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Title:
PROCESS FOR THE PRODUCTION OF (10/11/12)-PENTADECEN-15-OLIDE STARTING FROM 11- AND/OR 12-PENTADECEN-15-OLIDE
Document Type and Number:
WIPO Patent Application WO/2007/054429
Kind Code:
A1
Abstract:
A process is described for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, which process comprises the following step: partial isomerisation of (E1Z)-H - and/or (E,Z)-12-pentadecen-15-olide, such that the (E1Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.

Inventors:
KUHN WALTER (DE)
FRANKE OLIVER (DE)
Application Number:
EP2006/067748
Publication Date:
May 18, 2007
Filing Date:
October 25, 2006
Export Citation:
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Assignee:
SYMRISE GMBH & CO KG (DE)
KUHN WALTER (DE)
FRANKE OLIVER (DE)
International Classes:
C07D315/00
Domestic Patent References:
WO2005012315A12005-02-10
Other References:
FURSTNER, ALOIS ET AL: "Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands", CHEMISTRY--A EUROPEAN JOURNAL , 7(15), 3236-3253 CODEN: CEUJED; ISSN: 0947-6539, 2001, XP002418756
GRIECO P A ET AL: "Remote double bond migration via rhodium catalysis: a novel enone transposition", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 98, no. 22, 27 October 1976 (1976-10-27), pages 7102 - 7104, XP002354942, ISSN: 0002-7863
Attorney, Agent or Firm:
STILKENBÖHMER, Uwe et al. (Speiser & Partner P.O. Box 10 60 78, Bremen, DE)
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Claims:

Claims

1. A process for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, comprising the following step:

- partial isomerisation of (E 1 Z)-H- and/or (E 1 Z)-12-pentadecen-15-olide, such that the (E 1 Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.

2. A process according to claim 1 , wherein the isomer mixture comprises a proportion of at least 5 wt.% of (E 1 Z)-I O-pentadecen-15-olide, relative to the total quantity of (E 1 Z)-I O-, (E 1 Z)-H- and (E 1 Z)-12-pentadecen-15-olide, wherein the quantity of (E 1 Z)-I O-pentadecen-15-olide optionally already present in the educt mixture is not included in the calculation.

3. A process according to claim 1 , wherein an (E 1 Z)-(1 1/12)-pentadecen-15- olide isomer mixture is introduced into the isomerisation.

4. A process according to any one of the preceding claims, wherein the (E 1 Z)- 1 1- and/or (E 1 Z)-12-pentadecen-15-olide is brought into contact with

(I) a catalyst containing an element of subgroup VIII in such a manner,

that it partially isomerises to form the (E 1 Z)-(10/11/12)-pentadecen-15-olide isomer mixture.

5. A process according to claim 4, wherein the element of subgroup VIII is selected from the group consisting of ruthenium, rhodium, palladium and iridium.

6. A process according to claim 4 or claim 5, wherein the catalyst containing an element of subgroup VIII is present

(a) in elemental form,

(b) in complexed or uncomplexed form as a salt formally having an oxidation number of one to three,

or

(c) as a complex compound in which it is formally zero-valent.

7. A process according to any one of claims 4 to 6, wherein the catalyst containing an element of subgroup VIII is selected from the group consisting of rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(l)-bis- (triphenylphosphine)-carbonyl chloride, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(ll)-tris-(triphenylphosphine) chloride, iridium(l)-bis- (triphenylphosphine)-carbonyl chloride, palladium(ll)-bis-(benzonitrile) chloride, and palladium, preferably in the form of palladium on activated carbon.

8. A process according to any one of claims 4 to 7, wherein the quantity of catalyst is in the range from 0.05-5 wt.%, relative to the total mass of (E 1 Z)-11- and/or 12-pentadecen-15-olide introduced into the isomerisation.

9. A process according to any one of the preceding claims, wherein the isomerisation is performed at a temperature in the range from 40 to 250°C, preferably 150 to 230°C.

