CATALYST SYSTEM

Abstract

Proposed is a catalyst system specifically for the rearrangement of epoxides into allyl alcohols comprising or consisting of (a) a salt of formula (I) XY (I) in which X represents Zn.sup.2+ and/or Co.sup.2+ and Y represents an anion selected from the group formed from laurate, palmitate, stearate, picolinate, glycinate, gluconate, naphthenate, 2-hexyldecanoate, 2-octyldodecanoate, cyclohexane butyrate and mixtures thereof, and (b) at least one aminophenol.

Claims

1. A catalyst system, comprising or consisting of (a) a salt of formula (I)
XY(I) wherein X represents Zn.sup.2+ and/or Co.sup.2+ and Y represents an anion which is selected from the group consisting of laurate, palmitate, stearate, picolinate, glycinate, gluconate, naphthenate, 2-hexyldecanoate, 2-octyldodecanoate, cyclohexane butyrate, and the mixtures thereof, and (b) at least one aminophenol.

2. The catalyst system according to claim 1, wherein component (a) is selected from the group consisting of zinc stearate, cobalt stearate, zinc glycinate, zinc naphthenate, and mixtures thereof.

3. The catalyst system according to claim 1, wherein the aminophenol is 2-Aminophenol.

4. The catalyst system according to claim 1, wherein it represents the combination of (a) zinc stearate, cobalt stearate, zinc glycinate, zinc naphthenate, and mixtures thereof, and (b) 2-Aminophenol.

5. The catalyst system according to claim 1, wherein it is suitable both for the rearrangement of epoxides in allylic alcohols and production of alpha-beta-unsaturated carbonyl compounds.

6. A method for the rearrangement of epoxides in allylic alcohols, comprising the following steps: (a) Providing a starting compound having at least one epoxide group; (b) Providing a catalyst system according to claim 1; (c) Adding the catalyst system to the starting compound, and heating the mixture to temperatures within the range of from about 155 to about 250 C. over a period of from about 1 to about 10 hours; and (d) Allowing the mixture to cool, and, optionally, separation of the one or more allylic alcohols formed from the residue.

7. A method for the rearrangement of epoxides and Oppenauer oxidation, in alpha,beta-unsaturated carbonyl compounds, comprising the following steps: (a) Providing a starting compound having at least one epoxide group; (b) Providing a catalyst system according to claim 1; (c) Providing a consumption agent; (d) Adding the catalyst system to the starting compound and the consumption agent ketone, and heating the mixture to temperatures within the range of from about 170 to about 250 C. over a period of from about 1 to about 10 hours; and (e) Allowing the mixture to cool and, optionally, separation of the one or more alpha-beta-unsaturated carbonyl compounds formed from the residue.

8. The method according to claim 6, wherein the one or more reactions are performed at temperatures within the range of from about 200 to about 230 C.

9. The method according to claim 6, wherein catalyst component (a) is employed in amounts of from about 0.05 to about 5 mol %, and catalyst component (b) is employed in amounts of from about 0.01 to about 0.00001 mol % each based on the starting compounds.

10. The method according to claim 6, wherein the one or more reactions are carried out in the presence of a solvent.

11. The method according to claim 7, wherein the rearrangement and the Oppenauer oxidation are performed simultaneously as a one-pot reaction, or subsequently.

12. The method according to claim 7, wherein the consumption agent is added only in the course of reaction.

13. The method according to claim 7, wherein an aldehyde, a ketone, or a quinone is used as a consumption agent.

14. The method according to claim 7, wherein the alcohol formed from the consumption agent is periodically removed from the reaction mixture.

15. The method according to claim 6, wherein 1,2-Limonene epoxide is used as a starting compound.

16. A pre-formed catalyst, comprising at least one of the following structures (1) to (8): ##STR00008##

Description

DESCRIPTION OF THE INVENTION

[0017] A first subject matter of the invention relates to a catalyst system, particularly for the rearrangement of epoxides to allylic alcohols, and for the production of alpha,beta-unsaturated carbonyl compounds, comprising or consisting of [0018] (a) a salt of formula (I)

XY(I) [0019] Where X represents Zn.sup.2+ and/or Co.sup.2+ and Y represents an anion which is selected from the group consisting of laurate, palmitate, stearate, picolinate, glycinate, gluconate, naphthenate, 2-hexyldecanoate, 2-octyldodecanoate, cyclohexane butyrate and the mixtures thereof, and [0020] (b) at least one aminophenol.

