounds which can be carried out easily and advantageously on an industrial scale.

The I5> 9 -cyclododecatriene used as a starting material according to the invention is an unsaturated compound having carbon atoms which can easily be prepared by the trimeric cyclization of 1,3-butadiene, a product having a trans, trans, cis structure and an. Product having a trans, trans, trans-structure is obtained, each of both of the invention can be used as starting materials in accordance with the method. Also, cyclododecene of the invention used according to the starting material is a compound, which is obtained by hydrogenation of 1,5,9-pertielle Cyclodedeoatrien and a cis or trans structure has, on the can as cycloolefins having 8 carbon atoms, for example, 1.5 -Cyclooctadiene and 1,3-cyolooctadiene, which are obtained by the dimeric cyclization of butadiene , and also cyclooctene, which is obtained by partial hydrogenation of these dienes, are used.

The most important feature according to the invention is based on the oxidation of the above-specified cycloolefins " having more than 8 or at least 8 carbon atoms with an oxygen compound of selenium, with their I" öe "

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BATH ORIGINAL

possibility in the starting hydrocarbons or reaction liquids appropriate and preferably as selenium compounds selenium dioxide, jfelenous acid or an alkyl ester of selenous acid, e.g. methyl ester or ethyl ester of selenous acid (e.g. _{CH 5 OSeO 2} H, C ₂ H ₅ OSeO ₂ H, (CH ₅ O) ₂ SeO and (C ₂ H ₅ O) ₂ SeO), are used for the oxidation of 1,5,9-cyclododecatriene, while selenium dioxide, fine acid, an alkyl ester of selenous acid, e.g. methyl ester or ethyl ester of selenous acid (e.g. CH ₅ OSeO ₂ H, C ₂ H ₅ OSeO ₂ H, (CH ₅ O) ₂ SeO and (C ₂ H ₅ O) ₂ SeO), an acidic alkali salt of selenous acid, e.g. NaHSeO ₅ and KHSeO. ,, and an acidic one Alkaline earth salt of selenous acid, e.g. Ca (HSeO _{5 I 2} , can be used for the oxidation of cyclododecene and cycloolefins having 8 carbon atoms. In the oxidation of any of the above-mentioned cycloolefins, however, the catalytic effect of selenium dioxide and selenous acid is very remarkable.

There is no particular restriction on the amount of the above-mentioned catalyst, but if 0.005 to 0.2 mol, in particular 0.01 to 0.1 mol, of the catalyst is used per 1 mol of the starting hydrocarbon, a more economical space reaction rate is possible general can be expected.

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The process according to the invention is carried out in a solvent which is inactive to the reaction and any solvents which do not necessarily induce a secondary reaction with the starting material of hydrocarbon, hydrogen peroxide and the catalyst and the reaction products can be used . However, taking into account the solubility of the starting material and the catalyst in the solvent, the ease of handling and in view of economic advantages, primary alcohols, secondary alcohols and tertiary alcohols, for example methanol, ethanol, n-propanol, isopropanol, tert. -Butanol, n-butanol, isobutanol or the like. Used.

moreover, can in the method according to the invention as a solvent other than the above-mentioned alcohols, esters of aliphatic carboxylic acids such as methyl acetate, ethyl acetate, methyl propionate or the like., and chlorine derivatives of W saturated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane or the like., used will.

There is also no particular limitation on the are, however, generally using advantageously from 0.1 to 10 vol. Solvent per 1 parts by by volume portion of the starting hydrocarbon to be used amount of solvent.

