SK279092B6 - The method of higher aliphatic and/or cycloaliphatic ketones production - Google Patents

Abstract

The method of higher ketones of common formula R'COR'' production in which R' stands for, from propyl to hexadecyl with straight and/or branched chain, from cyclopenthyl to cyclododecyl; R'' stands for, from methyl to hexadecyl with straight and/or branched chain initiated addition of dialkylketones C3-C19 and/or cycloalkylketones C5-C12 in temperature ranging from 100 to 180 degrees Celsius during initial effect of, at least one organic peroxide (di-terc. buthylperoxide), or hydroperoxide with half-l ife decay during addition temperature lasting from 0,5 to 8 hours in molar ratio of alkene and/or cycloalkene : dialkyketone, and/or cycloalkylketone : organic peroxide, and/or hydroperoxide from 1 : 5 to 100 : 0,01 to 1 percent. Higher ketones are isolated from the reaction product and non-convertible material is recycled.

Description

Technical field

The invention provides a process for producing higher ketones by free radical addition of aliphatic or cycloaliphatic ketones to alkanes or cycloalkenes initiated by organic peroxides and / or hydroperoxides with defined half-life at the applied reaction temperature.

BACKGROUND OF THE INVENTION

It is known to produce alicyclic ketones by oxidation of cycloalkanes such as cyclohexanone by oxidation of cyclohexane, dehydrogenation of cycloalkanols, such as cyclohexanone by dehydrogenation of cyclohexanol, but also aliphatic ketones by oxidation of alkenes catalyzed by palladium, copper, thallium and other catalysts. as well as by thermal cleavage of the calcium and magnesium salts of carboxylic acids. However, these processes are sufficiently selective especially for the production of lower ketones, but are problematic in terms of the targeted preparation of higher ketones. Interesting techniques include contacting the aliphatic carboxylic acids with an MnO ₂ / Al ₂ O ₃ catalyst [Hausmann GP: US 4 754 074 (1988)] or ZrO ₂ [jap. pat. Application 57-197 237] in the vapor phase at 300-500 ° C. However, frequent catalyst reactivation is required, and for some of the higher ketones, precursors are technically difficult to obtain. Conversion of lower ketones, e.g. C ₃ to C ₆ and aliphatic aldehydes to ketones> C ₇ on a Cu / ZnO catalyst at 200 to 400 ° C are less selective and also have limited use [Eliott DJ: US 4,694,108 (1987)]. Noteworthy is a process for the catalytic preparation of higher ketones by reaction of olefins, C ₂ to C ₂₀ with steam in the presence of oxygen [Ch IEH. Y., Savini Ch .: US 4,560,804 (1985)] and catalysts based mainly on transition metals as well as alkan-2-ones by free-radical addition of acetaldehyde to 1-olefins at 140-180 ° C in the presence of cobalt catalyst and air [Stepanova GA et al .: Chim. thoughtfulness, no. 9, 523 (1984)], or the addition of acetone to 1-olefins under the catalytic action of silver peroxide [CS 173 870]. Similarly noteworthy is the free-radical addition of acetone as well as methyl ethyl ketone and acetophenone to 1-octene with an initiating effect [Alien JC et al .: J. Chem. Soc. 1965, p. 1918-1943] diisopropyl peroxydicarbonate or benzoyl peroxide, but even di-tert-butyl peroxide. However, the yields obtained of the adducts 1: 1 are low, since even in the latter case inappropriate reaction conditions were applied. Either an unsuitable initiator such as diisopropyl peroxydicarbonate and dibenzoyl peroxide was used at a temperature of about 60 ° C, or a suitable initiator such as di-tert-butyl peroxide, but at a temperature below 100 ° C at which its half-life is above 60 h. However, the method of the present invention solves the drawbacks of these processes.

