DE2223299A1 - Process for the preparation of alpha-substituted epoxy compounds - Google Patents

Description

2223293

P α t »π Κ η W ^ö '* * έ, BräuhauMfraB *

Gases
12/10 / ka.

SlTM HlOGEMI S.p.A., May land / Italy

Process for the preparation of a- * substituted epoxy compounds

The present invention "relates to a method of manufacture of α-substituted epoxy compounds *

In particular, the present invention relates to an oxidation process for alcohols with a functional group in the ß-position with respect to the hydroxyl group, with molecular oxygen, in Presence of a catalyst based on copper compounds.

Process for the preparation of substituted or unsubstituted Epoxid ^ connections are known »They are generally based on multistep reactions and are carried out using reagents that are difficult to obtain, which is economically viable the process is significantly affected.

In contrast, the production of such epoxies is not possible known by means of metal catalysis *

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It has now been found that it is possible to use substituted epoxy Compounds in a simple and cheap way to synthesize by a method that is acceptable from the industrial point of view seen is very interesting.

According to the present invention, functional epoxy yers bonds of the general formula

R "
R- I

_ ^ \ j ^^^ \ J - Ji-

obtained in which R, R 'and R ¹ ' hydrogen, hydrocarbon radicals with up to 12 carbon atoms, which can be identical or different, can be simple or substituted alkyl, cycloalkyl, aryl radicals, X is one of RCO-, -CN , -COOR, phenyl and substituted phenyl compounds, tinyl and the like is the selected functional group, in which R is as defined above.

The compounds are substituted by oxidation of the corresponding ß-substituted Alcohols obtained: the oxidation is carried out by molecular oxygen in the presence of copper compounds-Die The alcohols used have the general three-word formula

R "

^ C-CH-X
R '^ l
OH

wherein R, R ¹ , R ¹ 'and X have the above meanings.

The reaction proceeds with the formation of the substituted epoxides according to the following scheme:

R " _T R"

R \ I Cu ¹ R \ I

C-CH-X + f / 2 O ₉ CC-X + H ₀ O

OH

20 9 8 4-8 / 125 1

and is catalyzed by monovalent copper compounds.

Copper-I compounds in which copper is bonded to an anion, such as CuX ¹ , in which X ^{1 is} a halide ion such as chloride, bromide, iodide or fluoride or one from the group CN "", CEUOCCf ", enolate, can be used. Represents nitrate, perchlorate and the like selected anion.

In order to achieve better solubility and thus a higher reaction rate, monovalent copper complexes of the type CuX ¹ L can advantageously be used, in which η is an integer from 1 to 6, X ^{1 has} the above meanings and L is an unsubstituted coordinate base or is substituted and is selected from phenantrolines, dipyridylene, pyridines, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), phosphines, arsines, stibines, imidazole, piperidine, etc.

According to an interesting observation, show similar behavior like copper, all metals, with at least 2 valence states that are capable of easily changing from one to the other, such as Iron, manganese and cobalt.

A particular importance of the process according to the invention lies in the possibility of the monovalent reaction at the end of the oxidation reaction To obtain starting copper compound that can be "re-used", thereby closing the catalytic cycle.

The oxidation process according to the invention can be carried out easily; it leads to good yields and can be carried out over a wide pressure and temperature range. It is possible to work either in the presence or in the absence of solvents or diluents. In the latter case, the alcohol itself serves as the reaction medium.

In contrast, solvents can be used in the former case that come from the group of unsubstituted or sub-

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substituted alkyl, aromatic and cycloaliphatic hydrocarbons, Ethers and others or are selected from the bases mentioned above.

The reaction temperatures can vary within a wide range and should, like the working pressure, maintain the liquid phase.

Useful ranges for the temperature at 15 ° to 15O ⁰ C and the pressure at 1 to 30 atmospheres.

If compounds of the formula CuX ¹ Ii are used, they are prepared by customary techniques and can be introduced into the reaction ^{vessel as such or can be obtained starting from Cu X 1} and L in the course of the oxidation reaction itself.

Some other work peculiarities are illustrated by the following example shown, which serves to explain the invention without limiting it.

Example - manufacture of

CH-_

³ J ^ G ^ -HSH-CO-CH ₃

A mixture consisting of 48 g of diacetone alcohol and 3.5 g of pyridine was prepared. Therein were 2 g CuCl dissolved and the whole at 70 ⁰ C with oxygen bubbled (2 1 / hr.).

After 12 hours, 2.5 g of CuClPy were separated off by filtration under nitrogen; the reaction products were analyzed in the solution by gas chromatography. The conversion of the diacetone alcohol was 28 % with a selectivity of 95 % for the epoxide and 5 % for acetone. 12.5 g of the epoxide and 0.7 g of acetone were obtained.

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Claims (1)

1 *, teriahi ^ n for the preparation of α-substituted epoxy compounds of the; , general formula, \ _ "'";''""'";'"""_' / ''" R ^. I. Wherein R, R ^f and R ¹ 'hydrogen, Konlenwasserstoffreste with a number' from ^ up to · to; 12 ^ G-rAtomeni ^: die / equal -or TerscMeden sej.n _v KSfidfen, töisubstituierte, or substituted allsyl-j Cycloalkyl-- _v and aromatic radical ei .can j / X one. FttnlctiQnelle Gruppe,,. ■ selected from R00 ~ -, (SS _f GOORj is phenyl or substituted phenyl compounds and vinyl -, where R has the meanings given above, characterized in that ß- * substituted alcohols with the general formula: '·.; .. ■ · ,:.; -: - · _i; ^ -.-J., -., -.:.:.>: ■; -. _{:: V} ,. -. - ,. ' - ,, £ -.-; - .: C «OH - X where R, R *, R * * and X have the above meanings, oxidized in the presence of monovalent copper compounds as catalysts »'-''r''- 2. The method according to 'claim A ;''dkdürW marked ■■ dä ^ - ¹ a ^! ls "■ -monovalent" copper compound ¹ 'a' connectiondei ^ type ötuO * ve'r ^ winds "where X ¹ 'a' ffialoigenidion / wxe'Cl ^ Br" * ¹ ^ l ^ and '^ edei? Anion, such as οϊΠ, CH «OOO"", enolate, kitrat and perchlorate is used, where η means a whole 'number' from "V" to "6," X ¹ ' ⁰ % le has the meanings given in claim 2 and Ii is a' kooriina- is tive base, which can be unsubstituted or substituted and is selected from the phenantrolines, dipyridyls, pyridines, Dimethyl sulfoxide, dimethylformamide, phosphines, arsines, Stibines, imidazole and piperidine. 4. The method according to claim 1 or 2, characterized in that the reaction in the presence of the single alcohol as the solvent medium is carried out. 5. The method according to claim 1 or 2, characterized in that the reaction is carried out in the presence of a solvent is selected from the unsubstituted or substituted alkyl, aryl or cycloalkyl hydrocarbons and ethers will. 6. The method according to any one of claims 1 to 3 »characterized in that that the reaction is carried out in the presence of only the alcohol as the solvent medium. 7. The method according to any one of claims 1 to 3, characterized in that that the reaction is carried out in the presence of a solvent selected from the unsubstituted or substituted alkyl, aryl or cycloalkyl hydrocarbons, Ethers or from the coordinative bases listed in claim 3. 8. The method according to any one of the preceding claims, characterized in that the reaction! Temperatures is carried out in the range of 15 ° to 150 ⁰ G at. 9. The method according to any one of the preceding claims, characterized in that the reaction at a in the range of 1 to 30 atmospheres pressure is carried out « 209848/1251