[0021] Surprisingly, it was found that the catalyst system, particularly pre-formed catalysts, catalysed both the rearrangement of epoxides to allylic alcohols and also the Oppenauer oxidation of allylic alcohols to the corresponding alpha,beta-unsaturated carbonyl compounds, which was carried out at conversions of above 70% and with yields of more than 40%.

Catalyst System

[0022] The catalyst system according to the invention consists of two components, i.e., (a) primary catalyst and (b) an activator or modifier. Component (a) is a defined salt of divalent zinc or cobalt, particularly, zinc stearate, cobalt stearate, zinc glycinate, zinc naphthenate, and mixtures thereof. Herein, the term salt is understood to mean that it is an at least mainly ionic compound containing Zn.sup.2+ and/or Co.sup.2+ cations as well as a corresponding stoichiometric number of said anions, so that a neutral compound is present.

[0023] Component (b) has the task of activating component (a), as component (a) alone very often does not have any catalytic properties, or just very few. At the same time, being a modifier, it has the property to control selectivity. Suitable activators/modifiers are aminophenols, particularly, 2-Aminophenol.

[0024] Particularly preferred are catalyst systems which are a combination of (a) zinc stearate, cobalt stearate, zinc glycinate, zinc-2-ethyl hexanoate, zinc naphthenate, and mixtures thereof with (b) 2-Aminophenol.

[0025] The catalyst systems may include components (a) and (b) in a weight ratio of from about 10.000:1 to about 10:1, preferably, from about 5.000:1 to about 100:1, and particularly, from 1.000:1 to about 500:1.

Method

[0026] A second subject matter of the invention relates to a method for the rearrangement of epoxides to allylic alcohols, comprising or consisting of the following steps: [0027] (a) Providing a starting compound having at least one epoxide group; [0028] (b) Providing a catalyst system as described above; [0029] (c) Adding the catalyst system to the starting compound and heating the mixture to temperatures within the range of from about 155 to about 250 C. for a period of from about 1 to about 10 hours; [0030] (d) Allowing the mixture to cool, and, optionally, separation of the one or more allylic alcohols formed from the residue.

[0031] A third subject matter of the invention relates to a method for the rearrangement and Oppenauer oxidation of epoxides to alpha,beta-unsaturated carbonyl compounds, comprising or consisting of the following steps: [0032] (a) Providing a starting compound having at least one epoxide group; [0033] (b) Providing a catalyst system as described above; [0034] (c) Providing a consumption agent; [0035] (d) Adding the catalyst system to the starting compound and the consumption ketone, and heating the mixture to temperatures within the range of from about 170 to about 250 C. for a period of from about 1 to about 10 hours; [0036] (e) Allowing the mixture to cool, and, optionally, separation of the one or more alpha-beta-unsaturated carbonyl compounds formed from the residue.

[0037] According to the present invention, a broad spectrum of epoxides may be converted to allylic alcohols. Examples of terminal, cyclic, di-substituted, tri-substituted epoxides are 1,2-Limonene oxide, 8,9-Limonene oxide, alpha-Pinene oxide, beta-Pinene oxide, 2,3-Carene oxide, 3,4-Carene oxide, 1,2-Terpinolene oxide, 4,8-Terpinolene oxide, Sylvestrene oxide, 1,2-Menthene oxide, 2,3-Menthene oxide, 3,4-Menthene oxide, 7,8-Dihydromyrcene oxide, Caryophyllene oxide, 1,2-Epoxy cyclododecane, and the like. The rearrangement of epoxides to allylic alcohols according to the present invention may be performed by contacting epoxide with the catalyst system under suitable reaction conditions, e.g., at an increased temperature, usually under reflux. The epoxide rearrangement may be performed batch-wise or continuously. Other suitable steps may also be included into the rearrangement process. For example, it may be preferred to remove water, which is contained in the starting materials, or which has been formed during the process. In these instances, water may be removed before or during the rearrangement by known methods: if an allylic alcohol is a final product, rearrangement may be stopped, e.g., after all epoxide has been reacted, or when the desired conversion has been achieved. Furthermore, the following steps may be applied after rearrangement. For example, catalyst may be removed by any suitable method (filtration, cleaning, extraction, distillation, etc.), and product, e.g., allylic alcohol, may be isolated and purified using a method known in the art, such as, for example, by distillation or crystallisation.