SUMMARY OF THE INVENTION

The present invention provides a process for the preparation of higher aliphatic and / or cycloaliphatic ketones of the general formula R'COR, wherein R '= straight or branched chain propyl to hexadecyl, cyclopentyl to cyclododecyl, R = straight or branched chain methyl to hexadecyl, organic peroxides and / or hydroperoxides initiated by addition to the at least one dialkyl ketones of C ₃ through C _i9, and / or a cycloalkyl ketone, C ₅ to C ₁₂ treated at 100 to 180 ° C for at least one olefin C ₃ to C _t6 and / or cyclo-C ₅ to _1.2 with an initiating effect of at least one organic peroxide and / or hydroperoxide with a half-life at the reaction temperature of addition of 0.5 to 8 h, wherein the total molar ratio of alkene and / or cycloalkene: dialkylketone and / or cycloalkylketone: organic peroxide and / or hydroperoxide = 1: 5 to 100: 0.01 to 1, wherein the unconverted starting materials and by-products are separated.

The advantages of the process according to the invention are its flexibility, simple technology, feasibility, good yields, raw material availability and the possibility of recycling unconverted raw materials and the use of by-products. The process allows waste-free production, trouble-free storage and handling of major and by-products.

Preferred alkenes are straight chain or branched chain C ₁ to C ₁₆ 1-alkenes; less suitable but useful are n-alkenes having an internal double bond position. Next, cycloalkenes _C to ₁₂ C, such as cyclopentene, cyclohexene and the like. Among the ketones, the dialkyl ketones are C ₃ to C ₁₉ , with acetone being the most suitable, as it provides the same-chain alkan-2-one with the same 1-alkene, methylethyl octone, methyl isobutyl ketone, but also methyl alkyl ketones with C ₆ -C ₁₅ alkyl. Of the cycloaliphatic, in particular cyclopentanone, cyclohexanone, cyclooctanone and cyclodecanone.

Of the organic peroxides, they are most suitable with a half-life of 0.5 to 8 hours at a temperature of 100 to 180 ° C, and in particular a half-life of 2 to 5 hours at a temperature of about 140 ° C. When sensitive organic peroxides and hydroperoxides are used which have a half-life within these limits at a temperature below 80 ° C, a low initiation efficiency of addition and low selectivity to the desired product is achieved.

Di-tert-butyl peroxide is most suitable. Other free-radical formers within this temperature range are also useful, but less effective. The molar ratio of alkenes resp. cycloalkene: dialkyl ketone and / or cycloalkyl ketone: organic peroxide and / or hydroperoxide should be 1: 5 to 100: 0.01 to

1. With a lower content (except for the above limits) of the initial lower ketone, low selectivity is achieved, and at high, larger production equipment is needed and, moreover, much more energy is required to regenerate lower ketones and isolate higher ketones. In the case of a higher amount of initiator, the competitive oligomerization of the alkenes or the further addition of the alkenes to the already formed higher ketones takes place to a greater extent.

The unconverted reactants are isolated from the crude product by differential distillation, but in particular by reactivation, most preferably under reduced pressure. In the case of low separation efficiency of rectification or only using differential distillation, the main product according to the invention, in particular from the more volatile constituents, can also be isolated by fractional crystallization or resp. by crystallization. Particularly for dialkyl ketones with the highest molar mass, molecular distillation and zone melting are suitable.

The process according to the invention can be carried out batchwise, semi-continuously and continuously. In the case of low tonnage production, where the machinery so permits, the semi-continuous process, which, unlike the discontinuous process, provides higher selectivity, is the most appropriate. In carrying out the process, it is advantageous to prevent initiators from contacting the alkenes, respectively. cycloalkenes in the absence of a low molecular weight ketone. The absence of a ketone favors the oligomerization of alkenes and cycloalkenes.

The crude reaction product, especially if the retention time in its preparation was short and a thermally more stable initiator was applied, is desirable, especially for safety reasons, to dispose of residual decomposed peroxide or hydroperoxide. If there is sufficient residence time or temperature increase before the end of the batch, this effect is sufficient. In case of insufficient effect, admixtures of known reducing agents or transition metal salts are suitable for decomposing residual peroxides and hydroperoxides.

