LU82959A1 - PROCESS FOR THE PREPARATION OF CARBONYL COMPOUNDS CONTAINING AT LEAST ONE FUNCTIONAL GROUP IN ADDITION TO CARBONYL GROUPS, AND COMPOUNDS THUS OBTAINED - Google Patents

Description

4

Process for the preparation of carbonyl compounds containing at least one functional group in addition to the carbonyl groups, and compounds thus obtained.

The present invention relates to a process for syn-S thethlser carbonyl compounds containing one or more functional groups in addition to the carbonyl group in their structure.

The process consists in reacting a carbonyl compound with a compound containing at least one unsaturated bond (double or triple) and one or more functional groups, the reaction being carried out in the presence of catalytic amounts of peroxides.

The carbonyl compound can be a ketone or an aliphatic, aromatic or alicylic aldehyde; having a methyl or methylene group in the alpha position relative to the carbonyl group and ^ in particular ^ may be an alpha-methyl ketone.

s

The unsaturated compound, as we said; may contain one or more olefin bonds and / or one or more acetylenic bonds, an unsaturated bond in the terminal position being preferable, and may optionally contain one or more functional groups which may be chosen, for example, from -OH, -OOCCH ^, -Cl, -OCH ^, -OC ^, -CN, -C00H, -COOR.

The root addition reaction of ketones to alpha-olefins or cyclohexene has been known for some time and is caused, for example, by salts or oxides of transition metals. In this case, low yields of the final useful product are obtained. Organic peroxides or peroxyesters as radical sources have also been used in stoichiometric amounts relative to the Initial carbonyl compound. In addition to obtaining the final products with absolutely insufficient conversion and selectivity values, plus the presence of an excessive amount of peroxides, there has never been any mention of the possibility of preparing compounds containing groups " 55 extremely different functional groups, since the possibility of carrying out the reaction directly between the carbonyl compound and the unsaturated compound containing one or more functional groups has not been provided.

• 2

• I

The discovery, constituting the object of the present invention, was made by the applicant, that it is possible to react a carbamoyl compound with.

a compound containing at least one unsaturated bond in. same time as one or more functional groups in the presence of catalytic amounts of peroxide. In this way high conversion and selectivity values of the final useful product are obtained, the latter according to another aspect of the present invention also comprising compounds containing the carbonyl group simultaneously with one or more functional groups whose presence n has never been envisaged or planned at the same time as the carbonyl group. These compounds include the ethers and esters of 6-methylheptan-6-15 ol-2-one. The reaction is therefore carried out in the presence of a peroxide in an amount such that its molar ratio to the unsaturated compound varies from 1/1 to 0.005 / 1. The peroxides which can be used for this purpose are diacetyl-peroxide, diben-zoyl-peroxide, tert-butylhydroreroxide, dicyelohexyl-peroxydicarbonate etc., the use of di-tert-butylperoxide having proved to be particularly advantageous. The reaction can be carried out starting only from the substrates, or it can be carried out in the presence of water in an amount sufficient to constitute either a single phase or two liquid phases with the mixture of unsaturated compound and carbonyl compound brought in. react.

The feeding of these is such that the molar ratio of the carbonyl compound to the unsaturated er-npose varies from 500/1 to 3/1 and, in particular, from: jD / 1 to 5/1. Finally, it should be noted that the compounds formed according to the process of the present invention have various applications. For example, the product obtained p: a · this means starting from acetone and 2-methyl-3-butene-2-ol, in particular 6-methylheptan-6-ol-2-one, can constitute the poini starting for the production of numerous terpenic derivatives, for example hydroxylinalol, citral, hyiroxycitral, hydroxycitro-nellal, geranonitrile, ior.mesetc. etc.), used 3 | in aromas, perfumes, vitamins, drugs 3 and surfactants.

The methylheptanolone derivatives which have particularly valuable odorous characteristics * can be obtained from acetone and ethers or esters of 2-methyl-3-butene-2-ol by direct etherification or esterification of methylheptanolone . The present invention is illustrated by the following descriptive and nonlimiting examples.

_ EXAMPLE 1 10 -

The following products are reacted in a one liter capacity stainless steel autoclave equipped with a pressure gauge, a drain tube, a magnetic stirrer and incorporated electric heating resistors: 9 * 55 g of 2 -methyl-3-butene-2-ol} anhydrous, pure (MBE), 386.80 g of acetone, - 1 * 63 g of di-ter-butylperoxide (DTBP).