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When the concentration of hydrogen peroxide used as an oxidizing agent in the process according to the invention is higher, the extent of the reaction is higher and the reaction can be carried out at a lower reaction temperature. However, a lower concentration of hydrogen peroxide can be used by increasing the reaction temperature or increasing the concentration of the catalyst. Wt & Accessories Sounds is an aqueous solution having a Wasserstoffperoxyd- M Konzentratinn of about 10 to 95% is used. In addition, the amount of hydrogen peroxide per 1 mole of starting hydrocarbon must not be too high, since when an excessive amount of hydrogen peroxide is used, higher oxidation products, for example oxy compounds, are generated as by-products in addition to the monoepoxy compounds. In particular, when using less than 1.25 mol, preferably less than 1.0 mol, of hydrogen peroxide per 1 mol of starting material in the oxidation of a cycloolefin with more than 2 double bonds, for example of 1,5,9-cyclododecatriene, cyclooctadiene or the like. Like., the desired epoxy compound can be obtained with a high selectivity. The reaction according to the invention can be carried out at a temperature from 0 to 80 ⁰ C, which is however useful in the practice of 1st to carry out the reaction at a Tenperatur tm range of 20 to 60 ° C.

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In practicing the process according to the invention, the total amounts of aqueous hydrogen peroxide can be used and the starting cycloolefin mixed in a reactor together with the catalyst and the solvent however, in the case of using a large apparatus, the method according to the invention is preferred is carried out in such a way that one of the starting materials is first introduced into the reactor containing the catalyst and the solvent of cycloolefin and hydrogen peroxide introduces and then introduces the other starting material or continuously the two components in the large one introducing the catalyst and the solvent-containing reactor with sufficient removal of heat of reaction.

When the reaction system consists of a heterogeneous phase or when the reaction system consists of a homogeneous phase Phase consists, it is convenient and desirable to stir the reaction system in the reactor vigorously to remove the heat of reaction to remove.

The method according to the invention has several advantages. Such is the selectivity to the epoxy compound and the yield with respect to hydrogen peroxide is high. The oxidizing agent used according to the invention is inexpensive and there are no by-products such as formic acid, acetic acid or the like. The solvent and the oxidizing agent can

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can be handled with ease, and the catalyst used can also be easily removed from the reaction system after completion win the reaction by extracting it with water; will.

The invention is explained in more detail below with the aid of examples, in which the yield (A) for the epoxy compound based on the starting material, and the yield (B) for the epoxy compound based on the hydrogen peroxide in the following Ways are defined:

Epoxy compound produced (number of moles)

A = χ 100 {%)

Converted starting material (number of moles

Epoxy compound produced (number of moles)

B = x 100

Hydrogen peroxide used (MolzahH)

In addition, in the examples, the analysis for cycloolefin carried out by a gas chromatographic method and analysis for the epoxy compound was carried out by adding a sample to a mixed solution of hydrochloric acid and ^ and determining the amount of hydrogen chloride that is not with of the epoxy compound reacted, carried out by alkaline titration.

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example 1

5.0 g of selenium dioxide and 97.3 g (0.60 mol) of trans, trans, cis-1,5,9-cyclododecatriene were added to 200 ml of tert-butanol, followed by stirring. 8.29 ml (0.30 mol) of an aqueous hydrogen peroxide solution with a content of 1.2.30 g / ml of hydrogen peroxide (corresponding to a concentration of βϋ, 7% by weight ) were added to 100 ml of tert-butanol and the resulting solution was added Solution was slowly added dropwise to the above prepared solution of the cyclododecatriene over a period of about 2 hours. In this case, the temperature of the system was maintained at ⁰ C 25 to 3O. If the system was kept at the same temperature for 16 hours, free hydrogen peroxide was completely consumed. Thereafter, the reaction mixture was washed with an aqueous sodium sulfite solution and, after removing the solvent by distillation at normal pressure, the remaining liquid thus formed was distilled under reduced pressure -Cyclododecatriene passed, were obtained and then 37.2 g of fractions consisting mainly of 1,2-epoxy-5,9-cyclododecadiene with a boiling point in the range from 85 to Ö9 ° C / 12 mm Hg were obtained, with 9.9 g of a residue with a high boiling point after the distillation.

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stayed. The sum of the unconverted trans, trans, cis-1,5,9-cyclododecatriene in the initial fractions and the middle fractions that were obtained in this way was 57 * 2 g and there were 3 ^, 9 gl, 2- Obtained epoxy-5,9-cyelododecadiene. Thus, the yield for 1,2-epoxy-5,9-dyclododecadiene, based on the cyclododecatriene consumed, was 77 % and, based on the hydrogen peroxide added, 0%. The middle fractions obtained were again subjected to a distillation, a liquid with a boiling point of 96 to 97 ^° C./2 mm Hg being obtained.

