EP4558593A1

EP4558593A1 - New forms of ambrocenide®

Info

Publication number: EP4558593A1
Application number: EP23738687.5A
Authority: EP
Inventors: Daniela Knoop; Michael Michler; Marcus Eh; Clito HOEDICKE; Stefan Lambrecht
Original assignee: Symrise AG
Current assignee: Symrise AG
Priority date: 2023-07-04
Filing date: 2023-07-04
Publication date: 2025-05-28
Anticipated expiration: 2043-07-04
Also published as: EP4685139A2; CN121443709A; EP4558593B1; EP4685139A3; EP4558593C0; WO2025008051A1

Abstract

The present invention primarily relates to a method for producing a particulate product comprising or consisting of the steps as described herein. The invention further relates to a particulate product, preferably obtained or obtainable by a method as described herein, comprising 70 to 98 wt.-% compound of formula (la) as defined herein and 0.01 to 5 wt.-% compound of formula (lb) as defined herein, and to the use of a particulate product as described herein as a fragrance.

Description

Munich, 4 July 2023

Our Ref.: SM 6638-01 WO SOE/PAP

Applicant: Symrise AG

Serial Number: New application

Symrise AG

MuhlenfeldstraBe 1 , 37603 Holzminden, Germany

New forms of Ambrocenide®

Further aspects and preferred embodiments of the present invention result from the following explanations, the attached examples and, in particular, the attached patent claims. Ambrocenide®, a powerful fragrance substance with an ambery and woody scent, has the following chemical structure (formula A):

Formula A: Chemical structure of Ambrocenide®

The wavy lines in formula A may denote, independently of one another, an alpha- or beta configuration of the bond. Ambrocenide® may generally comprise one, two, three or all of the following diastereomers (formula B):

Formula B: Diastereomers of Ambrocenide® One possibility for manufacturing Ambrocenide® is disclosed in EP 0 857 723 B1 . First, (-)-alpha-cedrene (1) is converted to (-)-alpha cedrene epoxide (2) by treatment with peracetic acid. The epoxide obtained (2) is then converted into a mixture of the epimeric cedrane diols (3) by acid catalysed ring opening. Ambrocenide® ((4) with R = R' = CH3) can then be obtained from the diols (3) by conversion with dimethoxypropane under acid catalysis (formula C):

Formula C: Preparation of Ambrocenide® (4, R=R’=CH3)

Depending on the reaction conditions selected during the synthesis, the crude Ambrocenide® obtained from synthesis may comprise one, two, three or all of the diastereomers shown in formula B above.

WO 2017/186973 A2 describes a method for manufacturing a mixture comprising the compound of formula (la)

(la), wherein the mixture is free or essentially free of the other three diastereomers of Ambrocenide® as shown in formula B above. Said method is based on providing a starting mixture, containing or consisting essentially of alpha, alpha-cedranediol of formula (Illa) wherein the starting mixture is free or essentially free of beta.beta-cedranediol of formula (lllb), beta.alpha-cedranediol of formula (lllc) and alpha, beta-cedranediol of formula (Hid),

In the context of the studies underlying WO 2017/186973 A2, it was found by the applicant that the compound of formula (la) is much more olfactively active than the other three diastereomers of Ambrocenide® as shown in formula B above. The Ambrocenide® obtained according to this method therefore has particularly advantageous odour properties. In particular, it is possible to achieve the same or improved effects with a lower concentration in comparison to other diastereomeric mixtures of Ambrocenide® known in the state of the art in terms of enhancing or imparting a pleasant odour impression and/or masking or reducing an unpleasant odour impression. However, the crude Ambrocenide® obtained from synthesis, as for example described in WO 2017/186973 A2, is challenging to handle due to its amorphous state.

To date, Ambrocenide® has been marketed by the applicant in two different qualities. One of the qualities is so-called Ambrocenide® Cryst., a highly pure crystalline solid (> 99% GC area of the compound of formula (la) as defined herein), which is manufactured via an effortful solvent recrystallization of the amorphous crude Ambrocenide® obtained from synthesis. This purification method is associated with significant yield losses and hence substantial manufacturing costs. An alternative quality supplied by the applicant is so-called Ambrocenide® 10 DPG, which is a 10% solution of the amorphous crude Ambrocenide® obtained from synthesis in dipropylene glycol (DPG). The use of said solution in dipropylene glycol enables easy handling and is advantageous, since the dissolved crude Ambrocenide® obtained from synthesis can be used in the form of a liquid and therefore does not have to be melted before further use. Nevertheless, due to the high solvent content, it is not an optimal working material with respect to customer needs.

It was therefore an object of the present invention to provide a form of Ambrocenide® that overcomes the previously outlined drawbacks. Further objects underlying the present invention follow from the description below and the present patent claims.

According to a first aspect of the present invention, the stated object is surprisingly achieved by a method for producing a particulate product comprising or consisting of the following steps:

(i) Providing a mixture, preferably an unpurified synthesis product, comprising or consisting of 70 to 98 wt.-%, preferably 80 to 96 wt.-%, more preferably 80 to 95 wt.- %, of compound of formula (la) and 0.01 to 5 wt.-%, preferably 0.01 to 1 wt.-%, of compound of formula (lb)

(lb), based on the total weight of the mixture, optionally wherein the mixture, preferably the unpurified synthesis product, is at a temperature at which it is in the form of a partially or fully, preferably fully, molten mass (at a pressure of about 1 bar); (ii) if applicable, heating the mixture provided in step (la) to obtain a partially or fully, preferably fully, molten mass of said mixture;

(iii) contacting, preferably mixing, the partially or fully molten mass provided in step (i) or obtained in step (ii), with a, preferably odourless, solvent (in a liquid or gaseous state) having a boiling point that is lower than the boiling point of said mass, preferably with water, inside a vessel, preferably at a pressure of about 1 bar, and then adjusting the pressure and temperature inside the vessel such that the solvent, preferably water, is (essentially fully) evaporated or removed again from the mass, (and also removing the solvent from the vessel) to obtain a vapor-treated, partially or fully molten mass;

(iv) contacting the vapor-treated, partially or fully, preferably fully, molten mass obtained in step (iii) with a cold surface;

(v) cooling of the vapor-treated, partially or fully, preferably fully, molten mass (which is in contact with the cold surface), preferably through the contact with the cold surface, to obtain a solid product that is in contact with the cold surface;

(vi) removal , preferably by scraping, of the solid product from the cold surface, preferably with a blade, more preferably with a (discharge) knife, to obtain a particulate product.