[0038] Both methods may be performed at the same or very similar temperatures, particularly within the range of from about 200 to about 230 C., and particularly of from about 210 to about 220 C.

[0039] Catalyst component (a) is usually used in amounts of from about 0.05 to about 5 mol %, preferably, about 0.1 to about 1 mol %, and catalyst component (b) in amounts of from about 0.01 to about 0.00001 mol %, preferably, about 0.001 to about 0.0001 mol %, each based on the starting compound.

[0040] A further advantage of the invention is that the rearrangement and the Oppenauer oxidation may be performed either simultaneously as a one-pot reaction, or subsequently.

[0041] Within the context of the Oppenauer oxidation it is reasonable to use a consumption agent. If the reaction is performed as a one-pot reaction where both reactions are proceeding at the same time, it is possible, in principle, to use the consumption agent together with the catalyst system; however, it is more advantageous to firstly allow the reaction to proceed for a certain amount of time so that a sufficient amount of allylic alcohol is present, and to add the consumption agent only later, thus starting the oxidation process.

[0042] Suitable consumption agents are, particularly, aldehydes or ketones, including the quinones. Typical examples encompass benzaldehyde, acetone, cyclohexanone, benzoquinone, or isophorone. Typically, these are used in very low amounts, for example, from about 1 to about 100 mmol, preferably, from about 10 to about 50 mmol consumption agent, based on the amount of starting compound.

[0043] Further, it has proved to be advantageous to periodically remove the alcohol formed from the consumption agent, which, preferably, represents cyclohexanone, from the reaction mixture, as this way the balance is shifted to the product side.

EXAMPLES

General Scheme

[0044] The following scheme exemplarily illustrates the rearrangement of 1,2-Limonene epoxide to the corresponding allylic alcohol carveol on the one hand, and its further reaction by Oppenauer oxidation on the other, in order to form the alpha-beta-unsaturated carbonyl compound carvone.

##STR00004##

Examples 1 to 12, Comparison Examples V1 to V25

Rearrangement of 1,2-Limonene Epoxide to Carveol

[0045] 16 mmol 1,2-Limonene epoxide (LEcis:trans=58:42 (mol/mol)), 1.3 mol % of catalyst, and 2-Aminophenol (2AP) were placed into a three-neck flask equipped with a reflux cooler, an internal thermometre, and a capillary for dosing a gas. The mixture was heated to 205 to 210 C. while stirring, and was further continued to be stirred at this temperature for the time indicated. After cooling down, product composition was determined by means of gas chromatography. Table 1 summarises the results:

