MXPA97001589A

MXPA97001589A - Procedure to obtain compounds of carboniloó-hidroxi and / or alpha, ó-insatura

Info

Publication number: MXPA97001589A
Application number: MXPA/A/1997/001589A
Authority: MX
Inventors: Teissier Remy; Forunier Maurice
Original assignee: Elf Atochem Sa
Priority date: 1996-02-29
Filing date: 1997-02-28
Publication date: 1998-04-01

Abstract

The present invention relates to a process for obtaining carbonyl α-hydroxy compounds and / or α-unsaturated carbonyl compounds, further characterized in that at least one aldehyde or a ketone makes contact with a solid catalyst of general formula (I) : [(Mg2 +) 1-x (A13 +) x (OH-) 2] x + [(OH-) x] x + (H2O) n (i) with 0.20 < - x < - 0.33 and n <

Description

PROCEDURE FOR OBTAINING COMPOUNDS OF CflBrONlON ß-HIDRQXI AND / OR Tt, ß-INSflTURflDOS DESCRIPTION OF THE INVENTION The present invention relates to? Ncocodiin on novel to obtain compounds of carbo-ß-hydrox and / or aryloni compounds? c, ß-msaturados. You have divided your subject or procedure for aldolizacion and / or aidol ization-cr otation of aldehyde and / or cotona. Industrial processes based on the aldol condensation reaction of aldehydes and coconut use a basic catalyst such as dilute solutions of potassium hydroxide and sodium hydroxide. The separation of these catalysts at the end of the reaction, however, is not easy and requires the addition of acid solutions, especially sulfuric acid, to convert the catalysts into the corresponding salts, in addition, the removal of salts thus formed, which is necessary for the environment, is expensive for the industry. To overcome the aforementioned disadvantages the use of solid catalysts has been proposed. In this way, the copper oxide supported on an alumina t has been described in the patent of E.U.fl. 4739122 to catalyze the condensation reaction of aldol mixed between acetone and butal. The patent E.U.fl. 5 144 039 describes a procedure for the condensation of liquid phase aldol, especially in the convergence of Putanal at 2 - and ii -2-hexenal on the presence of a solid catalyst. The catalyst is a solid solution of magnesium oxide and aluminum oxide, derived from a hydrotalcite and having a spermatic surface greater than? 50 rn2 / y. Titanium dioxide has also been described as a catalyst for the aldol condensation reaction in the process to obtain aldehydes a, (1) urine (US * 9). of ion has also been used but without success, since the ream can not withstand a temperature greater than 90 ° 0. Moreover, once the ream is deactivated, it can no longer be regenerated. "It has discovered that the aforementioned disadvantages can be overcome by using a catalyst of the general formula (I): C (Mg2 +) __. "(013 +)" (OH-) _l? + i: (0H-)? - (H20) r, (T) with 0.20 < x < 0.33 &n < 1. The subject matter of the invention is therefore a process for obtaining carbohydrate ß-hydroxy compounds and / or carbon compounds c <, ß- 1 ns turados. This process is characterized in that at least one aldehyde or a ketone makes contact with a solid catalyst of the general formula fl): [(Mg2 +)? - "(R13 +)" (OH-) 2 - * + p? H-) «1« - (H20) n 'I) In lu most d > - lo1 ', ca o-, an aldehyde or a ?? which has at least one atom of hydrogen in the - < carbon < f < The functional graph < , ar-bon? io so employ. The procedure according to the present invention preferred to consist in reacting, in the presence of a catalyst. of the general formula (I), an aldehyde of the general formula Pi-FLIO, wherein R 1 deno in linear or branched alkyl radical containing from 1 to 1 (1 carbon atom, with optionally at least one compound chosen from another aldehy or of the formula R2-CH0 wherein R2 denotes a hydrogen atom or a linear or branched alkyl or cyclic radical containing from 1 to 10 carbon atoms or an ionic radical or a benzyl radical or an arachidyl radical and / or a ketone of the general formula R5-C0-RG wherein each S and R6, which are identical or different, denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms and capable of being bound to the It is also preferred to