Within the studies underlying the present invention, it was found that on a cold surface (at a temperature as defined below) the vapor-treated, partially or fully molten mass obtained in step (iii) of the method according to the invention (at a temperature as defined below) can be brought to solidification within only a few seconds.

Further, it was surprisingly found that the particulate product obtained in step (vi) of the method according to the invention advantageously exhibits an almost identical X-ray powder diffraction pattern to the one of the highly pure compound Ambrocenide® Cryst. (> 99% GC area of the compound of formula (la) as defined herein; cf. Figure 1 and Example 2 below). This finding was particularly surprising, because the mixture, preferably unpurified synthesis product, provided in step (i), and accordingly the vapor-treated, partially or fully molten mass obtained in step (iii) of the method according to the invention, comprises only 70 to 98 wt.-% of the compound of formula (la) and a further five to seven minor components, which are the compound of formula (lb) and educts and side-products from synthesis (cf. further below for details). The high crystallinity of the particulate product obtained in step (vi) of the method according to the invention was thus very surprising, especially considering the amorphous nature of the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention at room temperature and the absence of any purification steps, which would be capable of removing any remaining educts and side-products from synthesis, in the method according to the invention. Moreover, when samples of Ambrocenide® Cryst. (> 99% GC area of the compound of formula (la) as defined herein) and of the particulate product obtained in step (vi) of the method according to the invention were compared against one another by a trained panel, a large proportion of the trained panelists were not able to distinguish the two samples based on their olfactive properties (cf. Example 3 below for further details).

The method according to the invention thus advantageously gives access to a particulate product as defined herein, i.e. to a particulate form of Ambrocenide®, which is easy to produce and convenient to handle due to its solid, particulate, and crystalline form, and which has almost identical crystallinity and olfactive properties as the highly purified product Ambrocenide® Cryst. with > 99% GC area of compound of formula (la) as defined herein (cf. Figure 1 and Examples 2 and 3 below).

Overall, the method according to the invention was found to have the following advantages:

The use of organic solvents is not required in the method according to the invention, no yield losses occur, i.e. very high yields of the particulate product are obtained, the production costs of the particulate product are low, the raw material consumption is low, it does not encompass any purification steps, which would be capable of removing any educts and side-products from synthesis, and the obtained particulate product is easy to handle for consumers due to its solid, particulate, and crystalline form.

Within the framework of the present text, an unpurified synthesis product relates to a product obtained from chemical synthesis (e.g. as described below in Example 1), which may have been washed after synthesis, but which has not been subjected to any purification procedures such as fractional distillation or recrystallization.

According to a preferred embodiment of the method according to the invention, the mixture provided in step (i) comprises or consists of 70 to 98 wt.-% of compound of formula (la) and 0.01 to 5 wt.-% of compound of formula (lb), based on the total weight of the mixture.

According to another preferred embodiment of the method according to the invention, the mixture provided in step (i) comprises or consists of 80 to 96 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the mixture. According to another preferred embodiment of the method according to the invention, the mixture provided in step (i) comprises or consists of 80 to 95 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the mixture.

According to another preferred embodiment of the method according to the invention, the mixture provided in step (i) is at an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C. Providing the mixture at this temperature is particularly advantageous, because it then is in the form of a partially or fully molten mass.

According to a particularly preferred embodiment, the mixture, preferably the unpurified synthesis product, is provided at a temperature that is sufficiently high for the mixture to be in the form of a fully molten mass, i.e. a mass that is essentially free from any solid form of the mixture, preferably unpurified synthesis product, in step (i).

According to an alternative embodiment of the method according to the invention, the mixture, preferably unpurified synthesis product, is provided at a temperature for the mixture, preferably unpurified synthesis product, to be in the form of a partially molten mass, i.e. a mass that contains a solid form of the mixture, preferably unpurified synthesis product, in step (i). The partially molten mass provided may, for example, contain from more than 0 to 65 wt.%, preferably more than 0 to 10 wt.%, most preferably more than 0 to 2 wt.% of solid mixture, preferably unpurified synthesis product.

According to another preferred embodiment of the method according to the invention, the partially or fully molten mass contacted with a solvent having a boiling point that is lower than the boiling point of said mass, preferably with water, in step (iii) of the method according to the invention is at an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C, when first contacting the solvent.

The mixture, preferably the (amorphous) unpurified synthesis product, provided in step (i) of the method according to the invention is subjected to a vapor, preferably steam, treatment in step (iii) of the method according to the invention. Said vapor, preferably steam, treatment advantageously removes unpleasant and/or undesired olfactory notes from the mixture, preferably unpurified synthesis product, caused e.g. by remaining (low boiling) solvent residues from the synthesis of the mixture, preferably unpurified synthesis product. Preferably, the vessel holding the partially or fully molten mass in step (iii) of the method according to the invention is held at a temperature that is high enough for the partially or fully molten mass not to solidify during the contacting with the solvent.

Preferably, the solvent used in step (iii) of the method according to the invention is water, more preferably is tap water.

Preferably, the solvent, more preferably the water, is at room temperature when first contacting the partially or fully molten mass in step (iii) of the method according to the invention.

In a preferred embodiment of step (iii) of the method according to the invention, after the contacting of the partially or fully molten mass with the solvent, preferably water, the pressure and temperature inside the vessel are adjusted to 7 - 1013 mbar and 30 - 100 °C, preferably to 60 - 500 mbar and 60 - 90°C, more preferably to 125 - 250 mbar and 70 - 80 °C. By adjusting the pressure and temperature inside the vessel to said preferred pressure and temperature, the solvent, preferably the water, is evaporated again from the mass (if added in liquid state) or is removed again from the mass (if added in gaseous state).