Elemental analysis of the 1,2-epoxy-5,9 ~ prepared in this way cyclododecadiene:

Calc .: C 80.85 % H 10.18 %
Found: C 80.77 % H 10.15 %

In the infrared absorption spectrum analysis of the product, there were 2 strong absorptions representing the characteristic of trans-CH = CH- and cis-CH = CH- at about 975 cm or at about 700 cm ".

Example 2

5.0 g of selenium dioxide and 97 * 3 g (0.60 mol) of trans, trans, cis-1,5,9-cyclododecatriene were added to 200 ml of isopropanol admit, after which it was stirred, in order to add the selenium dioxide to solve. Then 8.29 ml (0, ^ 0 mol) of an aqueous Hydrogen peroxide solution with a content of 1.2 ^ 0 g / ml of hydrogen peroxide (corresponding to a Konaantratinn of

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88.7 wt .- ^) is mixed with 100 ml of isopropanol and the mixture was slowly added dropwise to the solution of the cyclododecatrienes, prepared as above, was added over a period of about 2 hrs., Whereby the temperature of the system at 25 to 30 ⁰ C was held. After the system was kept at the same temperature for 40 hours, the reaction mixture was washed with an aqueous solution of sodium sulfite, and thereafter the solvent and water were removed from the reaction system by distillation at normal pressure. The remaining liquid was subjected to distillation under reduced pressure to obtain initial fractions and middle fractions as in Example 1 above, while leaving only high-boiling materials as the distillation residue. The amount of the intermediate fractions having a boiling point range of 99 to 10J ⁰ 5 mm Hg, which were obtained in such a way was 39.1 g, and it was found that this product consisted mainly of 1,2-epoxy-5,9-cyclododecadiene; the product was examined by means of gas chromatography and infrared absorption analysis. On the other hand, the amount of the high-boiling residue was only 3.1 g. The sum of Vans, trans, cis Ij5j9-cyclododecatriene in the initial and middle fractions thus obtained was 52.4 g. The amount of epoxy compound,

in
the middle fraction (s) was 37.3 g,

calculated as 1,2-epoxy-5,9-cyclododecadiene. From these he-

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As a result, the yield for the cyclododeeadiene was calculated to be 92 % _t, based on the trans, trans, cis-1,5 * 9-cyclododec-triene consumed, and 70 %, based on the added hydrogen peroxide.

Examples 3 and 4

The same procedure as in Example 2 was repeated using the same amount of a different alcohol as a solvent in place of isopropanol to produce the oxadatins of trans, trans, cis-1,519-cyclododecatriene, whereupon the yield for the cyclododecatriene was calculated . When using n-propanol as solvent, the yield of Cyclododeeadien 92 # was, based on the Cyclododecatrienverbrauch, and J55% _$ based on the added hydrogen peroxide and using ethanol as solvent, the yield 8 ^ $, based on the Cyclododecatrienverbrauch, and 26 %, based on the added hydrogen peroxide.

Example 5

The same procedure as indicated in Example 2 was repeated, with only the reaction temperature was changed, namely, wherein the aqueous hydrogen peroxide solution was added dropwise at 45 to 50 ⁰ C and the reaction mixture for a further 5 hrs. At room

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temperature was maintained. The amount of 1,2- epoxy-5,9-cyclododecadiene produced was 26.4 g, while the amount of high-boiling residue was 5.5 g. The yield for the cyclododecadiene was 83%, based on the consumed -Cyclododecatrien, and # 49, based on the added hydrogen peroxide.

Examples 6 and 7

The same procedure as in Example 2 was repeated, the concentration of the aqueous hydrogen peroxide being varied; the influence of the concentration of hydrogen peroxide on the yield of 1,2- epoxy-59-cyclododecadiene was observed. In Example 6, an aqueous hydrogen peroxide solution with a content of 0.730 g / ml hydrogen peroxide (corresponding to a concentration of 59.0 wt .- ^) was used in the same molar amount as in Example 2, with 30.8 g of cyclododecadiene and 5.1 g of high-boiling materials were obtained . The yield for the cyclododecadiene was 87 %, based on the cyclododecatriene consumed, and 58%, based on the hydrogen peroxide added.