Description:

Symrise GmbH & Co. KG Mϋhlenfeldstraβe 1 , 37603 Holzminden

Process for the production of (10/11/12)-pentadecen-15-olide starting from 11- and/or 12-pentadecen-15-olide

The present invention relates to a process for the production of a mixture of (10/1 1/12)-pentadecen-15-olide starting from 11 - and/or 12-pentadecen-15-olide.

The compounds 1 1-pentadecen-15-olide and 12-pentadecen-15-olide and mixtures thereof ((1 1/12)-pentadecen-15-olides) are known and important musk fragrances. Both the particular (E) and (Z) forms and the mixtures thereof are here also of interest from the point of view of odour. EP 0 424 787 describes the odorous properties of these substances. It is likewise known that 15- pentadecanolide (15-hydroxypentadecanoic acid lactone), which is likewise usable as a musk fragrance, may be obtained by means of hydrogenation from 1 1 (12)-pentadecen-15-olides.

(1 1/12)-Pentadecen-15-olides may advantageously be produced starting from 13-oxabicyclo[10.4.0]hexadec-1 (12)-ene (DDP, see for example US 3,856,815). 1 -Hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (DDP-hydroperoxide, DDP- OOH) is obtained by acid-catalysed addition of hydrogen peroxide onto DDP. In

a second step in the synthesis to yield the 1 1 (12)-pentadecen-15-olides, DDP- OOH is cleaved to form the macrocyclic ring. This cleavage is usually performed in the presence of catalysts such as Cu(OAc) 2 (see for example EP 1 375 491 or WO 2005/035519) and optionally FeSO 4 .

US 4,490,404 describes the production of 10-pentadecen-15-olide. Starting from undecylenic acid methyl ester and hexenol, the corresponding undecylenic acid hexenol ester is produced, which, after intramolecular metathesis, yields 10- pentadecen-15-olide. 10-Pentadecen-15-olide (with E or Z configuration) is distinguished by a sweet, coumarin-like, animal musk odour, which is in part combined with tonka features.

Mixtures of 10-, 11 - and 12-pentadecen-15-olide are musk fragrance compositions which are of great interest from the point of view of odour. In such a mixture, each of the double bond isomers 10-, 11 - or 12-pentadecen-15-olide may here assume the form of the E and/or Z isomer. The mixtures of 10-, 11 - and 12-pentadecen-15-olide with any desired configuration at the particular double bond (E or Z) are hereinafter denoted (E,Z)-10,11 ,12-pentadecen-15-olide.

A simple and efficient process is accordingly sought for the production of a mixture of (10/1 1/12)-pentadecen-15-olides (respectively having E and/or Z configuration), which comprises all the characteristic features of the musk odour of the individual isomers and is furthermore suitable for large scale industrial production.

It has surprisingly been found that an isomer mixture of (10/11/12)-pentadecen- 15-olides may simply be obtained by isomerising 1 1- and/or 12-pentadecen-15- olide. The corresponding reaction is shown diagrammatically below for the 11- /12-pentadecen-15-olide isomer mixture as starting material (educt): in the starting material, each of the introduced 11- and/or 12-pentadecen-15-olides may assume the form of the E and/or Z isomer.

The present invention accordingly relates to a process for the production of an (E,Z)-10,11 ,12-pentadecen-15-olide isomer mixture, comprising the following step:

partial isomerisation of (E 1 Z)-H- and/or (E 1 Z)-12-pentadecen-15-olide, such that the (E 1 Z)-(10/1 1/12)-pentadecen-15-olide isomer mixture is obtained.

An (E 1 Z)-(1 1/12)-pentadecen-15-olide isomer mixture, as is obtainable for example according to EP 1 375 491 or WO 2005/035519, is preferably introduced into the isomerisation.

While isomerisation reactions of aliphatic olefins, such as for example allyl rearrangements, are comprehensively described in the literature, there are no references in the literature to shifting double bonds in macrocyclic ring systems by just one carbon atom.

The Journal of the Chemical Society, 1963, 4091-4096 describes a double bond isomerisation with triethylborane at 200°C for macrocyclic alkadienes with a ring size of 12 to 22 ring atoms. However, under these conditions, a double bond isomer mixture is obtained which has a random distribution of the theoretically possible double bond isomers. In the Journal of the Chemical Society, 1965, 3118-3126, the same authors also report a random product distribution on the isomerisation of macrocyclic alkadienes with potassium tert.-butylate.