react with a ketone of the general formula R3-00-R * wherein each R3 and 4, which on identical or different, denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms, with optionally at least one compound selected from an aldehyde or of the general formula R2-CH0 wherein 2 denotes a hydrogen atom or a linear or branched alkyl or cyclic radical containing from 1 to 10 carbon atoms or a femlo radical or a i? d? radical urai chyl, and / or another ketone of the formula R5-C0-R6, wherein each R5 and R6, which are identical or different, denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms and capable of being bound when forming a ring, in the presence of a catalyst, of the general formula (T), the mixture of the present invention is very traditionally an aldolization process and / or to the pain of rotating at least one aldehyde or one ketone (with the exclusion of the process of selective acetonization to di acetone alcohol) in the presence of a catalyst of the formula (L). The process according to the present invention advantageously includes bringing a ketone of the generic formula to the R3-C0-R and an aldehyde of the general formula R2-CH0 in contact with a catalyst of the formula (D. T to a preferably it is chosen from those where R3 or R * denotes a methyl radical, such as acetone in particular, ethylmethyl tone or ketone (1 rne iipropyl. The ketone is par ticularly preferred. The aldehyde is advantageously chosen from methanal, ethanal, propanal, butanal, isobutanal and benzaldehyde. Butanal or isobutanal is preferably used. The process advantageously also includes carrying an aldehyde R1 -0H0 and optionally another aldehyde R2-CH0 in contact with the catalyst whose formula (I) is given above. The aldehyde Ri-CHO is advantageously chosen from ethanal, propanal, butanal, isebutanal, l-ethanal, hexenal and hef) ton. The aldehyde R2-CH0 is advantageously chosen from methanal, ethanal, propanal, butanal, isobutanal and benzaldehyde. Proferí blernente mettanal, butanal or isobutanal. Etanai, butanal or isobutanal is advantageously used for the process of aldolization and / or aldolization-crotonization of an aldehyde. Particularly preferred is butanal. The β-hydroxy and or, β-unsaturated carbonyl compounds which are advantageously manufactured in accordance with the process of the present invention, are those such as, specifically, silyl oxide, 2-et? I- hexenal, 5 - met il -3- hexene- -one, 3-hetene-2-one and 2,2 ', 4-tp et j 1 - 3 - hid ro xi pe nta na i. The carbom a, ß-ins compounds obtained in accordance with the process of the present invention can be subjected to selective hydrogenation, using known catalysts, to give corresponding saturated carbomyl compounds as aldehydes or ketones having a higher molecular weight. of that or those that are used, or to a total hydrogenation, to give the corresponding saturated alcohols. These aldehydes or ketones or -llo-holos, on industrialized soil, as well as with industrial solvents or solvents, are used in the manufacturing industry. The procedure for obtaining ilo ß-hydr'oxi and / or cornr >compoundscarbonyl ions, fl ats, according to the present invention can perform it at a temperature within the limits that are also separated, ranging from f) ° C to approximately 2G0 ° O. In most cases, the operation is carried out at a temperature of approximately 0 ° C and i (1 rox i nnadarnent e 1 f) "C. An inlet temperature around 0 ° C and preferably 100 ° C. is preferably used The pressure at which the operation is carried out is such that the reactable materials (aldehydes and / or ketones) are in the liquid state at the aldolization or aldolization-croto temperature. Although it is possible to work at a pressure higher than atmospheric pressure, in most cases it is preferred to operate at atmospheric pressure The process according to the invention can be carried out equally well continuously and not continuously. powder dust is preferred When operating continuously, the process consists in introducing at least one aldehyde and / or a ketone 25 through a stationary bed