In Example 7, an aqueous hydrogen peroxide solution with a concentration of 34.1 % by weight was used in the same molar amount as in Example 2, with 21.2 g of 1,2-epoxy-5,9-cyclododecadiene and 3.1 g of a high-boiling residue

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were obtained. The yield for the cyclododecadiene was 87 %, based on the cyclododecatriene consumption, and 40%, based on the added hydrogen peroxide.

Example 8

8.0 g of selenium dioxide and 97.5 g (0.0 mol) of trans, trans, cis-1,5,9-cyclododecatriene were added to 200 ml of isopropanol added and then a mixture of jX), 8 ml (0.66 mol) of an aqueous hydrogen peroxide solution with a Concentration of 59.0 wt .- ^ (with a content of 0.750 g / ml Hydrogen peroxide) and 50 ml of isopropanol slowly drop by drop added to the above-prepared solution of the cyclododeeatria over a period of 3 hours, the temperature of the system has been adjusted to 25 to j50 C. After this the system was kept at the same temperature for 16 hours, the system was then operated according to the usual one Treated manner and then subjected to a distillation. Then the amount of 1,2-epoxy-5,9-cyclododecadiene measured.

The amount of cyclododecadiene was 70.8 g, the amount of high-boiling materials was 16.4 g, and the amount of unreacted trans, trans, cis-1,5,9-olododecatriene was 17.2 g. The yield of cyclododecadiene based on the consumed cyclododecatriene was thus 80.4 %.

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Example 9

The same procedure as in Example 2 was repeated using 5 * 8 g of selenous acid (HpSe (X) instead of 5.0 g of selenium dioxide, 36.9 g of 2-epoxy-5,9-cyclododecadlene and 4.1 The yield of the obtained cyclododecadiene g of high boiling residue. was 88.3 U "based on trans, trans, cis-1,5,9-Cjclododecatrienverbrauch, and 69.0% based on added hydrogen peroxide.

Example 10

In 200 ml of isopropanol, 97.3 g (0.60 mol) of trans, trans, trans-l, 5> 9-cyclododecatriene and 5 * 0 g of selenium dioxide dissolved and then a mixture * of 14.0 ml (0.30 mol) of an aqueous hydrogen peroxide solution with a concentration of 59 * 0 wt .- ^ and 100 ml of isopropanol dropwise that of the above prepared solution over a period of 2 hours.

o ben, with the system at a temperature of 25 to 30 C was held. After the system was kept at room temperature for another 40 hours, the system became treated in the usual way. After removing the solvents by distillation, the remaining liquid became one Subjected to distillation under reduced pressure to initially

trans,
unreacted / trans, transyl, 5,9-cyclododecatriene and

then 38.6 g of a fraction with a «boiling point range of

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Distill 90 to 93 ° C / 2 mm Hg. The epoxy compound in the latter fraction was analyzed quantitatively. The result showed that it contained 0.0553 mol / g of an epoxy group, this being in agreement with the theoretical value (0.0562 mol / g) of the epoxy group in 1,2-epoxy-5,9-cyclododecadiene. In addition, the infrared absorption spectrum showed the presence of strong absorptions which are the characteristics show of trans double bonds.

Example 11

Using the same procedure as in Example 2, 9.7 g of ethyl selenite (C ₂ H ₅ OSeO ₂ H) were used instead of 5.0 g of selenium dioxide and the system was reacted ^{at 25 to JO 0 C for 16 hours.}

From the results of a gas chromatographic analysis of the product, it was confirmed that 25.5 g of 2-epoxy-5,9-cyclododecadiene had been formed, which corresponded to a yield of 48 % based on the added hydrogen peroxide.