Further data on carrying out the process of the invention as well as other advantages are apparent from the examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

10 g of 1-decene, 41.5 g of acetone and 2.7 g of dilauroyl peroxide are metered into a high-pressure stainless steel autoclave of 300 cm ³ . 1-Decene + + acetone: dilauroyl peroxide molar ratio = 1: 10: 0.1. While stirring, the autoclave was heated to 60 ° C and maintained at this temperature to + 2 ° C for 6 h. At this temperature, the half-life of dilauroyl peroxide is 10 h. The conversion of 1-decene is 20% and the selectivity to tridecan-2-one (methylundecyl ketone) is 2.4%. With a batch of 10 g of 1-decene, 82 g of acetone, 2.8 g of dilauroyl peroxide at 67 ° C, at which its half-life is approximately 4.5 h, during 5 h the conversion of 1-decene reaches 5% and selectivity to tridecane- 2-one 4.5%.

Example 2

The procedure is as in Example 1, only the reactant weights, the type of peroxide and the reaction temperature vary. Weigh 5 g of 1-decene, 104 g of acetone, 1 g of bis (2-ethylhexyl) peroxydicarbonate (mol ratio = 1: 50: 0.1), 56 + 1 ° C and a reaction time of 12 h. The half-life of peroxide at this temperature is 2.5 h. The 1-decene conversion reached 10% and the selectivity to tridecan-2-one 42.4%.

Example 3

The procedure is similar to that of Example 1, except that the effect of temperature and the use of other peroxides is investigated. The batch for each experiment consisted of 10 g of 1-decene, 82.7 g of acetone and 1.3 g of di-tert-butylperoxide, with a molar ratio of 1:20: 0.13. The applied temperature, experiment time, 1-decene conversion, selectivity to tridecan-2-one (methylenedecyl ketone) and yield are shown in Table 1.

Table 1

temperature [ 'Cl Half-life of di-tert-butylproxide (hl Experiment time [hl Konveraa 1-decene j%] 1-Decene selectivity to TNF-2-δ [1% Yield% of theory on 1-decene! 100 120 > 4o 20 r 3.5 64.7 17, J 13.3 §,about 8.6 132 4.1 4.5 99.3 39.4 39.1 136 3.1 5 99.2 43.3 42.9 138 2.8 5.5 99.1 42.0 41.6 145 1.3 5.5 98.7 58.1 57.3 150 0.75 4.5 99.8 40.2 40.1 150 0.75 5 99.0 59.5 58.9 160 0.55 4 98.9 36.7 56.2 170 0.25 5 96.2 35.0 33.7 200 30 8 0.5 97.4 33.9 33.0

Example 4

Using the autoclave and discontinuous procedure described in Example 1, the effects of the acetone / 1-decene molar ratio and the di-tert-butylperoxide / 1-decene molar ratio in isochronous (5 h) experiments, 1-decene conversion and selectivity to tridecane- 2-one (methylenedecyl ketone) and its yield based on 1-decene applied. The other reaction conditions and results are shown in Table 2.

Example 5

A weighing of 72.6 g of acetone is weighed into the 0.3 dm ³ autoclave equipped with an electromagnetic stirrer, after removal of air, and after heating the autoclave to 150 ° C, a mixture of 10 g 1-decene with 10 g acetone and 1.0 g di tert-butylperoxide (molar ratio = 1: 20: 0.1) for 2.5 h and then allowed to react for a further 2.5 h. Thereafter, the autoclave is cooled, the reaction product is quantitatively removed, weighed (93.5 g) and further distilled. Unreacted acetone is distilled off at 60 ° C / 101 kPa. The distillation residue, analyzed by liquid-gas chromatography, in an amount of 14.7 g contains 1.6 wt. % Of 1-decene and 48.4 wt. methylenedecylketone, indicating a 1-decene conversion of 97.6%, selectivity to methyllundecylketone 51.5%, and a yield of 50.3% of the theory calculated for the applied 1-decene. Under otherwise similar conditions, but using only 50 g of acetone but additionally 50 g of cyclohexanone, the conversion of 1-decene reaches 98.2% and the yield of methylundecyl ketone 40.8% and cyclohexylundecyl ketone 32.5%.