The Journal of the American Chemical Society, 1976, 98, 7102-7104 has described for α-alkyl-substituted cycloalkenones with 6 to 8 ring atoms a migration of the double bond over the ring to form the more stable α,β- unsaturated isomers by 3 hours' heating with rhodium(lll) chloride trihydrate.

It is utterly surprising and unexpected that, starting from (E 1 Z)-1 1 ,12-pentadecen- 15-olides, a selective shift of the double bond by just one or two carbon atoms is obtained. In the process according to the invention, the resultant (E 1 Z)- (10/1 1/12)-pentadecen-15-olide isomer mixture regularly comprises a proportion of at least 5 wt.% of (E 1 Z)-I O-pentadecen-15-olide, relative to the total quantity of (E 1 Z)-I O-, (E 1 Z)-H- and (E 1 Z)-12-pentadecen-15-olide. If the educt to be introduced into the isomerisation already comprises (E 1 Z)-I O-pentadecen-15- olide, with this however preferably not being the case, the corresponding quantity of (E 1 Z)-I O-pentadecen-15-olide is not included in the calculation. Isomer mixtures in which the proportion of (E 1 Z)-I O-pentadecen-15-olide is in the range from 5-20 wt.%, relative to the total quantity of (E 1 Z)-I O-, (E 1 Z)-H- and (E 1 Z)-12- pentadecen-15-olide, are particularly valuable from the point of view of odour.

The process according to the invention is preferably performed in such a manner that at least a yield of 3% of (E 1 Z)-10-pentadecen-15-olide is obtained, the product mixture still additionally comprising at least 40 wt.% of (E 1 Z)-I O-, (E 1 Z)- 1 1- and (E 1 Z)-12-pentadecen-15-olides, relative to the introduced quantity of (E 1 Z)-H- and (E 1 Z)-12-pentadecen-15-olide. The following thus preferably applies:

A. [n(productiθ) - n(educt10) + n(productH ) + n(product12)] : [n(educt1 1 ) + n(educt12)] > 0.4

and simultaneously

B. [n(productiθ) - n(educt10)] : [n(educt1 1 ) + n(educt12)] > 0.03.

In the above inequalities:

n(educt10) means the quantity of (E 1 Z)-10-pentadecen-15-olide in the educt mixture n(educt1 1 ) means the quantity of (E 1 Z)-11-pentadecen-15-olide in the educt mixture n(educt12) means the quantity of (E,Z)-12-pentadecen-15-olide in the educt mixture

n(producti θ) means the quantity of (E 1 Z)-I O-pentadecen-15-olide in the product mixture n(product1 1 ) means the quantity of (E 1 Z)-11-pentadecen-15-olide in the product mixture n(product12) means the quantity of (E 1 Z)-12-pentadecen-15-olide in the product mixture

The process according to the invention is preferably performed in such a manner that the (E 1 Z)-H- and/or (E 1 Z)-12-pentadecen-15-olide is brought into contact with

(i) a catalyst containing an element of subgroup VIII in such a manner

that it partially isomerises to form the (E 1 Z)-(10/11/12)-pentadecen-15-olide isomer mixture. When the stated catalyst is used, the yields and product mixtures characterised by the above inequalities A and B may particularly straightforwardly be obtained; the person skilled in the art can determine by means of a few preliminary tests how the process conditions (in particular reaction temperature and reaction time) should be adjusted in order to satisfy the above inequalities.

When a catalyst containing an element of subgroup VIII is used, the resultant (E 1 Z)-10,11 ,12-pentadecen-15-olide isomer mixture conventionally contains 5-15 wt. % of (E 1 Z)-I O-pentadecen-15-olide (wherein any (E 1 Z)-I O-pentadecen-15- olide already present in the educt mixture is not included in the calculation), 4-40 wt. % of (E 1 Z)-11-pentadecen-15-olide and 30-50 wt.% of (E 1 Z)-12-pentadecen- 15-olide isomers, in each case relative to the total quantity of the stated isomers. A reaction according to the invention using a catalyst containing an element of subgroup VIII results in only small quantities of other double bond isomers, lsomerisation with a random distribution of the double bond isomers is not observed.