Example 12

To 104 g (0.60 mol) of cyclododecene with a purity of 96 % (molar ratio of trans form to cis form: 68:32 ; content of small amounts of cyclododecane and cyclododecane

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176G530

serve as impurities) 200 ml of isopropanol and 5.0 g of selenium dioxide were added, followed by stirring, and a solution obtained by diluting 16.58 ml (0.60 mol) of an aqueous hydrogen peroxide solution with a content of 1.2 ^ 0 g / ml of hydrogen peroxide (corresponding to a concentration of 88.7 wt -.%) was obtained with 100 ml isopropanol, was added dropwise to the above prepared solution and in the course of 2 hours was added, while the temperature of the system at 25 to 3O ⁰ C was held. After stirring the system for further 16 hours at the same temperature range, the reaction mixture was washed with a 5 # aqueous sodium sulfite solution, and after removing the solvent by distillation under reduced pressure, the remaining liquid was distilled under reduced pressure with a small amount of an initial fraction, which mainly contained unreacted cyclododecene, and thereafter 91.5 g of a fraction having a boiling point range of 125 to 130 ° C./1O mm Hg and mainly containing 1,2-epoxycyclododecane was obtained. In addition, the amount of high-boiling residue was only 3.9 6, and the amount of unreacted cyclododecene remaining in the reaction liquid was 7 ^ 6. Moreover, the sum of 1,2-epoxycyclododecane was that in the initial fraction

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and in the middle fraction obtained, 90.9 g. From the above results, the yield for 1.2%) oxycyelododecane was 96 %, based on the cyclododecene consumed, and 83 %, based on the added hydrogen peroxide, calculated.

The middle action won above was again distilled to give a colorless liquid with a boiling point of 116 to H7 ° C / 5 mm Hg.

Elemental analysis of the product as 1,2-epoxycyclododecane: Calc .: C 79.06 % H 12.17 £
Found: C 79.05 % H 12.08 %

The product was found to be 5.45 χ 10 ~ · ^ mol / g absorbed in hydrogen chloride in Dloxan at room temperature and it was also determined by gas chromatography that the product consisted of a mixture of the two isomers (trans-form / cis-form about 72/28).

Example I3

To 300 ml of tert-butanol was added 5.0 g of selenium dioxide and 14.92 ml (0.54 mol) of an 88.7 $ strength aqueous hydrogen per oxide solution added, whereupon to dissolve the Selenium dioxide was stirred. Then 104 g (0.60 mol)

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Cyclododecene has a purity of about 96 % (same as
in Example 12) slowly dropwise ± the above
prepared solution in the course of 2 hours. Using a
Dropping funnel added, the temperature of the system at 25 to 30 ⁰ C was kept. After allowing the system to stand overnight at the same temperature, the reaction mixture was washed with an aqueous sodium sulfite solution. After removing the solvent and water from the reaction mixture by distillation under normal pressure, the remaining liquid was then subjected to distillation under reduced pressure to obtain an initial fraction and an intermediate fraction as in Example 12,
while only a high-boiling residue remained as a distillate residue. The amount of the middle fraction
with a high boiling point range of 102-107 ° C / 3 mm Hg that was recovered contributed 62.15 g and the product was found to consist of a fraction consisting mainly of 1,2-epoxyeye-iododecane with a minor proportion of cyclododecene , the product being subjected to gas chromatographic analysis. On the other hand was fraudulent
the amount of high-boiling residue just 8.0 g and the amount of unreacted cyclododecene, which in the initial

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fraction and remained in the middle fraction, was 37.1 g. The amount of the epoxy compound quantitatively analyzed in the middle fraction was 60.9 g, calculated as 1,2-epoxycyclododecane. From the above results, the yield for the epoxycyclododecane 89% was based on the consumed cyclododecene, and 62% _s in relation to the added hydrogen peroxide, calculated "

Example 14

The same procedure as in Example 12 was repeated using 34.6 g (0.6o mol) of a 59.0 # strength aqueous hydrogen peroxide solution instead of 16.58 ml of an 88.7 # strength aqueous hydrogen peroxide solution, and the products became the Yield determined for the 1,2-epoxycyclododecane. The yield was 94 #, based on the consumed cyclododecene, and 77 $>"based on the added hydrogen peroxide.