Example 6

As in Example 5, only 1-decene and di-tert-butyl peroxide are dosed separately so that all 1-decene and di-tert-butyl peroxide are dosed over 2.5 h. The reaction mixture was allowed to react for an additional 2.5 h with stirring. The conversion of 1-decene is 99.5%, the selectivity to methyllundecyl ketone 55.2% and the yield 54.9%.

Example 7

Following the procedure of Example 6, only the molar acetone / 1-decene ratio was raised to 30 and the reaction temperature was maintained at 145 + 2 ° C (batch: 10 g 1-decene, 122.6 g acetone, 1.0 g). di-t-butyl peroxide). The conversion of 1-decene is 98.2% and the selectivity to methyllundecyl ketone is 64.5%.

Example 8

To a stainless steel autoclave of a volume of 10 dm ^3, equipped with a propeller stirrer, duplicators and conventional removal of the accessory, the air weighed 4000 g of acetone, and heated up to 140 ° C, especially in 3.5 h by pump charged with 500 g of 1-decene 50 g of di-tert-butyl peroxide and 2 g

Tert-butyl hydroperoxide with 146 g of acetone. This is followed by reacting for 2 h, cooling the autoclave and draining the product through a condenser. The crude product weighing 4680 g was analyzed and distilled. Differential distillation to 60 ° C / 101 kPa distilled off a substantial portion of acetone (3890 g), which was reused for further preparation of methylenedecyl ketone. The distillation residue (783 g) contained 1.4 wt. 1-decene and 52.2% methylenedecylcene. Thus, the conversion of 1-decene is 97.8%, the selectivity to tridecan-2-one 60.4% and the theoretical yield 59.1%. Pure methylenedecyl ketone of 98.9% purity is obtained by rectification under reduced pressure (2.13 kPa). From the front fraction containing 73.2 wt. The methyllundecyl ketone is isolated by crystallization upon cooling to about room temperature and filtration.

Example 9.

Using the autoclave described in Example 1, at mol. The ratio of 1-decene: acetone: organic peroxide of separately dosed peroxides and 1-decene, similar to Example 6, investigates the effect of various organic peroxides and reaction temperature on the conversion of 1-decene and selectivity to methylenedecyl ketone. Further reaction conditions and achieved results are summarized in Tab. Third

Table 3

The reaction Ortumckv Deroxjd time conversion Selective on temperature [’C] kind of half-life th] pokussu {hl 1-decene l%] Tridecan-2-one (%) 180 di-tert with tert-butyl hydroperoxide (4: D 0.05 and 5 5 87.3 54.2 160 (Urumylperotód with kuntéahydroperoxidom (4.1) 0,1 and 8 6 89.2 56.2 120 terc.butyiperoxybenzoát 2.2 5 93.7 57.1 115 terc.butyĺpcroxyBcctát 2.5 5 93.9 59.2 135 tert-butylcumyl peroxide 2.4 5J 92.8 57.2 105 1,1-Di-tert-butylfertylisobutyral 2.3 4 / 90.7 54.2 140 dicumylperoxide O, ή 6 94.0 3.3 56 dibenzoyiperoxid > 40 11 25.7 14.1 160 diisopropylbenzene monohydroperoxide with di-tert-butyperaxon (1: 1) 4 and 0.3 6 96.8 62.1 82 dibenzoyiperoxid 2.6 5 15.8 8.8 5b a + Z-etylhejryipefoxydikaibonát 1.8 12 IN 42.4

Example 10

The autoclave of Example 1 is weighed with 72.6 g of acetone and, after closing and evacuating the air, the contents of the autoclave are heated to 150 ° C and a mixture of 10 g of 1-decene, 10 g of acetone and 1.0 g is metered into the autoclave. of di-tert-butyl peroxide for 2.5 h. The reaction mixture was allowed to react for a further 2.5 h. The autoclave was cooled, and the reaction product (93.5 g) was freed from acetone by differential distillation (fraction to m.p. = 60 ° C at 101 kPa), which was used for further production. The distillation residue in an amount of 14.7 g contains 1.6% 1-decene and 48.4% by weight. tridecane-2-one. Thus, the conversion of 1-decene reaches 97.6%, the selectivity to tricecan-2-one 51.5% and to the diundecyl ketone 23.2%.