»Added urfî ·" The acetone / MBE / catalyst molar ratio is therefore about 60/1 / 0.1. Said mixture is heated with added stirring ^ ^ • '250C. After 1 hour and A5 minutes of reaction, the conver - ajuuu; 20 moles a word, sion of MBE ((initial moles MBB- / final y of MBE). 100 / moles φ initial of MBE) is 66% and the selectivity with respect to the adduct 1: 1 ( moles of product, 100 / moles of reacted MBE) is 86 #.

After 5 hours the conversion is 98 # and the selectivity is around 82 #. . -

The 1: 1 adduct thus formed is 6-hydroxy-> 6-methyl-heptane-2-one (or 6-methylheptane-6-ol-2-one): i T3; 3 ° T- C = 0 / Γ2 0¾

35 GH

C-OH

/ \ ch ch; 3 3 whose structure is confirmed by the mass spectra ^ IR and rmn.

EXAMPLE 2

The process of Example 1 is repeated but with an acetone / MBE / DTBP molar ratio of 60/1 / 0.025.

After 8 hours of reaction at 125 ° C the conversion is 63 / ¾ and the selectivity of 88 #.

EXAMPLE 3 The apparatus of Example 1 is supplied with 19.13 g of hydroxylinalol 1, or 15 ^ 387 g of acetone,

1.62 g DTBP

corresponding to an acetone / (I) / DTBP molar ratio of 60/1 / 0.1. After 6 hours at 125 ° C, the conversion of (I) is 20 88 # and the selectivity in terms of adduct 1: 1

Cil 1 0 1125 n / v oh - is 57 #.

* EXAMPLE -'l · The apparatus of Example 1 is supplied with 116 g of pure acetone 30 3800 g of 2-methyl-2-ethoxy-3-butene (II)

0.50 g DTBP

giving an acetone / (II) / DTBP molar ratio of approximately 60/1 / 0.1.

After 3 hours at 125 ° C. a 1: 1 radical adduct is formed which is 6-rrethylheptane-6-ethoxy-2-one

/ CO

ΐ c

JUoCJL

% "5 with a conversion of $ 90 from (II) and a selectivity of approximately $ 88, its structure being confirmed by liquid gas chromatography and mass spectrum.

EXAMPLE 5 The procedure of Example 4 is followed, but the mixture is fed with 6.33 g of 2-methyl-3-butene-2-yl (III) henzoate in place of 2-methyl-2-ethoxy -3-butene so that the acetone / (III) / DTBP molar ratio is still approximately 60/1 / 0.1.

10 After 3 hours at 125 ° C., 6-methylheptane-2-one-6-yl benzoate is formed

CO

·; 15

,> Ar 000 "(S

Γ 'with a conversion of 88 $ (III) and a selectivity of envi-added a ron 86 $, the structure of the product being further confirmed by m0 ^ 20 gas-liquid chromatographic analysis / mass spoeii e EXAMPLE 6

A 5 liter capacity stainless steel autoclave, fitted with a pressure gauge, a tube for supplying the reagents by means of a metering pump, a magnetic stirrer and incorporated electric heating resistors, is supplied with : - 2978.35 g of acetone (51.208 moles) 75.97 g of 2-methyl-3-butene-2-ol (0.883 ^ 1 mole) (MBE).

The mixture is heated with stirring, at 130 ° a mixture of 12.91 g of dl-ter-butylperoxide (0.0883 mole) (DTBP) and 100 g of acetone (1.816 mole) is fed by means of the pump .

The flow rate of the pump is adjusted so that the solution of the peroxide in acetone is supplied within 2 hours 15 minutes.

The acetone / MBE / LTBP molar ratio is 60/1 / 0.1.

After 5 hours of reaction (calculated® from the start of the peroxide feed) the conversion of MBE is $ 82.5 and the selectivity in terms of 6-methylheptane-6 - 6 ^% ol-2-one is 8511 mol% relative to the MBE.

The conversion and selectivity values are i j - determined by gas chromatography in | using the Internal standard process.

5 EXAMPLE 7

The process of the previous example is repeated, but with an acetone / MBE / DTBP molar ratio of 60/1 / 0.05.

The DTBP solution in acetone is pumped over a 2.5 hour period.