The amount of solvent, preferably water, used per vapour, preferably steam, treatment of the partially or fully molten mass preferably is 5 to 400 wt.-%, more preferably 5 to 300 wt.- %, more preferably 5 to 200 wt.-%, more preferably 5 to 100 wt.-%, more preferably 10 to 50 wt.-%, most preferably 20 to 25 wt.-%, of the weight of the molten mass treated in step (iii) of the method according to the invention. The vapour, preferably steam, treatment of step (iii) of the method according to the invention may be repeated once to ten times, preferably twice to five times, most preferably three to four times. It advantageously removes low boiling organic solvents from the partially or fully molten mass provided in step (i), if applicable, or obtained in step (ii), which may still be present in the mixture as provided in step (i) from synthesis. However, it is not capable of removing any educts and side-products from synthesis due to their higher boiling points.

Preferably, in step (iv) of the method according to the invention, the contacting of the vapor, preferably steam, treated partially or fully molten mass obtained in step (iii) of the method with a cold surface takes place over a period of 2 to 60 seconds, preferably 4 to 40 seconds, particularly preferably 5 to 25 seconds. According to a preferred embodiment of the method according to the invention, the vapor, preferably steam, treated partially or fully molten mass obtained in step (iii) and contacted with a cold surface in step (iv) of the method according to the invention does not comprise any solvents, more preferably does not comprise any organic solvents, most preferably is essentially free of organic solvents, after the vapor treatment of step (iii).

Preferably, the vapor, preferably steam, treated partially or fully molten mass obtained in step (iii) of the method according to the invention is not a solution of the mixture, preferably unpurified synthesis product, as provided in step (i) of the method in one or more solvents.

Preferably, the total amount of solids, in wt.-%, based on the total weight of the partially molten mass, contained in a partially molten mass provided in step (i) and/or obtained in step (ii), if applicable, and/or obtained in step (iii) and/or contacted with a cold surface in step (iv) of the method according to the invention is from more than 0 to 65 wt.-%, preferably more than 0 to 10 wt.-%, most preferably more than 0 to 2 wt.-%.

Preferably, the method according to the invention does not comprise any fractional distillation and/or recrystallization steps.

Thus, preferably, the solid product that is in contact with the cold surface, which is obtained in step (v) of the method according to the invention, comprises or consists of essentially the same amount of compound of formula (la) and compound of formula (lb), in percentage terms, as defined above for the mixture provided in step (i) of the method.

According to a preferred embodiment of the method according to the invention, the solid product obtained in step (v) comprises or consists of 70 to 98 wt.-% of compound of formula (la) and 0.01 to 5 wt.-% of compound of formula (lb), based on the total weight of the solid product.

According to another preferred embodiment of the method according to the invention, the solid product obtained in step (v) comprises or consists of 80 to 96 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the solid product.

According to another preferred embodiment of the method according to the invention, the solid product obtained in step (v) comprises or consists of 80 to 95 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the solid product. Within the framework of the present text, the term “solid” has the usual meaning in the field of natural sciences. The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural rigidity and resistance to a force applied to the surface. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire available volume like a gas.

According to a preferred embodiment of the method according to the invention, the blade, preferably the (discharge) knife, used to remove of the solid product from the cold surface in step (vi) is used at an angle of 10 to 70°, preferably 20 to 65°, more preferably 30° to 60°, relative to the surface of the solid product. The removal of the solid product from the cold surface, preferably with a blade, more preferably with a (discharge) knife, leads to the formation of a particulate product (preferably as further defined below).

According to a preferred embodiment of the method according to the invention, the removal of the solid product from the cold surface to obtain a particulate product in step (vi) is performed by scraping the solid product off the cold surface, preferably with a blade, more preferably with a (discharge) knife.

Preferably, after removal of the solid product from the cold surface to obtain a particulate product in step (vi) of the method according to the invention, no further crushing steps and/or other size changes of the obtained particulate product is/are carried out.

Preferably, the particulate product obtained in step (vi) of the method according to the invention comprises or consists of essentially the same amount of compound of formula (la) and compound of formula (lb), in percentage terms, as defined above for the mixture provided in step (i) of the method and for the solid product obtained in step (v).

According to a preferred embodiment of the method according to the invention, the particulate product obtained in step (vi) comprises or consists of 70 to 98 wt.-% of compound of formula (la) and 0.01 to 5 wt.-% of compound of formula (lb), based on the total weight of the particulate product.

According to another preferred embodiment of the method according to the invention, the particulate product obtained in step (vi) comprises or consists of 80 to 96 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the particulate product. According to another preferred embodiment of the method according to the invention, the particulate product obtained in step (vi) comprises or consists of 80 to 95 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the particulate product. According to another preferred embodiment, the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises one or several compound(s) of formula (II) a and/or of formula (IV) and/or of formula (V)

a

According to another preferred embodiment, the solid product obtained in step (v) of the method according to the invention (that is in contact with the cold surface) further comprises one or several compound(s) of formula (II) a and/or of formula (IV) and/or of formula (VI)

According to another preferred embodiment, the particulate product obtained in step (vi) of the method according to the invention further comprises one or several compound(s) of formula (II)

a and/or of formula (IV) and/or of formula (VI)

According to another preferred embodiment, the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises comprises one or several compound(s) of formula (II), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (II) in the mixture is 500 : 1 to 3 : 1 , preferably 350 : 1 to 5 : 1 , particularly preferably 300 : 1 to 8 : 1 , and/or the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises one or several compound(s) of formula