or stirred ceiling of solid catalyst of the general formula (I). can materials be changed or repaired or replaced? The pump is completely pre-cooled with the sides of the reactor introduced into the reactor. They can also be introduced into the reactor either simultaneously or successively. The method of operation depends on its relative reactivity and the desired final product. In general, when two aldehydes or two ketones or a ketone and an aldehyde having different reactants make contact in the presence of the catalyst of the general formula (D, an excess of the active compound is always used, the ratio molar of the aldehyde or less active ketone to active aldehyde or ketone is generally between approximately 1.2 and approximately 12 and preferably between about 1.5 and apr-ox a. , the amount of catalyst used relative to the total charge of reactable materials introduced into the reactor in general is between approximately 0.5% and approximately 20%, preferably between about 2% and approximately 15%. The catalyst used in the total charge of reactable materials introduced between about 3% and about 10% is particularly preferred.The catalyst of the general formula (I *): HMg2 +) _- "(013+)" (OH ") 2]« + r (0H-) "_ * - (H20)" (I) which has a value n n that can vary from 0.5 and 0.75 in most cases is used in the procedure of t or f orinity with 1 »present invention. A catalyst of the general formula (T) having a value n equal to or close to 0.81-x is advantageously chosen, such f '^ as ineixnepta especially of formula: I (2+ J? .7s (fll3 +)? 2S < OH-) 2l0-2S + pQ? -) o.2S-_ í 1-120) o.5 E71 catalyst- of the general formula (I) can be prepared according to the method described by G. Mascolo 0 y O Marino in My neralogí cal Magaz e March 1980, Vol. 43 p. 619. This method of preparation consists of suspending gei of alumina and MgO, obtained by calcining basic magnesium carbonate at B50 ° C, in distilled water in a closed teflon receptacle, with stirring, for one week at 80 ° C. The suspension is then filtered with protection against CO2 and finally the collected solid is dried on silica gel. This catalyst can also be prepared by hydration of double magnesium aluminum oxide Mgi-0? Hl? O_ +? in the absence of C02. The hydration is carried out with water in the liquid phase or in the vapor phase. Mixed double oxide can be a commercial product or one obtained by calcining-hydrotalcites, with a value of x that can vary from 0. 2 to 0.33, at a temperature lower than 800 ° C. After the hydration step in accordance with any of the methods described above, the solid can be dried by evaporation under reduced pressure at a temperature below G0 ° C or by rinsing with a solvent mixed in water as, i-for example, acetone. To prepare the catalyst of the general formula (T) a commercial double oxide is advantageously and preferably chosen from the Japanese company Kyowa, reference number K 2000 and having a value of x close to 0.3. In most cases, the Joble oxide is hydrated in the liquid phase and the solid obtained in this way is successfully rinsed with a solvent mixed in water and preferably with acetone. The invention will be better understood from the following non-limiting examples: EXAMPLE 1 Preparation of catalyst. The mixed double oxide KU 2000 that has the following characteristics is hydrated with water in liquid phase: Chemical formula: 4.5 Mg0.fll2? 3 (x = 0.3077) Bulk density: 44 rnl / 1.0 g Appearance: fine white powder without odor BET = 172 rn2 / g Average particle size: 70 urn. Absorbing property: absorbs at most 70-80 parts of water per 100 parts of FU 2000. In this way, grams of KU 2000 are added with agitation to 200 ml of decarbonised water (exchanged of V ions after flowing water) . The mixture is left stirring for 3 hours and the solid is then separated. The isolated solid is then rinsed several times with acetone before being stored with protection against C02. 9 g of solid are obtained from the general formula (I) where x has the value 0.3077 and has a crystal structure of the type hydr-ot lcit or ixne ita.