If catalysts comprising an element of subgroup VIII are used as catalysts for the isomerisation, said elements in particular comprise ruthenium, rhodium,

palladium, osmium, iridium and platinum. It is particularly preferred to use ruthenium, rhodium, palladium and iridium as the element of subgroup VIII in a or as the catalyst for the isomerisation reaction.

The stated elements of subgroup VIII may be used as catalyst in the elemental, metallic form, in which case they are generally applied onto a support. Support materials such as activated carbon, aluminium oxide or silicon oxide are preferred for this purpose. The concentration of the elemental catalyst present in metallic form on the support material is here preferably between 5 and 10 wt.%, relative to the weight of the support material.

In order to enhance activity and/or selectivity, the elements of subgroup VIII are preferably used in a form complexed with ligands. In the transition metal compounds, the (optionally complexed) elements of subgroup VIII are generally present formally in zero-valent form or bearing a single, double or triple positive charge. Counterions which may be used are, for example, chloride, bromide, iodide, sulfate, nitrate, sulfonate, or borate. Suitable ligands are, for example, acetonitrile, benzonitrile, diethyl ether, carbon monoxide, tetrahydrofuran, hydrogen, amines, ketones, phosphanes, ethyl acetate, dimethyl sulfoxide, dimethylformamide or hexamethylphosphoric acid triamide.

In summary, preferred processes according to the invention using a catalyst containing an element of subgroup VIII are those in which the element of subgroup VIII is present

(a) in elemental form,

(b) in complexed or uncomplexed form as a salt formally having an oxidation number of one to three,

or

(c) as a complex compound in which it is formally zero-valent.

The following catalysts may be mentioned by way of example:

Rhodium catalysts:

rhodium(lll) bromide hydrate, rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(lll) iodide hydrate, rhodium(lll) nitrate, rhodium(lll) phosphate, rhodium(lll) sulfate, rhodium(ll) acetate dimer, rhodium(lll) acetonylacetonate, rhodium(l)-bis-(1 ,5-cyclooctadiene) tetrafluoroborate hydrate, rhodium(l)-bis-(1 ,5- cyclooctadiene) acetylacetonate, rhodium(l)-bis-(1 ,5-cyclooctadiene) chloride dimer, rhodium(l)-bis-(1 ,5-cyclooctadiene) trifluoromethanesulfonate dimer, rhodium(l)-[1 ,4-bis-(diphenylphosphino)-butane]-(1 c,5c)-cyclooctadiene) tetrafluoroborate, rhodium(l)-[1 ,4-bis-(diphenylphosphino)-butane]-((2,5- norbornanediene) tetrafluoroborate, rhodium(l)-(2,5-norbornanediene) perchlorate, rhodium(l)-bis-(triphenylphosphine)-carbonyl chloride, rhodium(ll) trifluoroacetate dimer, rhodium(l)-tris-(triphenylphosphine) bromide, rhodium(l)- tris-(triphenylphosphine) chloride, rhodium(l) dicarbonyl acetylacetonate, rhodium(l) dicarbonyl chloride dimer,

Ruthenium catalysts:

ruthenium(lll) bromide hydrate, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(lll) iodide, ruthenium carbonyl, ruthenium(l) acetate polymer, ruthenium(lll) acetonylacetonate, ruthenium(ll)-(1 ,5-cyclooctadiene) chloride polymer, ruthenium(ll)-tris-(triphenylphosphine) chloride, ruthenium(ll) tricarbonyl chloride dimer, ruthenium(ll) carbonyldihydrido-tris-(triphenylphosphine), ruthenium(lll) 2,4-pentanedionate,

Palladium catalysts:

palladium(ll) acetate, palladium(ll) acetonylacetonate, palladium(ll)-bis- (acetonitrile) chloride, palladium(ll)-bis-(benzonitrile) chloride, palladium(ll)-[1 ,2- bis-(diphenylphosphino)-ethane] chloride, palladium(ll)-bis-