(HI), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (III) in the mixture is at least 50 : 1 , preferably at least 100 : 1 , particularly preferably at least 150 : 1 , and/or the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises one or several compound(s) of formula (IV), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (IV) in the mixture is at least 40 : 1 , preferably at least 50 : 1 , particularly preferably at least 60 : 1 , and/or the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises one or several compound(s) of formula (V), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (V) in the mixture is at least 30 : 1 , preferably at least 40 : 1 , more preferably at least 50 : 1 , and/or the mixture, preferably unpurified synthesis product, provided in step (i) of the method according to the invention further comprises one or several compound(s) of formula (VI),

wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (VI) in the mixture is at least 4 : 1 , preferably at least 6 : 1 , particularly preferably at least 8 : 1. According to another preferred embodiment, the solid product obtained in step (v) of the method according to the invention further comprises comprises one or several compound(s) of formula (II), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (II) in the product is 500 : 1 to 3 : 1 , preferably 350 : 1 to 5 : 1 , particularly preferably 300 : 1 to 8 : 1 , and/orthe solid product obtained in step (v) of the method according to the invention further comprises one or several compound(s) of formula (III), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (III) in the product is at least 50 : 1 , preferably at least 100 : 1 , particularly preferably at least 150 : 1 , and/orthe solid product obtained in step (v) of the method according to the invention further comprises one or several compound(s) of formula (IV), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (IV) in the product is at least 40 : 1 , preferably at least 50 : 1 , particularly preferably at least 60 : 1 , and/orthe solid product obtained in step (v) of the method according to the invention further comprises one or several compound(s) of formula (V), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (V) in the product is at least 30 : 1 , preferably at least 40 : 1 , more preferably at least 50 : 1 , and/orthe solid product obtained in step (v) of the method according to the invention further comprises one or several compound(s) of formula (VI),

wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (VI) in the product is at least 4 : 1 , preferably at least 6 : 1 , particularly preferably at least 8 : 1. According to another preferred embodiment, the particulate product obtained in step (vi) of the method according to the invention further comprises comprises one or several compound(s) of formula (II), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (II) in the product is 500 : 1 to 3 : 1 , preferably 350 : 1 to 5 : 1 , particularly preferably 300 : 1 to 8 : 1 , and/orthe particulate product obtained in step (vi) of the method according to the invention further comprises one or several compound(s) of formula (III), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (III) in the product is at least 50 : 1 , preferably at least 100 : 1 , particularly preferably at least 150 : 1 , and/orthe particulate product obtained in step (vi) of the method according to the invention further comprises one or several compound(s) of formula (IV), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (IV) in the product is at least 40 : 1 , preferably at least 50 : 1 , particularly preferably at least 60 : 1 , and/orthe particulate product obtained in step (vi) of the method according to the invention further comprises one or several compound(s) of formula (V), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (V) in the product is at least 30 : 1 , preferably at least 40 : 1 , more preferably at least 50 : 1 , and/orthe particulate product obtained in step (vi) of the method according to the invention further comprises one or several compound(s) of formula (VI), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (VI) in the product is at least 4 : 1 , preferably at least 6 : 1 , particularly preferably at least 8 : 1.

Preferably, the particulate product obtained in step (vi) is crystalline.

According to a preferred embodiment of the method according to the invention, the mixture, preferably unpurified synthesis product, provided in step (i) is heated to an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C, in step (ii), if present.

According to a particularly preferred embodiment, the mixture, preferably the unpurified synthesis product, provided in step (i) is heated in step (ii), if present, to a sufficiently high temperature to obtain a fully molten mass, i.e. a mass that is essentially free from any solid form of the mixture, preferably unpurified synthesis product.

According to an alternative embodiment of the method according to the invention, the mixture, preferably unpurified synthesis product, provided in step (i) is only heated to a temperature that leads to partial melting of the mixture, preferably unpurified synthesis product, i.e. to a partially molten mass, in step (ii), if present. The partially molten mass obtained may, for example, contain from more than 0 to 65 wt.%, preferably more than 0 to 10 wt.%, most preferably more than 0 to 2 wt.% of solid mixture, preferably unpurified synthesis product.

According to a preferred embodiment of the method according to the invention, the vapor- treated, partially or fully molten mass obtained in step (iii) is at an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C, when first contacting the cold surface in step (iv). Preferably, the cold surface with which the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted in step (iv), has an average (essentially constant) temperature of from 0 to 25 °C, more preferably from 0 to 20 °C, more preferably from 5 to 15 °C, most preferably from 8 to 12 °C (especially when first contacting the partially or fully molten mass in step (iv) of the method according to the invention).

Particularly preferably, the cold surface with which the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted in step (iv) of the method, is constantly kept at an average temperature of from 0 to 25 °C, more preferably from 0 to 20 °C, more preferably from 5 to 15 °C, most preferably from 8 to 12 °C, by way of cooling means.

Preferably, in step (v) of the method according to the invention, the vapor-treated, partially or fully molten mass is cooled - preferably through the contact with the cold surface - to an average temperature of from 0 to 25 °C, more preferably from 0 to 20 °C, more preferably from 5 to 15 °C, most preferably from 8 to 12 °C.

Preferably, the solid product obtained in step (v) of the method according to the invention is crystalline.

According to a preferred embodiment of the method according to invention, the particulate product obtained in step (vi) is in the form of flakes.

Preferably, a particle of the particulate product, more preferably a flake, obtained in step (vi) of the method according to the invention has a length of from 1 to 50 mm, preferably from 2 to 40 mm, more preferably from 5 to 30 mm, and/or a width of from 0.5 to 30 mm, preferably from 2 to 20 mm, more preferably from 3 to 10 mm, and/or a thickness of from 0.1 to 5 mm, preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm.

More preferably, a particle of the particulate product, more preferably a flake, obtained in step (vi) of the method according to the invention has a length of from 1 to 50 mm, preferably from 2 to 40 mm, more preferably from 5 to 30 mm, and a width of from 0.5 to 30 mm, preferably from 2 to 20 mm, more preferably from 3 to 10 mm, and a thickness of from 0.1 to 5 mm, preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm.

Preferably, the particles of the particulate product, preferably the flakes, obtained in step (vi) of the method according to the invention have an average length of from 5 to 30 mm, and/or an average width of from 3 to 10 mm, and/or an average thickness of from 1 to 2 mm. Preferably, the particles of the particulate product, preferably the flakes, obtained in step (vi) of the method according to the invention have an average length of from 5 to 30 mm, and an average width of from 3 to 10 mm, and an average thickness of from 1 to 2 mm.

More preferably, the particles of the particulate product, preferably the flakes, obtained in step (vi) of the method according to the invention are elongated and/or needle-like.