EXAMPLE 2 4. 9 g of the catalyst of Example 1, followed by 37 g of acetone, are introduced at room temperature into a stirred reactor and flushed with a stream of nitrogen. The charge is then heated with stirring at 5D ° C for 30 minutes. 100 g of a mixture containing 75% by weight of acetone and 25% by weight of isobutanal are then introduced for 2 hours. After the end of the introduction of the mixture the reaction is allowed to proceed for one hour 30 minutes at 50 ° C. At the end of the reaction the catalyst is filtered and the final solution is analyzed by gas phase chromatography. The cro agraph employed is a Perl-ín-Elimer-8420 equipped with a FID detector, a 3 »Ul DB 1701 capillary type column 25 n in diameter and 30 n in length.

J L the injector temperature is 230 ° C and that of the detector 1 '5"C, 1 1 injector em gives an de of p ml / min 1 furnace prog-amado with a gradient of! ° C / mm from the initial temperature of B0 ° 0 to the final temperature of 200 ° C. The physical analysis of the solution f in l gives an isobutanal conversion of -38% , a selectivity for 5-inet 1 -i -hi dr'oxi - -he xa nona of 34% and that for 5 -inet ii -3-hexene-2-one of 45%, the total selectivity for β-carbonyl compounds -hydroxy ya, ß- unsaturated is 9% " EXAMPLE 3 The procedure is identical to Example 2 but butanal is used instead of isobutanal. The results obtained at the end of the reaction are: Conversion of but-anal - 96% Selectivity for 4-hydroxy-2-heptanone = 41% Selectivity for 3-he-teno-2-one = 30% Total selectivity for β-hydroxy and cf, β-unsaturated carbonium compounds = 71%.

EXAMPLE 4 (COMPARATIVE) The procedure is identical to Example 3 but 4.9 g of the commercial double oxide KW 2000 was used instead of the catalyst of example 1. The results obtained at the end of the reaction are: Butanal conversion - 7% Selectivity for 4-h ? drox? -2-heptanone = 37% Selectivity par-a 3-hepteno- -ona - 5% Total selectivity for ß-hydroxy and a, ß-unsaturated carbonyl compounds • - 42%.

EXAMPLE 5 (COMPARATIVE) The procedure is identical to Example 2 but 4.9 g of commercial double oxide KU 2000 was used instead of the catalyst of Example 1. The results obtained at the end of the reaction are: Conversion of isobutanal - 7% Selectivity for 5-rnethyl-4-hydroxyl-2-hexanone - 40% Selectivity for 5-methyl-3-hexene-2-one --- 10% Total selectivity for ß-hydroxy and, ß ~? Nsaturated carbonyl compounds = 50% EXAMPLE 6 (COMPARATIVE) The procedure is identical to Example 2 but 10 g of 2N methanol sodium hydroxide, ie 0.8 g of pure sodium hydroxide, were used instead of the catalyst of Example 1.

The results obtained at the end of the reaction are: Conversion of isobutanal 09% Selectivity for 5-rnet? L -4 - h? Drox? -2-hexanone - 13% Selectivity for 5-rnet? L-3 ~ hexene-2 - ona - b% Total selectivity for ß-hydroxy and or, ß-? nsaturated carbonyl compounds = 19% EXAMPLE 7 g of the catalyst of example 1, followed by 100 g of butanal, are introduced at room temperature in a stirred reactor of 0.5 liters, thermosetting purged with a stream of nitrogen. The load is then heated to 75 ° C for 30 minutes and allowed to cool for 3 hours. At the end of the reaction the catalyst is filtered and the final solution is analyzed by gas phase chromatography in the same way as in example 2. A butanal conversion of 77%, a selectivity for 2-et? L-2- hexenal of 57% and one for 2-et? l ~ 3-hydrox? 10% hexanal are obtained. The total selectivity for β-hydroxy and cf, β-β-unsaturated carbonyl compounds is 57%.

EXAMPLE 8 (COMPARATIVE) The procedure is identical to Example 7, but commercial double oxide KU 2000 is employed instead of l? catalyst of example 1. final 3-hr. a butanal conversion of 0% and a selectivity for 2-et? i- -hexenal of 30% and a selectivity for 2 -et? l-3-h? 50% hexanal droxy are obtained. the total selectivity for β-hydroxy and ot, β-L-unsaturated carbonyl compounds is 80%.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A procedure to obtain compounds of < a bomlo ß-hi roxi and / or carbomlo cr, ß-nisaturados compounds, further characterized because at least one aldehyde or a cotone makes contact with a solid catalyst of the general formula (I): [f Mg2 +)? - x (013+) "(OH ~) 2] x +!" (0H ~) H] x + p-l20) n (J) with 0.20 <x < 0.33 yn < 1.