TABLE-US-00001 TABLE 1 Rearrangement of 1,2-Limonene oxide (conversions and yields in GC %) Yields 2AP Conversion Iso- Exp. Catalyst (mmol) t(h) LE Carveol Carveol Carvone V1 Zn.sub.3(citrate).sub.2 2 H.sub.2O 0.32 4 22.2 0.5 1.2 0.3 V2 Cu(stearate).sub.2 0.33 4 21.8 1.7 1.9 0 V3 Li-stearate 0.33 4 17.1 0.9 2.3 0 V4 CdO 0.32 4 8 2.1 3.9 2 V5 Zn(gluconate).sub.2 H.sub.2O 0.32 4 8.7 4.2 4.1 V6 Pr(NO.sub.3).sub.3 6 H.sub.2O 0.32 4 73.4 8.4 5.4 7.1 V7 Ca(stearate).sub.2 0.32 4 8.3 3 5.5 1.2 V8 In(tetramethylheptanedione).sub.3 0.32 4 19 9.3 5.7 0.6 V9 Co-naphthenate 0.32 4 98.5 12.1 6.7 10.7 V10 Cd(acetate).sub.2 0.32 4 36.9 8 7.2 8.4 V11 Mg-stearate 0.32 4 59.4 4.3 8.3 3.2 V12 In(acetylacetonate).sub.3 0.32 4 41 19.8 10.6 2.6 V13 Fe-naphthenate 0.32 4 90.3 15 14.1 7.8 V14 Ga(tetramethylheptanedione).sub.3 0.32 4 59.4 22.8 15.4 2.3 V15 NdCl.sub.3 0.32 4 74.5 8.9 15.4 7.5 V16 Sn(acetylacetonate).sub.2 0.32 4 70.6 31.2 15.8 2.6 V17 Zn-orotate 2 H.sub.2O 0.32 4 63.2 18.1 16.1 1 V18 In(acetate).sub.3 0.32 4 65.5 34.9 16.9 2.6 V19 Zn(acetylacetonate).sub.2 0.32 4 81.3 9.2 26.6 8.7 V20 Ni(acetylacetonate).sub.2 0.32 4 50.1 3.9 27 4.3 V21 Zn(octoate).sub.2 0.32 3 66.1 7.5 29.2 8.4 V22 Zn(tetramethylheptanedione).sub.2 0.32 4 52.1 7.7 30 5.7 V23 Fe(acetylacetonate).sub.3 0.32 4 84.5 15.1 37.4 4.8 V24 Zn(tetradecyloctadecanoate).sub.2 0.32 4 82.4 4.1 37.5 16.1 V25 Zn(octoate).sub.2 0.32 4 75.7 7.9 38.7 13.5 1 Zn(2-octyldodecanoate).sub.2 0.32 4 83.7 5.3 40.0 12.6 2 Zn(cyclohexane butyrate).sub.2 0.32 4 82.5 12.4 40.0 17 3 Zn(stearate).sub.2 3.00 7 99.3 4.5 41.9 8.1 4 Zn(2-hexyldecanoate).sub.2 0.32 4 84.7 4.5 43.3 13.7 5 Zn(palmitate).sub.2 0.32 4 81.4 8.2 45 17.8 6 Zn(picolinate).sub.2 0.32 4 99.5 13.1 48.7 12 7 Zn(laurinate).sub.2 0.32 4 73.1 8 49 16.8 8 Zn(picolinate).sub.2 0.32 4 99.7 10.4 49.7 9.9 9 Co(stearate).sub.2 0.33 4 90.6 9.2 49.8 13 10 Zn(glycinate).sub.2 H.sub.2O 0.32 4 97.4 13.3 53.5 15.4 11 Zn-naphthenate 0.32 4 86.2 8.8 54.7 13.9 12 Zn(stearate).sub.2 0.32 4 93.6 13.7 55.2 20.4

[0046] Examples and comparison examples show that the object of achieving yields of carveol of at least 40% may only be achieved with the catalyst system according to the invention.

Examples 13 to 19

Combination of Rearrangement and Oppenauer Oxidation

[0047] 16 mmol 1,2-Limonene epoxide (cis:trans=58:42 (mol/mol)), half of the amount of catalyst, and the phenol were placed into a three-necked flask equipped with a reflux cooler, an internal thermometre, and a capillary for dosing a gas. While stirring, the amount was heated to 205 to 210 C. with the reflux cooler switched off, and was continued to be stirred at this temperature for the time indicated (e.g., 3/2). After cooling down to 180 to 190 C., the second half of the amount of catalyst and the consumption agent were added and continued to be stirred at this temperature under reflux for the time indicated (e.g., 3/2). After cooling down, product composition was determined by means of gas chromatography. Results are summarised in Table 2.