Advantageously, the size and/or shape of the particles of the particulate product, preferably flakes, can be influenced by the kind of blade, preferably (discharge) knife, used in step (vi) of the method according to the invention and/or by the removal angle set for the blade, preferably (discharge) knife. A smaller angle of the blade, preferably (discharge) knife, used to remove, preferably scrape, the solid product from the cold surface, relative to the surface of the solid product, for instance, leads to a finer particulate product (e.g. finer flakes), whereas a larger angle of the blade, preferably (discharge) knife, relative to the surface of the solid product, leads to a more coarse particulate product (e.g. larger flakes).

According to a preferred embodiment, the contacting of the vapor-treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) of the method according to the invention comprises or consists of the following step:

Partially or fully submerging the cold surface in the molten mass followed by removal of the cold surface from the molten mass to form a layer of the molten mass on at least parts of the cold surface.

According to a particularly preferred embodiment, residual seed crystals of the particulate product from a previous application of the method according to the invention are still present on the cold surface. This is particularly advantageous, since it facilitates the formation of the solid product (preferably in crystalline form) on the cold surface.

According to an alternative preferred embodiment of the method according to the invention, the contacting of the vapor-treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) comprises or consists of the following step:

Depositing the molten mass on the cold surface to form a layer of the molten mass on at least parts of the cold surface. Preferably, the cold surface is the outer surface of a cooling roll that rotates while parts of its outer surface (e.g. its top or bottom outer surface) are in contact with the molten mass. According to an alternative embodiment, the cold surface is the outer surface of a cooling roll that rotates while the molten mass is poured onto it. In both cases, a thin layer of the molten mass is deposited on and adheres to the outer surface of the rotating cooling roll in a continuous process. Since the average temperature of the outer surface of the cooling roll is lower than the average temperature of the molten mass, preferably is below the crystallization temperature of the molten mass, a layer of the solid product is formed on the outer surface of the cooling roll. After the roll has turned through almost a full revolution, the solid product is removed from its surface, for example by a blade, preferably a (discharge) knife, scraper. Thereby, the solid product is comminuted to the particulate product, which may be in the form of flakes (cf. Figures 2 and 3).

Preferably, the rotation speed of the cooling roll, if used in the method according to the invention, is 0.5 to 12 rpm, more preferably 1 to 8 rpm, most preferably 2 to 4 rpm. If the rotation speed of the cooling roll is too slow, the space-time-yield of the particulate product obtained in step (vi) can be unsatisfactory. If the rotation speed of the cooling roll is too fast, the molten mass may not have enough time to cool down and solidify and an undesired waxy mass may be obtained in step (v) of the method instead of a solid product.

According to a preferred embodiment of the method according to the invention, the molten mass is in contact with the cold surface for a time of from 2 to 60 seconds, preferably from 4 to 40 seconds, more preferably from 5 to 25 seconds. Accordingly, the cooling time in step (v) of the method according to the invention preferably is from 2 to 60 seconds, more preferably from 4 to 40 seconds, most preferably from 5 to 25 seconds.

According to a preferred embodiment, a drum flaker can be used in the method according to the invention.

Preferably, the layer of the molten mass, formed on the cold surface by contacting the vapor-treated, partially or fully molten mass with the cold surface in step (iv) of the method according to the invention, has an average thickness of from 0.1 to 5 mm, more preferably 0.5 to 3 mm, most preferably 1 to 2 mm.

Preferably, the layer of the molten mass, formed on the cold surface by contacting the vapor-treated, partially or fully molten mass with the cold surface in step (iv) of the method according to the invention, has a dimension which essentially corresponds to the area of the cold surface, preferably corresponds to 90, 80, 70, 60, or 50% of the area of the cold surface (i.e. preferably, the cold surface is essentially fully covered with the vapor-treated, partially or fully molten mass).

According to another preferred embodiment, the cold surface with which the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted in step (iv) of the method, is the upper surface of a cooling belt that rotates while the molten mass is poured onto it. Since the average temperature of the cooling belt preferably is adjusted to be lower than the average temperature of the molten mass, preferably is adjusted to be below the crystallization temperature of the molten mass, a layer of the solid product is formed on the upper surface of the cooling belt in step (v) of the method according to the invention.

According to another preferred embodiment, the cold surface with which the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted in step (iv) of the method, is the upper surface of a lower cooling belt that rotates while the molten mass is poured onto it. Then, the molten mass on the lower cooling belt is also contacted with lower surface of an upper cooling belt from the top. Since the average temperature of one or both of the lower and upper cooling belt(s), which are then both in contact with the molten mass, is adjusted to be lower than the average temperature of the molten mass, preferably is adjusted to be below the crystallization temperature of the molten mass, a layer of the solid product is formed on the surface of one or both of the lower and upper cooling belt(s) in step (v) of the method according to the invention.

According to an alternative preferred embodiment of the method according to the invention, the particulate product obtained in step (vi) is in the form of pastilles.

Preferably, the particulate product, preferably the pastilles, obtained in step (vi) of the method according to the invention have an average diameter of from 2 to 12 mm, more preferably 3 to 10 mm, most preferably 4 to 8 mm (top view), and/or average height of from 1 to 10 mm, more preferably 2 to 8 mm, most preferably 3 to 6 mm (side view).

Thus, preferably the contacting of the vapor-treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) comprises or consists of the following step:

Depositing the molten mass on the cold surface to form one or more separate droplets of the molten mass on the cold surface. Preferably, the formed droplets of the molten mass on the cold surface have an average diameter of from 2 to 12 mm, more preferably 3 to 10 mm, most preferably 4 to 8 mm (top view) and/or have an average height of from 1 to 10 mm, more preferably 2 to 8 mm, most preferably 3 to 6 mm (side view).

The deposition of separate droplets of the vapor-treated, partially or fully molten mass on the cold surface in step (vi) of the method according to the invention makes the solid product, and respectively, the particulate product obtainable in the form of pastilles.

Preferably, the pastilles obtained in step (v) of the method according to the invention are removed from the cold surface with a blade, preferably a (discharge) knife, in step (vi) of the method according to the invention. Most preferably, the size and/or shape of the pastilles is essentially not changed during the removal from the cold surface.

Particularly preferably, the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) of the method according to the invention is the outer surface of a (rotatable) cooling roll (cf. Figure 2).