Example 15 The same procedure as in Example I3 was followed

Ethanol Use of 300 ml $ & $ // $$ £ &&% instead of 3OO ml

tert-Buta.nol as a solvent and of 0.60 mol of a 34.1% aqueous hydrogen peroxide solution instead of 0.54 mol of 88.7% aqueous hydrogen peroxide solution, whereupon the system was repeated for 40 hours at 25 to 30 ⁰ O

A ;

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was allowed to implement. The yield of 1,2-epoxyoyolododecane, which had been prepared in this way, was 95 % based on the consumed cyclododecene and 84% based on the added hydrogen peroxide.

Example 16

The same procedure as in Example 12 was repeated using 8.0 g of selenous acid (HgSeO-,) instead of 5.0 g of selenium dioxide, the temperature being kept at 50 to 55 ° C during the dropwise addition of the hydrogen peroxide solution. After the addition of the hydrogen peroxide solution was completed, the reaction system was kept at the same temperature for 5 hours and then subjected to post-treatment and distillation in the usual manner. In this reaction, 78.5 g of 1,2-epoxycyclododecane were obtained, the amount of the high-boiling residue being 9 # 7 g and the amount of the unreacted cyclododecene being 19.6 g. Thus, the yield for the epoxy compound was 89 % based on the consumed cyclododecene and 72% based on the added hydrogen peroxide.

Example I7

The same procedure as in Example 12 was carried out using 10 8 g (0.60 mol) of cis-cyclododecene with a purity of about 93 % (containing about 7 percent by weight

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on cyclododecane as contamination) as the starting material. The cis-cyclododecene was obtained by reducing trans, trans, cis-cyclododeeatria have been produced.

In this process, 89.8 g of an epoxy compound having a boiling point of 100 to 104 ° C / 4 mmHg was obtained. Gas chromatographic analysis showed only one peak for an epoxy compound and the peak coincided with one of the two peaks indicated by a mixture of trans-cyclododecene and cis -cyelododecene. The yield for 1,2-epoxycyelododecane was 81 % _t based on the added hydrogen peroxide.

Example 18

A mixture of 1.11 g of selenium dioxide, 0.40 g of sodium hydroxide and 5 g of distilled water was reacted to obtain a suspension of acidic sodium selenite. To this suspension were added 30 ml of isopropanol and 17.3 cyclododecene having a purity of about 96 % which was the same as specified in Example 12, and then f, Q g of a 34% aqueous hydrogen peroxide solution was added to the resultant Mixture added with stirring. After stirring the system for 3 hours at room temperature, the reaction liquid thus formed was analyzed by gas chromatography to find that 1.6 g of 1,2-epoxycyclododecane was produced.

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BATH ORIGINAL Example 19

To 1.11 g of selenium dioxide and 1 ^, 3 g of cyclododecene with a purity of 96% _t which is the same as was in Example 12 was added 30 ml of ethyl acetate or chloroform, and then 7.0 g of a 3 ^ #igen aqueous hydrogen peroxide solution was added, followed by stirring for 5 hours. vigorously at about 3O ⁰ C. The reaction liquid thus formed was analyzed, whereby the formation of 1,2-epoxycyclododecane was confirmed. When ethyl acetate was used as the solvent, its amount was 1.8 g, and when chloroform was used, it was 2.3 g.

Example 20

The same procedure as in Example 12 was _{repeated using 9.7 g of ethyl selenite (CgH 5} OSeO ₂ H) as a catalyst. The yield for 1,2-epoxycyclododecane was 53 %, based on the added hydrogen peroxide.

Example 21

The same procedure as in Example 12 was repeated using 8.0 g of selenious acid as a catalyst and 6.3 g of triethylamine as a basic material, said reacting for KQ hr. At 25 to 3O ⁰ C was carried out. The amount of 1,2-epoxycyclododecane thus formed was 32 g and the yield was 29 %, based on the added hydrogen peroxide.

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BATH ORIGINAL

Example 22

Ij5.3 g of selenium dioxide were dissolved in 250 ml of isopropanol and then I30 g (1.2 mol) of 1,5-cyclooctadiene were added to the solution thus prepared. Thereafter, a mixture of 16.6 ml (0.6 MPI) an aqueous hydrogen peroxide solution and 90 #igen 50 ml of isopropanol was dropwise added over 2 hrs., The reaction temperature was maintained at ⁰ C to 35 J50.