10 After 5 hours of reaction (calculated from the start of the peroxide feed) the conversion of MBE is $ 73 and the selectivity in terms of 6-methylheptane-6-ol-2-one is $ 8,918 in mole per compared to MBE.

The DTBP conversion is 59.1%.

Example 8 The 5-liter autoclave described above is supplied with 3078 g of acetone (52.996 moles) and 74.825 g of MBE (0.8γ0 moles).

The mixture is heated with stirring. At 130 ° C the feeding of di-ter-butylperoxide is started. The reactor is fed for 1 hour with 6.946 g of DTBP (0.0475 mole). 30 minutes after the start of the DTBP feeding, the feeding of MBE is started and 40.320 g of MBE (0.469 mole) are fed in the space of 3 hours.

After 6 and a half hours of reaction (calculated from the start of the peroxide feed) conversion; v the MBE is $ 88.2 and the selectivity is $ 75.9 in moles.

The final acetone / MBE / DTBP molar ratio is 59.6 / 1 / 0.035. :

30 EXAMPLE Q

A 22 liter stainless steel autoclave of I capacity? having the same characteristics as those described in the previous example, is supplied with 12.342 kg of acetone (212.1 moles) and 0.609 kg of MBE (7.083 moles).

The mixture is heated with stirring. At 130 ° C, 0.1036 kg of DTBP (0.7083 mole) is supplied within 2 hours. After 5 hours of reaction (calculated from

1 ~ "S

; "1“ t "· ~ · ----,. ....... : · If. · I * 7 at the start of the DTBP feed) The autoclave is cooled.

The reaction mixture is distilled through a column of Oldenshaw perforated trays to give 495 g of pure 6-methyl-heptane-6-ol-2-one. The molar yield relative to the 5 MBE fed for the reaction is 48.5. At the end of the feeding, the acetone /, MBE / DTBP molar ratio is 30/1 / 0.1. 1

Claims (14)

1. Process for the preparation of carbonyl compounds i which also contain one or more other functional groups in their structure, characterized in that it consists in reacting a carbonyl compound with an unsaturated compound containing one or more functional groups in | presence of a catalyst consisting of a peroxide. 2. Method according to claim 1, characterized by the fact that the carbonyl compound is a ketone or an aliphatic, alicyclic or aromatic aldehyde * comprising a methyl or methylene group in the alpha position relative to the 'carbonyl group. 3. Method according to claim 1, characterized in that the carbonyl compound is an alpha-methyl ketone 15 e ^ preferably * either acetone or methyl ethyl ketone. 4. Method according to any one of claims; 1 to 3 / characterized in that the unsaturated compound contains i | at least one ethylenic or acetylenic bond in the terminal position and one or more functional groups. 5. Method according to any one of claims 1 and 4, characterized in that the unsaturated compound contains at least one functional group chosen p ^ null-OH, -OOCCH ^,! -Cl, -ÛCHy “° CgH5, -CN, -C00H and -COOR in addition to the unsaturated route. 6. Process according to claim 5, characterized by the fact that the unsaturated compound is chosen from 2-methyl- * 3-butene-2-ol, 2-methyl-3-butene-2-yl acetate, , hydroxylineol, 2-methyl-2-ethoxy-3 ~ butene and benzoate of 2-methyl-3-butene-2-ylî. · 30 7- A method according to claim 1, characterized in that the peroxide is chosen from di-tert-butyl-peroxide, diacetyl-peroxide, dibenzoyl-peroxide, tert-butyl-hydroperoxide and dicyclohexylperoxydicarbonate. 8. Method according to claim 7, characterized in that the peroxide is preferably di-tert-butyl peroxide. 9. The method of claim 1, characterized by f Ie the fact that the molar ratio of carbonyl compound compound s' c "* 9 unsaturated is between 500 and 3. 10. The method of claim 9 # characterized in that the molar ratio of the carbonyl compound to the unsaturated compound is preferably between 300 and 5. 11. Method according to claim 1, characterized in that the molar ratio of peroxide to the unsaturated compound is between 1/1 and 0.005 / 1. 12. A new compound, in particular 6-methylheptane-6-ethoxy-2-one. 13. A new compound, notably 6-methylheptane-2-one-6-yl benzoate. * '14. The new compounds, namely derivatives of 6-methylheptane-6-ol-2-one in which the hydroxyl group has been etherified or esterified.