Preferably, the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) of the method according to the invention is the outer surface of a cooling roll having a maximum diameter of about 2000 mm, more preferably of about 1500 mm, more preferably of about 1000 mm, most preferably of about 500 mm.

According to an alternative preferable embodiment of the method according to the invention, the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) of the method is the upper or lower surface of a (rotatable) cooling belt.

Preferably, the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) of the method according to the invention has a roughness of 0.1 to 2 pm, preferably of 0.4 to 0.8 pm.

Another aspect of the present invention relates to a particulate product, preferably obtained or obtainable by a method according to the invention as described herein, comprising 70 to 98 wt.-% preferably 80 to 96 wt.-%, more preferably 80 to 95 wt.-%, compound of formula (la)

and 0.01 to 5 wt.-%, preferably 0.01 to 1 wt.-%, compound of formula (lb) based on the total weight of the product. According to a preferred embodiment of the particulate product according to the invention, the product comprises or consists of 70 to 98 wt.-% of compound of formula (la) and 0.01 to 5 wt.-% of compound of formula (lb), based on the total weight of the product.

According to another preferred embodiment of the particulate product according to the invention, the product comprises or consists of 80 to 96 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the product.

According to another preferred embodiment of the particulate product according to the invention, the product comprises or consists of 80 to 95 wt.-% of compound of formula (la) and 0.01 to 1 wt.-% of compound of formula (lb), based on the total weight of the product. According to another preferred embodiment of the particulate product according to the invention, the product further comprises one or several compound(s) of formula (II) and/or of formula (IV) and/or of formula (VI)

Preferably, the particulate product further comprises one or several compound(s) of formula (II), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (II) in the product is 500 : 1 to 3 : 1 , preferably 350 : 1 to 5 : 1 , particularly preferably 300 : 1 to 8 : 1 , and/or the particulate product further comprises one or several compound(s) of formula (III), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (III) in the product is at least 50 : 1 , preferably at least 100 : 1 , particularly preferably at least 150 : 1 , and/or the particulate product further comprises one or several compound(s) of formula

(IV), wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (IV) in the product is at least 40 : 1 , preferably at least 50 : 1 , particularly preferably at least 60 : 1 , and/or the particulate product further comprises one or several compound(s) of formula

(V), wherein the weight ratio ofthe total amount of compound of formula (la) to the total amount of compound(s) of formula (V) in the product is at least 30 : 1 , preferably at least 40 : 1 , more preferably at least 50 : 1 , and/or the particulate product further comprises one or several compound(s) of formula

(VI),

( D wherein the weight ratio of the total amount of compound of formula (la) to the total amount of compound(s) of formula (VI) in the product is at least 4 : 1 , preferably at least 6 : 1 , particularly preferably at least 8 : 1.

Preferably, the particulate product according to the invention is in the form of flakes.

Preferably, a particle of the particulate product, more preferably a flake, according to the invention has a length of from 1 to 50 mm, preferably from 2 to 40 mm, more preferably from 5 to 30 cm, and/or a width of from 0.5 to 30 mm, preferably from 2 to 20 mm, more preferably from 3 to 10 mm, and/or a thickness of from 0.1 to 5 mm, preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm.

Preferably, a particle of the particulate product, more preferably a flake, according to the invention has a length of from 1 to 50 mm, preferably from 2 to 40 mm, more preferably from 5 to 30 cm, and a width of from 0.5 to 30 mm, preferably from 2 to 20 mm, more preferably from 3 to 10 mm, and a thickness of from 0.1 to 5 mm, preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm.

Preferably, the particles of the particulate product, preferably the flakes, according to the invention have an average length of from 5 to 30 mm, and/or an average width of from 3 to 10 mm, and/or an average thickness of from 1 to 2 mm.

Preferably, the particles of the particulate product, preferably the flakes, according to the invention have an average length of from 5 to 30 mm, and an average width of from 3 to 10 mm, and an average thickness of from 1 to 2 mm.

More preferably, the particles of the particulate product, preferably the flakes, according to the invention are elongated and/or needle-like. According to an alternative preferred embodiment of the invention, the particulate product according to the invention is in the form of pastilles.

Preferably, the particulate product, preferably the pastilles, according to the invention have an average diameter of from 2 to 12 mm, more preferably 3 to 10 mm, most preferably 4 to 8 mm (top view), and/or average height of from 1 to 10 mm, more preferably 2 to 8 mm, most preferably 3 to 6 mm (side view).

The particulate product according to the invention is particularly advantageous as it is easy and convenient to handle for consumers, such as perfumers, due to its solid, particulate and crystalline form. Due to the method according to the invention (as described above), it is more easily accessible than Ambrocenide® Cryst., a highly pure crystalline solid with > 99% GC area of the compound of formula (la) as defined herein, which is manufactured via an effortful solvent recrystallization of the amorphous crude Ambrocenide® obtained from synthesis, while displaying essentially identical olfactive properties to Ambrocenide® Cryst. (cf. Examples 3 to 9 below). The solid, particulate and crystalline form of the particulate product according to the invention also makes its dissolution in solvents, such as in dipropylene glycol (DPG), redundant as the product according to the invention can be directly used by consumers, such as perfumers, due to its solid, particulate and crystalline form.

Another aspect of the present invention relates to the use of a particulate product according to the invention as a fragrance, in particular for the preparation of a perfume oil.

Preferably, the particulate product according to the invention is used as a fragrance for imparting, modifying and/or enhancing one or more odour notes selected from the group consisting of ambery, wood, and amber.

What has been stated above for the embodiments of the method according to the invention applies accordingly to the embodiments of the particulate product according to the invention and vice versa. What has been stated above for the embodiments of the method according to the invention applies accordingly to the embodiments of the use according to the invention and vice versa. What has been stated above for the embodiments of the particulate product according to the invention applies accordingly to the embodiments of the use according to the invention and vice versa. Moreover, the embodiments described herein can be arbitrarily combined with each other as long as it makes technical sense. Figure 1 : Top: X-ray powder diffraction patern of a particulate product according to the invention; bottom: X-ray powder diffraction pattern of the highly pure compound Ambrocenide® Cryst. (> 99% GC area of the compound of formula (la) as defined herein); the y-axis shows the absolute intensity and the x-axis the 20 values, respectively

Figure 2: Photograph of the contacting of a vapor-treated, fully molten mass with a cooling roll (cf. step (iv) of the method according to the invention)

Figure 3: Photograph of the removal of the solid product from a cooling roll with a discharge knife to obtain a particulate product (Ambrocenide® flakes) according to the invention (cf. step (vi) of the method according to the invention)

This invention is explained in more detail using the following examples. Unless otherwise stated, all specifications refer to the weight.