After stirring the system for a further 2 hours at the same temperature, the reaction mixture was washed with an aqueous sodium chloride solution, a 5% aqueous acidic sodium sulfite solution and then with a 5% aqueous sodium carbonate solution in the order given. The aqueous phase of the washing liquid was extracted with ether and the ether phase was combined with the reaction mixture. After drying with sodium sulfate, the mixture obtained was distilled under normal pressure, inter alia ^ first to remove the ether and then the isopropanol together with some of the 1,5-cyclooctadiene. The remaining liquid was under reduced pressure to obtain an initial _{fraction P 1} , which was mainly composed of 1,5-cyclooctadiene, and dapn of 51.9 g of a middle fraction Fg with a

boiling point

from JO bi · 71 ° C / 12 μHg, which mainly consists of

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ORiGlNAL INSPECTED

consisted «distilled. The amount of the high-boiling residue was 6.2 g. In addition, 73.5 g of 1,5-cyelooctadiene remained unexposed in the reaction mixture. The sum of the epoxy compounds (epoxy group) contained in fraction P ₁ and in fraction F ₂ was 56.0 g, calculated as l ^ -epoxy-S-cyclooctene. Based on the above results, the 1,2-epoxy-5-cyolooctene was found to have a yield of £ 87, based on the 1,5-cyoloootadiene consumed, and 75 %, based on the hydrogen peroxide added.

Example 23

_{dissolved, 1O 4} O g of selenium dioxide were added in 200 μl of isopropanol and then

g of cyclooctene (1.2 mol) were added to the solution thus prepared. A solution of 33.2 ml (1.2 mol) of a 90 pounds aqueous hydrogen peroxide solution and 100 ml of isopropanol was then added dropwise to the solution prepared above! History "has been said Realetionstemperatur at 30 to 35 ⁰ C held added of 3 hrs. With stirring. After stirring for a further 8 hours at the same temperature, the reaction mixture was then washed with a 30 pounds aqueous sodium chloride solution, a 5 pounds aqueous acidic sodium sulfite solution and then a 5 % aqueous sodium carbonate solution in the order given. Dl aqueous

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BAD ORlGiNAL

Phase of the washing liquids obtained above
extracted with ether and the ether phase was extracted with the
Reactive mixture combined. After drying with sodium sulfate, the mixture was subjected to distillation under normal pressure
subjected to first removing ether and then isopropanol. The remaining liquid was distilled under reduced pressure, initially using a small amount of isopropanol and unreacted cyclooctene and then
63 * 5 g of a fraction having a boiling point of 68 to ^"0 Jl C / W% 2 mm Hg, which mainly consisted of 1,2-epoxycyclooctane, were obtained. The amount of the high-boiling residue was only 4.6 g. Fraction of 1,2-epoxycyclooctane
was in a solid state at room temperature and its melting point was 49 to 55 ° C. Analysis of the content of epoxy groups in it showed that the fraction contained 59 * 6 g of 1,2-epoxycyclooctane, which corresponded to a yield of 79 % based on the hydrogen peroxide added. When the fraction was distilled under reduced pressure, 1,2-epoxy-cyclooctane with a boiling point of 64 to 65 ° C./9 mmHg
and a melting point of 56 to 57 ° C.

Example 24

The same procedure as in Example 22 was carried out using the same amount of 1,3-cyclooctadiene in place

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of 1,5-cyclooctadiene to carry out the oxidation of 1,3-cyclooctadiene. After the completion of the reaction, the reaction product was washed, extracted, dried and then subjected to distillation at normal pressure to remove ether and isopropanol. When the remaining liquid was distilled under reduced pressure, a fraction F ₁ , which consisted mainly of unreacted! The amount of epoxy groups contained in fraction Fg was 0.43 mol and the yield for the 1,2-epoxy-3-cyclooetene was 72 %, based on the hydrogen peroxide added.