Example 11

Following the procedure of Example 10, only half of the di-tert-butyl peroxide (i.e. 0.5 g) was fed into the autoclave with acetone over 2.5 h. The 1-decene conversion reached 81.7% and the selectivity to tridecan-2-one 41.2%.

If, instead of the other half (0.5 g) of di-tert-butyl peroxide, only 0.25 g but still 10 g of cumene hydroperoxide and 0.15 g of tetrahydrofuran hydroperoxide are given, the conversion of 1-decene is 90.3% and the selectivity to tridecan-2 -one 49.8%.

Example 12

The procedure is similar to Example 11, only the total amount of acetone is increased, the 1-decene: acetone molar ratio is increased to 1:50. The 1-decene conversion reaches 98.2% and the selectivity to tridecan-2-one (methylenedecylketone) increases to 69.5% and diundecyl ketone 21.2%. At mol. a ratio of 1:80 and a simultaneous increase in the amount of di-tert-butylperoxide by 0.2 g achieves virtually complete conversion of 1-decene, selectivity to methylenedecyl ketone 72.1% diundecyl ketone 21.7%.

Example 13

Weigh 4,000 g of acetone into a 10 dm ³ autoclave with a propeller stirrer, and after air removal and heating to 140 ° C, 500 g of 1-decene and 52 g of di-tert-butylperoxide with 140 g were continuously charged. acetone for 3 h. Thus the final molar ratio of 1-decene: acetone: di-tert-butylperoxide = 1: 20: 0.1. After dosing is complete, the reaction is allowed to continue for 2 h. The reaction product (4680 g) was distilled by differential distillation, and 3890 g of acetone were recovered. The distillation residue in an amount of 780 g contains 1.4 wt. 1-decene, 52.2 wt. tridecan-2-one, the remainder to 100% being mainly 1-decene oligomers and dialkyl ketone C ₂₃ . The 1-decene conversion reached 97.8% and the selectivity to tridecan-2-one (methylenedecyl ketone) 60.4%.

The distillation residue is rectified under reduced pressure to give tridecan-2-one with a purity of 99.1%. The residue (II) from this vacuum rectification has a molar mass of 430 ± 30 g.mol ¹ , a bromine number of 41.6 ± 2 g Br / 100 g; % wt. CO = 1.6 ± 0.3% by weight, containing, according to IR, long hydrocarbon chains, branched chains and keto groups. This suggests the presence of said oligomers and dimers. 1 H-NMR and ¹³ C-NMR also showed the presence of 1-decene oligomers and higher ketones.

Again under vacuum differential distillation of the distillation residue after separation of 1-decene and fraction of b.p. 143-160 ° C / 2.67 kPa contains 95.4 wt. tridecan-2-one, from which, by fractional crystallization at a temperature of 24.6 to 23.6 ° C, a crystalline fraction is obtained which, after suctioning, contains 98.1% by weight of trisecan-2-one. tridecane-2-one.

Example 14

100 g of acetone are charged to the autoclave specified in Example 1, the air is removed, heated to 150 ° C and a mixture of 10 g of 1-hexene, 38 g of acetone and 1.7 g of di-tert-butylperoxide is metered over 3 h. Response for 1.5 h after dosing. The crude product obtained (148.2 g) was differentially distilled, whereby the distilled acetone (133.3 g) was reused for further production of nonan-2-one. The distillation residue was differentially vacuum distilled, the fraction of b.p. 7.5 to 82 DEG-92 DEG C./173 kPa contains 97% nonan-2-one (b.p. nonan-2-one = 80 DEG to 82 DEG C./2.0 kPa). The yield of nonan-2-one reached 44.4% of theory.