(tricyclohexylphosphine) chloride, palladium(ll)-bis-(triphenylphosphine) chloride, palladium(ll)-bis-(triphenylphosphine) bromide, palladium(ll) bromide, palladium(ll) chloride, palladium(ll) diammine chloride, palladium(ll) iodide, palladium(ll) nitrate, palladium(ll) 2,5-norbornadiene chloride, palladium(ll)

sulfate, palladium(ll) tetrammine chloride, palladium(ll)-[1 ,1 '- ferrocenylbis(diphenylphosphane)] dichloride dichloromethane, palladium on activated carbon, palladium on aluminium oxide,

Iridium catalysts:

iridium acetate, iridium(lll) acetylacetonate, iridium(l)-bis-(triphenylphosphine) carbonyl chloride, iridium(lll) bromide hydrate, iridium carbonyl, iridium(lll) chloride, iridium(lll) chloride hydrate, iridium(l) (1 ,5-cyclooctadiene) acetylacetonate.

Particularly preferred catalysts are rhodium(lll) chloride, rhodium(lll) chloride hydrate, rhodium(l)-bis-(triphenylphosphine)carbonyl chloride, ruthenium(lll) chloride, ruthenium(lll) chloride hydrate, ruthenium(ll)-tris-(triphenylphosphine) chloride, iridium(l)-bis-(triphenylphosphine)carbonyl chloride, palladium(ll)-bis- (benzonitrile) chloride, and palladium, preferably in the form of palladium on activated carbon.

The isomerisation catalysed by such a metal catalyst is preferably performed in the temperature range from 40 to 250°C, longer reaction times being required at lower temperatures and, in particular at higher temperatures, decomposition reactions possibly occurring to a certain extent. A particularly preferred temperature range is between 150 and 230°C.

Isomerisation is performed preferably using quantities or concentrations of catalyst of at least 0.03 wt.%, preferred concentrations are in the range from

0.05-5 wt.%, preferably 0.05-1 wt.%, in each case relative to the total mass of

(E 1 Z)-1 1- and/or (E 1 Z)-12-pentadecen-15-olide introduced into the isomerisation.

The support material is here not regarded as a constituent of the catalyst. It goes without saying that the catalyst in turn preferably contains an element of subgroup VIII; the above explanations regarding preferred catalysts also apply in connection with the preferred concentrations.

The isomerisation according to the invention, which is preferably catalysed by one of the above-stated catalysts, may be performed not only using an inert

solvent such as for example toluene, xylene, cyclohexane but also without solvent, the latter variant being particularly preferred.

Examples

The educt used in the isomerisation examples contained

48.6%- (E 1 Z)-1 1-pentadecen-15-olide (mixture of E and Z isomer) 44.7%- (E 1 Z)-12-pentadecen-15-olide (mixture of E and Z isomer)

and contained no (E 1 Z)-I O-pentadecen-15-olide.

Transisomerisation with catalysts based on metals of subgroup VIII

Example 1

Reaction conditions: catalyst: ruthenium(ll)-tris-(triphenylphosphine) chloride (0.3 wt.%), no solvent; temperature: 170°C, reaction time: 16 hours

100 g of (E 1 Z)-1 1 ,12-pentadecen-15-olide are heated for 16 hours at 170°C with 0.3 g of ruthenium(ll)-tris-(triphenylphosphine) chloride, then fractionally distilled and the majority distillate is subjected to steam distillation. 67 g of product (yield: 67% of theoretical) of the following composition are obtained (values in wt.% relative to the total mass of the product):

Example 2

Reaction conditions: catalyst: palladium on activated carbon (type 87L Paste, source: Johnson Matthey Catalysts) (Pd content: 5 %, water content: 58.9 %, corresponding to a Pd concentration of 2.055 wt.%); no solvent; temperature: 220°C, reaction time: 8 hours

100 g of (E 1 Z)-1 1 ,12-pentadecen-15-olide are heated for 8 hours at 220°C with 3 g of type 87L Paste palladium on activated carbon, then fractionally distilled and the majority distillate is subjected to steam distillation. 70 g of product (yield: 70% of theoretical) of the following composition are obtained (values in wt.% relative to the total mass of the product):