Example 25

Oxidation of 1,5-cyclooctadiene was carried out using the same procedure as in Example 22 of tert-butanol instead of isopropanol and also of

iger
15.5 g of selenic acid carried out instead of selenium dioxide.

The amount of 1,2-epoxy-5-cyclooctene thus formed, determined by gas chromatographic analysis, was 5 ^ * 5 g # during the value obtained by quantitative analysis of the epoxy value using the hydrochloric acid method was 53 * 1 g. This

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Value was equivalent to a yield of about $ 72 based on the indicated hydrogen peroxide.

Example 26

The oxidation of cyclooctene (1.2 mol) was carried out by the same procedure as in Example 23 using 200 ml of ethanol as the solvent instead of isopropanol and also a mixture of 106.5 ml (1.2 mol) of a ^ 33 > 5 show aqueous hydrogen peroxide solution and 100 ml of ethanol executed as hydrogen peroxide solution. The reaction was carried out at 45 to 50 ^° C. for 16 hours.

The reaction product was subjected to distillation under reduced pressure to obtain 67.9 g of a fraction consisting of 1,2-epoxycyclooctane, having a boiling point 75-78 ⁰ C (14 mm Hg) and 10.4 g of a high boiling Praktion were obtained . The yield for 1,2-poxycyclooctane was 63 %, based on cyclooctene and added hydrogen peroxide. ^

Example 27

To 30 "ml of methyl acetate or chloroform was added 11.0 g (0.1 mol) of cyclooctene and 1.11 g of selenium dioxide were added, and 2.77 ml (0.1 mol) of an 88.8% aqueous Hydrogen peroxide solution to the mixture thus prepared added, followed by vigorous stirring. After implementing the

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Systems During 5 hours at 30 to 35 ° C, the reaction product was formed by gas chromatography with reference to the Analyzed amount of 1,2-epoxycyclooctane. The amount thus obtained was 1.5 g using methyl acetate as the Solvent and 1.2 g when using chloroform.

Example 28

The oxidation of 1,5-cyclooctadiene was carried out according to the same procedure as in Example 22 using 15.5 g of selenous acid instead of 13 * 3 g of selenium dioxide and also using 6.5 g of triethylamine as the basic material, ^ after carrying out the reaction for 8 hours at 30 to 35 ^° C. 45.2 g of 2-epoxy-5-cyclooctene were obtained. The yield of product was 61 #, based on the added hydrogen peroxide.

Example 29

A mixture of 11.0 g (0.1 mole) cyclooctene, 1.5 g of acid sodium selenite, 100 ml of ethanol and 8.8 ml (0.1 mol) of a 33.5 # aqueous hydrogen peroxide solution was during Vigorously stirred for 40 hours at room temperature. By gas chromatographic analysis it was found that 3.7 g 1,2-epoxycyclooctane had been formed.

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example

The same procedure as in Example 22 was repeated using 12 g Äthylselenit (CoHLOSeOgH) instead of l j>, repeated 5 g selenium dioxide, whereby 52.3 g of 1,2-epoxy-5-eycloocten were obtained.

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Claims (1)

Claims Λ, a process for producing monoepoxy compounds, characterized in that a cycloolefin with at least 8?: Carbon atoms is oxidized with V ^ass erstoffperox.vd in a solvent in the presence of an oxygen compound of gels as a catalyst. 2. The method according to claim 1, characterized in that as a cycloolefin with at least 8 carbon atoms, 1,5,9-cyclododecatriene to 1,2-epoxy-5,9-C7-clododecadiene oxidized as the main product. 5. The method according to claim 1, characterized in that as the cycloolefin having at least 8 carbon atoms, cyclododecene is oxidized to 1,2-epoxycyclododecane as the main product. 4. The method according to claim 1, characterized in that one is a C-cycloolefin with 8 carbon atoms, in particular Cyclooctene, 1,5-cyclooctadiene or 1,3-cyclooctadiene implements. 5. The method according to any one of claims 1 to 4, characterized in that the oxidation is carried out at a reaction temperature of 0 to 80 ° C. 109839/1671 BATH ORIGINAL