Under otherwise similar conditions, but the olefin: acetone: di-tert-butyl peroxide molar ratio = 1:20: 0.1 at 150 ± 1 ° C, additional higher ketones were prepared. Additional reaction conditions and results are summarized in Table 4.

SK 279092 Β6

Table 4

Alkene Product notes emit ketone yield (% of theory) 1-buién hcptán-2-one * 23.7 fragrance 1-octene undecane-2-one 50.1 scented fabric cyklobexén cyklohesylacetón 35.2 1-hexene 2-hexykyklohexanôn 17.5 instead of acetone cyclobexaeone l-dodecene pentadekárv-2-όη 58.3 cyclododecene cyklododecyhcetón 47/3 cyclooctene cyclooctyl acetone dicyclooctylacetone 38.1 17.1

Example 15

The procedure is as in Example 14 except that other ketones are applied instead of acetone. Thus, 1-decene with diethyl ketone gives a yield of ethyl isododecyl ketone of 63.2% and a diisododecyl ketone

15.2%; 1-Decene with methyl isobutyl ketone gives a yield of a mixture of methyl isobutyldodecyl ketones of 59.2%. 1-Decene with an equimolium mixture of cyclopentanone and cyclohexanone under otherwise comparable conditions yields a yield of cyclopentylundecylketone of 29.2% and cyclohexylundecylketone

38.3%. However, under otherwise similar conditions with cyclododecanone mixed with butylcyclododecanone, the yield of cyclododecylundecyl ketone is 25.3% and butylcyclodecylundecyl ketone is 31.3%.

Industrial usability

The process according to the invention is suitable for the production of higher methyls of hexylalkyl ketones and cycloalkylmethyl to cycloalkylhexyl ketones as an intermediate for the production of drug substances, fragrances and other organic products.

Claims (5)

PATENT CLAIMS A process for the preparation of higher aliphatic and / or cycloaliphatic ketones of the general formula R'COR, in which R 'is straight or branched chain propyl to hexadecyl, cyclopentyl to cyclododecyl, R is straight or branched chain methyl to hexadecyl, organic peroxides and / or or hydroperoxides initiated by the addition, characterized in that the at least one dialkyl C ₃ to C ₁₉ and / or the cycloalkyl ketone, C ₅ to C _I2 treated at 100 to 180 ° C for at least one olefin C ₃ to C ₁₆ and / or cyclo-olefin C ₅ to ₁₂ with an initiating effect of at least one organic peroxide and / or hydroperoxide with a half-life at the reaction temperature of addition of 0.5 to 8 hours, wherein the total molar ratio of alkene and / or cycloalkene: dialkylketone and / or cycloalkylketone: organic peroxide and / or the hydroperoxide is 1: 5 to 100: 0.01 to 1, wherein the unconverted starting materials and by-products are separated. Method according to claim 1, characterized in that the unconverted starting materials and the main products or the main products as well as the by-products are separated by distillation and / or rectification, the main products and the high-boiling by-product by distillation and / or rectification under reduced pressure. and / or fractional crystallization. Method according to claims 1 and 2, characterized in that it is carried out semi-continuously or continuously, so that at least one alkene is continuously or continuously fed to a part of the at least one starting material and / or by-product and / or reaction product and and / or the cycloalkene and / or ketone and the initiator and the crude reaction product are discharged in a single, semi-continuous or continuous manner for separation. The process according to claims 1 to 3, characterized in that the crude reaction product is separated in a one-time, semi-continuous or continuous manner after a preliminary thermal or thermo-catalytic decomposition of the residues of the decomposed initiator. The process according to claims 1 to 4, characterized in that the initiator comprises at least one organic peroxide and / or hydroperoxide selected from di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide, tert-butylperoxyisobutyrate, tert-butyl carbonate tert-butylcumyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,2-di-tert-butylperoxybutane, tert-butylperoxybenzoate, tert-butylperoxyacetate and tert-butylperoxy-3,5,5-trimethylhexoate.