Example 20

Rearrangement/Oppenauer Reaction as a One-Pot Reaction with Intermediate Removal of Cyclohexanol Formed

[0048] 16 mmol 1,2-Limonene epoxide (cis:trans=58:42 (mol/mol)), half of the amount of catalyst, and the phenol were placed into a three-necked flask equipped with a reflux cooler, an internal thermometre, and a capillary for dosing a gas. While stirring, the mixture was heated to 205 to 210 C., and was continued to be stirred at this temperature for the time indicated (e.g., 2/2/2). After cooling down to 180 to 190 C., the second half of the amount of catalyst and half of the amount of cyclohexanone were added, and were continued to be stirred under reflux for the time indicated (e.g., 2/2/2). Subsequently, the mixture was cooled and distilled over a distilling link cyclohexanol/unreacted cyclohexanone placed onto the flask. Then, the second half of the amount of cyclohexanone was added to the reaction mixture, and the content of the flask was again brought to reflux for the time indicated (e.g., 2/2/2). After cooling down, product composition was determined by means of gas chromatography; results are also shown in Table 2.

TABLE-US-00002 TABLE 2 Rearrangement/Oppenauer oxidation of 1,2-Limonene oxide (conversions and yields in GC %) Consump- tion Yields Catalyst Phenol Consumption agent t Conversion Iso- Exp. Catalyst [mol %] Phenol [mmol] agent [mmol] [h] LE carveol Carveol Carvone 13 Zn(laurate).sub.2 1.3 2-Aminophenol 0.6 Cyclohexanone 14.2 3/4 95 4 33.1 40.1 14 Co(stearate).sub.2 1.3 2-Aminophenol 0.32 Cyclohexanone 14.2 3/3 94.4 7.6 12.4 40.6 15 Zn(stearate).sub.2 1.3 2-Aminophenol 0.6 Cyclohexanone 14.2 3.5/4 96.7 4.2 23.2 42.4 16 Zn(palmitate).sub.2 1.3 2-Aminophenol 0.6 Cyclohexanone 14.2 3/4 94.6 4.5 18.6 43.5 17 Zn(stearate).sub.2 1.3 2-Aminophenol 0.6 Cyclohexanone 28.4 3/2 96.4 6.3 27.8 45.4 18 Zn(glycinate).sub.2 H.sub.2O 1.3 2-Aminophenol 0.6 Cyclohexanone 14.2 3/4 99.3 6 29 47 19 Zn-naphthenate 1.3 2-Aminophenol 0.6 Cyclohexanone 14.2 3/4 97.4 4.9 18.1 56.1 20 Zn(stearate).sub.2 1.3 2-Aminophenol 0.6 Cyclohexanone 28.4 2/2/2 87.9 5.3 38.4 43.8

Examples 21 to 31

Rearrangements Using Pre-Formed Catalysts

[0049] cis-Limonene-1,2-epoxide may be rearranged faster than trans-Limonene-1,2-epoxide. The rearrangement of trans-Limonene-1,2-epoxide is facilitated if cis-Limonene-1,2-epoxide is present in the reaction mixture. Therefore, it is advantageous to utilise as the substrate either pure cis-Limonene-1,2-epoxide or a mixture of cis- and trans-Limonene-1,2-epoxides having a high cis-proportion.

[0050] Particularly preferred catalysts are also pre-formed Zn(aminophenolate).sub.2 complexes 1-8. These allow the rearrangement of the epoxide already at milder reaction temperatures of from 155 C. (see Table, examples 2, 4, 5). They could be produced in analogy to a method of production found in literature (H. R. Hoppe, K. Andr, Z. Chem. 26 (1986)) as follows:

[0051] Under protective gas, 2.5 mL ZnEt.sub.2 in dry toluene (16.3%, 3 mmol) were filled into a dried 100 mL Schlenk flask. While stirring and with a slight flow of argon, 0.635 g (6 mmol) 2-Aminophenol was added in doses via a septum at a temperature of 25 C. within 10-15 mins. A colourless solid precipitated, and the formation of ethane was observed. Crystals attached to the flask wall were carefully washed back into the reaction mixture using 5 mL dry toluene. When addition was completed, the Schlenk flask was heated to 88 C. in an oil bath, and was stirred at this temperature for two hours. Subsequently, the hot reaction mixture was filtered, and the solid obtained was treated with dry toluene until reaching colourlessness of the purifying solvent. Then, the crystals were also washed with dry heptane, dried within the oil pump vacuum, and used as catalysts. As an example, 0.78 g (93% yield) were isolated from Zn(2-Aminophenolate).sub.2. Structures of pre-formed catalysts are shown below (reference numbers correspond to those in Table 3):

##STR00005##

[0052] The use of 2-Aminophenols alkylated with cis- or trans-Limonene-1,2-epoxide instead of 2-Aminophenol, in combination with Zn-2-ethylhexanoate also yielded very high yields of carveol plus carvone. With this catalyst system significant differences in reactivity of cis- and trans-(+)-Limonene-1,2-epoxide were determined. Alkylated aminophenols 9-11 were produced as follows:

[0053] 270 mg (1.77 mmol) cis-(+)-Limonene-1,2-epoxide, 110 mg (0.99 mmol) 2-Aminophenol and 10 mg (0.036 mmol) Zn(2-Aminophenolate).sub.2 were placed into a 2-necked pear-shaped flask (10 mL) equipped with a reflux cooler and a thermometre. The apparatus was fixed in a preheated oil bath. Internal temperature was 166 C. The reaction mixture was stirred for 2 h 15 mins. After cooling down, products were separated by column chromatography (eluent: ethyl acetate/heptane 3.5:5). Fractions 15-26 (95 mg) contained the monoalkylated product 9. Mono- and dialkylated products 10 and 11 with trans-(+)-Limonene-1,2-epoxide were produced in analogy to this method, separated by column chromatography, and purified. Structures of alkylated aminophenols are given below:

##STR00006## ##STR00007##

Catalytic Reactions

[0054] 19.7 mmol 1,2-Limonene epoxide (LEcis:trans-=63:37 (mol/mol)) and 0.4 mol % of catalyst were placed into a three-necked flask equipped with a reflux cooler, an internal thermometre, and a capillary for dosing a gas. While stirring, the mixture was heated in an argon atmosphere to the temperature indicated, and was continued to be stirred at this temperature for the time indicated. After cooling down, product composition was determined by means of gas chromatography. Table 1 summarises the results:

TABLE-US-00003 TABLE 3 Rearrangement of 1,2-Limonene epoxide with pre-formed zinc catalysts conver- Yields [%] sion Isocarveol + T LE Dihydro- Exp. Cat. [ C.] t [h] [%] carvone Carveol Carvone 21 1 200-224 0.5 98.8 3.6 80.2 7.2 22 1 155 6 79.3 2.1 68.9 1.2 23 2 200-224 0.5 99.7 4.6 70.3 12.2 24 2 160 3 76.2 3.0 67.2 2.1 25 2 186 6 99.0 3.6 79.3 7.8 26 3 200-224 2 98.5 4.0 77.0 7.7 27 4 200-224 0.5 99.1 3.8 77.3 7.9 3 99.7 4.3 64.4 20.7 28 5 200-224 3 96.0 5.4 57.4 18.1 29 6 200-224 2.5 98.7 5.6 76.2 9.6 30 7 200-224 1,5 99.6 6.1 43.3 29.7 4.5 100 5.0 17.8 46.4 31 8 200-224 0.25 92.2 6.0 68.4 5.3 3 100 5.9 32.3 40.7

[0055] 19.7 mmol (+)-Limonene-1,2-epoxide, the indicated amount of Zn-2-Ethylhexanoate, and the indicated amount of aminophenol were placed into a three-necked flask equipped with a reflux cooler, an internal thermometre, and a capillary for dosing a gas. While stirring, the mixture was heated to 200 to 224 C. in an argon atmosphere, and was continued to be stirred at this temperature for the time indicated. After cooling down, product composition was determined by means of gas chromatography. Table 1 summarises the results.