Example 1 : Preparation of a mixture comprising the compound of formula (la) and the compound of formula (lb) (as provided in step (i) of the method according to the invention)

Cedar wood oil (CAS No. 91722-61-1 ; CAS No. 68608-32-2), containing about 73 wt.-% of alpha-cedrene, was fractionally distilled to obtain a fraction comprising about 93 wt.-% of alpha-cedrene. Said fraction is then treated as disclosed in example 2 of WO 2022/223117 A1 :

1) The fraction comprising alpha-cedrene (purity ca. 93 wt.-%, 100 g, 0.46 mol, 1 .0 eq) is provided in tert-butanol (720 g) and water (360 g) and brought to 20 °C.

2) Within about 5 h, a mixture of potassium permanganate (98 g, 0.62 mol, 1.35 eq), water (1320 g), and NaOH (22.4 g, 0.56 mol, 1 .22 eq) is added while keeping the temperature of the reaction mixture at 20-24 °C (slightly exothermic reaction). During the addition, nitrogen is continuously bubbled through the mixture and/or the mixture is continuously stirred. A brown mixture with a precipitate is formed. 3) The tert-butanol is removed as an azeotrope with about 20% of water until 140 mbar are reached. During this time, the heating is set to 80 °C. In total, about 910 g of distillate are obtained. The tert-butanol obtained can be re-used for the reaction.

4) Subsequently, it is cooled to 40 °C and ethyl acetate (700 g) is added.

5) At 40 °C, sulphuric acid (40 %, 200 g) are added.

6) At about 40 °C, sodium hydrogen sulphite solution (40 %, 215 g) is added and, towards the end of the addition, the heating is increased to 55 °C. Two clear phases form and some cedranediol precipitates.

7) The aqueous phase (ca. 2300 g) is separated.

8) Ethyl acetate (700 g), soda (40 g), and water (360 g) are added, which re-dissolves the precipitated cedranediol.

9) The mixture is brought to 55 °C and well mixed.

10) The aqueous phase is separated.

11) Sodium chloride (30 g) and water (270 g) are added.

12) The mixture is again brought to 55 °C and well mixed.

13) The aqueous phase is separated.

The product is dissolved in the ethyl acetate phase and the cedranediol partially precipitates during cooling of the organic phase. When the solvent is removed, a starting mixture comprising 93 wt.-% of alpha, alpha-cedranediol of formula (Illa) (ca. 102 g) and 0.12 wt.-% of the compound of formula (llle) is obtained the starting mixture being free of beta.beta-cedranediol of formula (lllb), beta.alpha- cedranediol of formula (lllc) and alpha, beta-cedranediol of formula (Hid)

The reaction described above can be scaled up accordingly for production of the starting mixture on a larger scale, as required.

70 kg of dimethoxypropane (95 %) in 62 kg of acetone are placed in a stirring vessel and 50 kg of the starting mixture are added.

A solution consisting of 53 kg of acetone and 0.167 kg of technical sulphuric acid is then added at a temperature of not more than 30 °C for a period of 2 hours. After a further stirring time of 4 hours, the reaction mixture is adjusted to a pH of at least 8 with a slurry consisting of 1 .6 kg of calcined soda in 5 kg of water. During subsequent distillation, the low boilers are removed from the reaction mixture to such an extent that a sump temperature of 95 °C is not exceeded. When the distillation is complete, 38 kg of methyl-tert.-butyl ether are added to the distillation residue and stirred at a temperature of about 35 °C for about 30 minutes. The reaction mixture is then left to rest until a clear two-phase mixture is obtained. The aqueous phase is separated off and 12 kg of water are added to the remaining organic phase. The mixture obtained is stirred at a temperature of about 35 °C for about 30 minutes. The reaction mixture is then left to rest until a clear two-phase mixture is obtained. The aqueous phase is separated off and methyl-tert.-butyl ether is removed during subsequent distillation of the organic phase, to such an extent that a sump temperature of 95 °C is not exceeded at 40 mbar, to obtain an unpurified synthesis product in the form of a fully molten mass. Water is added to the fully molten mass, which leads to a sump temperature of 70 °C at 1013 mbar. The evaporation of the water is performed by increasing the sump temperature up to 95°C and simultaneously lowering the pressure down to 40 mbar.

The obtained (water) vapor-treated fully molten mass comprises 89.2 wt.-% of compound of formula (la) and 0.13 wt.-% of compound of formula (lb) as defined herein:

It is laid on top of a chilled cooling belt, as drops (to create pastilles) or closed layer (to create flakes), or it is laid as a closed layer (to create flakes) between two chilled double cooling belts (upper and lower) for solidification to obtain a solid product according to the invention. After the solidification, the solid product is removed from the belt by a discharge knife and hereafter used and packaged as a solid, particulate product (flakes or pastilles comprising 89.2 wt.-% of compound of formula (la) and 0.13 wt.-% of compound of formula (lb) as defined herein ). Example 2:

X-ray powder diffraction paterns of Ambrocenide® Cryst. (a highly pure crystalline solid with > 99% GC area of the compound of formula (la) as defined herein) and of the Ambrocenide® flakes obtained according to Example 1 (comprising ca. 89.2 wt.-% of compound of formula (la) and 0.13 wt.-% of compound of formula (lb)), respectively, were recorded at 22 °C with a STOE STADI P diffractometer in transmission geometry in the area of 2.87 ° to 79.85 ° 20 with a step width of 0.015 ° by using Co-Kai irradiation. The results of the measurements are summarized in the tables below and depicted in Figure 1. For the sample of Ambrocenide® Cryst., the following main diffraction angles were recorded:

20 in °

12.01 ± 0.2

13.44 ± 0.2

14.50 ± 0.2

15.93 ± 0.2

19.58 ± 0.2

22.12 ± 0.2

23.11 ± 0.2

26.67 ± 0.2

29.40 ± 0.2

For the sample of Ambrocenide® flakes obtained according to Example 1 , the following main diffraction angles were recorded:

20 in °

8.81 ± 0.2

12.05 ± 0.2

13.49 ± 0.2

14.55 ± 0.2

14.89 ± 0.2 15.98 ± 0.2

19.63 ± 0.2

22.15 ± 0.2

23.18 ± 0.2

26.75 ± 0.2

29.47 ± 0.2

As can be taken from the above tables and Figure 1 , the x-ray powder diffraction patterns of the two samples are almost identical with the only exception that the sample of Ambrocenide® Cryst. does not contain the Bragg reflexes at 8.81 ° and 14.89 °, because due to its high purity it is essentially free of cedranediol.

Example 3:

0.01 wt.-% of Ambrocenide® Cryst. (a highly pure crystalline solid with > 99% GC area of the compound of formula (la) as defined herein) and 0.01 wt.-% of the Ambrocenide® flakes obtained according to Example 1 (comprising ca. 89.2 wt.-% of compound of formula (la) and 0.13 wt.-% of compound of formula (lb)) are dissolved in dipropylene glycol (DPG), respectively, and the two samples are compared to one another in a triangle test by a trained panel of 20 participants. The following results were obtained: 8 correct and 12 incorrect (i.e. the olfactive difference between the two samples was not statistically significant). A large proportion of the trained panel was not able to distinguish the two samples in terms of their odour.

Both samples were described by the trained panel to have the following odour characteristics: Ambery, dry woody, ambery-woody.

Moreover, within further testing, both samples were described as follows by perfumers and perfumery experts:

Powerful and long-lasting top to base booster

Lends power to woody and ambery accords

Gives radiance and enhances citrus and aldehydic notes at low use levels Propels musk notes to be perceived in the top note Gives volume and strength to floral heart notes Example 4:

No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities enhance the aldehydic, watery facet of the accord and provide overall strength.

Example 5:

No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities support the citrus, top note elements of the accord and give substantivity. Example 6:

No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities underline the warm, rooty part of the iris note and support the substantivity.

Example 7:

No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities underline the woody character and add ambery elements to the formulations.

Example 8:

No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities underline woody, ambery elements of the accord. Example 9: No significant differences in the effect of the two Ambrocenide® qualities are perceived between the two formulations by a panel comprising 6 perfumers and perfume experts. Both qualities underline the musk note and add warm woody ambery undertones.

Claims

Patent claims:

1 . Method for producing a particulate product comprising or consisting of the following steps:

(i) Providing a mixture comprising or consisting of 70 to 98 wt.-% of compound and 0.01 to 5 wt.-% of compound of formula (lb) based on the total weight of the mixture, optionally wherein the mixture is at a temperature at which it is in the form of a partially or fully molten mass;

(ii) if applicable, heating the mixture provided in step (i) to obtain a partially or fully molten mass of said mixture; (iii) contacting the partially or fully molten mass provided in step (i) or obtained in step (ii), with a solvent having a boiling point that is lower than the boiling point of said mass, preferably with water, inside a vessel and then adjusting the pressure and temperature inside the vessel such that the solvent, preferably water, is evaporated or removed again from the mass, to obtain a vapor- treated, partially or fully molten mass;

(iv) contacting the vapor-treated, partially or fully molten mass obtained in step (iii) with a cold surface;

(v) cooling of the vapor-treated, partially or fully molten mass to obtain a solid product that is in contact with the cold surface;

(vi) removal of the solid product from the cold surface, preferably with a blade, to obtain a particulate product.

2. Method according to claim 1 , wherein in step (ii), if present, the mixture provided in step (i) is heated to an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C.

3. Method according to claim 1 or 2, wherein the vapor-treated, partially or fully molten mass obtained in step (iii) is at an average temperature of from 35 to 85 °C, preferably from 55 to 85 °C, most preferably from 80 to 85 °C, when first contacting the cold surface in step (iv).

4. Method according to any of the preceding claims, wherein the cold surface with which the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted in step (iv), has an average temperature of from 0 to 25 °C, preferably from 5 to 15 °C, most preferably from 8 to 12 °C.

5. Method according to any of the preceding claims, wherein the particulate product obtained in step (vi) is in the form of flakes.

6. Method according to any of the preceding claims, wherein the contacting of the vapor-treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) comprises or consists of the following step:

7. Method according to any of the claims 1 to 5, wherein the contacting of the vapor- treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) comprises or consists of the following step:

Depositing the molten mass on the cold surface to form a layer of the molten mass on at least parts of the cold surface.

8. Method according to any of the claims 1 to 4, wherein the particulate product obtained in step (vi) is in the form of pastilles.

9. Method according to claim 8, wherein the contacting of the vapor-treated, partially or fully molten mass obtained in step (iii) with the cold surface in step (iv) comprises or consists of the following step:

Depositing the molten mass on the cold surface to form one or more separate droplets of the molten mass on the cold surface.

10. Method according to any of the preceding claims, wherein the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) is the outer surface of a cooling roll.

11 . Method according to any of the preceding claims, wherein the cold surface that the vapor-treated, partially or fully molten mass obtained in step (iii) is contacted with in step (iv) is the upper or lower surface of a cooling belt.

12. Method according to any of the preceding claims, wherein the cold surface has a roughness of 0.1 to 2 pm, preferably of 0.4 to 0.8 pm.

13. Particulate product, preferably obtained or obtainable by a method according to any of claims 1 to 12, comprising 70 to 98 wt.-% compound of formula (la)

and 0.01 to 5 wt.-% compound of formula (lb) based on the total weight of the product.

14. Use of a particulate product according to claim 13 as a fragrance, in particular for the preparation of a perfume oil.

15. Use according to claim 14, for imparting, modifying and/or enhancing one or more odour notes selected from the group consisting of ambery, dry woody, and ambery- woody.