2. A procedure in accordance with the claim 1, further characterized in that at least one aldehyde or a ketone has a hydrogen atom in the carbon of the carbomium functional group

3. A process according to claim 1 or 2, further characterized in that an aldehyde of the general formula R * -CHO wherein R 1 denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms, is reacted with optionally at least one compound chosen from another aldehyde of the general formula R 2 -CH 0 in where R2 denotes a hydrogen atom or a linear or branched alkyl or cyclic radical containing from 1 to 10 atoms of carbon or a radical femlo or a radical benzyl or an aralkyl radical and / or a ketone of the formula R5-C0-R6 wherein each RS or R6, which are identical or different, denotes a linear or branched alkyl radical containing 1 to 10 Ib carbon atoms and capable of being joined to the other to form a ring.

4. A compliance procedure according to the description 1 or 2, characterized by a ketone of the general formula R3 -CH-R in where each R3 and R, which are identical or different, denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms, it is reacted with optionally at least one compound selected from an aldehyde of ia. general formula R2-CHO wherein R2 denotes a hydrogen atom or a linear or branched alkyl or cyclic radical containing 10 L atoms of carbon or a phenyl radical or a benzyl radical or an aralkyl radical and / or another ketone of the formula R5-C0-R6 wherein each R5 or 6, which are identical or different, denotes a linear or branched alkyl radical containing from 1 to 10 carbon atoms and capable of being bound to the other to form a ring.

5. A process according to claim 3, further characterized in that the aldehyde of the general formula Ri-CHO is chosen from ethanal, pro-anayl, butanal, isobutanal, pentanal, hexanal and heptanal.

6. A process according to claim 5, further characterized in that the aldehyde is butanal or isobutanal.

7. A process according to one of claims 3 to 5, further characterized in that the aldehyde of the general formula R2-CH0 is chosen from methanal, ethanal, propanai, butanal, isobutanal and benzylaldehyde.

8. A process of conformity with claim 7, further compounded because the aldehyde is methyl, butanal or isobutanal.

9. A process according to claim 4, 7 or 8, further characterized in that the ketone of the general formula R3-C0-R is chosen from acetone, ethyl methyl ketone and inet 11 propyl ketone.

10. A process according to claim 9, further characterized in that the ketone is acetone.

11. A process according to any of claims 1 to 10, further characterized in that the catalyst of the general formula (T) has a value n that varies from 0.5 to 0.75.

12. A method according to claim 11, further characterized in that the value of n is equal to or close to 0.81-x.

13. A method according to any of claims 1 to 12, further characterized in that the operation is carried out at a temperature between 0 and 200 ° C.

14. A method according to claim 13, further characterized in that the temperature is between 0 and 140 ° C.

15. A method according to claim 14, further characterized in that the temperature

16. .- A ?? procedure to obtain -hydrox i - 2 hept anona and / or 3 -hept ene-2-one in accordance with any of the re fections of 1 to 15. 17.- A procedure to obtain 5 -meti -4- hi dro i-2-hexanone and / or 5-rnet? I -''-hexene-2-one according to any of claims 1 to 1., 10. A process for obtaining 2-et? L -3-h? droxy hexanal and / or 2 -et 11 -2 -hexenal according to any of claims I to 3, 5 to 8 and ll to l5. 19. A specific means for making use of the process according to any of claims 1 to 15, a catalyst of the general formula (I) that results from a hydration in the absence of C02 of the double oxide Mg? -? Alx0? + X, obtained by calcining a hydrotalcite, followed by rinsing with a solvent mixed in water. 20. A process according to claim 19, further characterized in that the solvent is acetone.