The present invention primarily relates to a method for producing a particulate
product comprising or consisting of the steps as described herein. The invention
5 further relates to a particulate product, preferably obtained or obtainable by a
method as described herein, comprising 70 to 98 wt.-% compound of formula (Ia)
as defined herein and 0.01 to 5 wt.-% compound of formula (Ib) as defined herein,
and to the use of a particulate product as described herein as a fragrance.
Further aspects and preferred embodiments of the present invention result from
10 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):
15 Formula A: Chemical structure of Ambrocenide®
The wavy lines in formula A may denote, independently of one another, an alphaor beta configuration of the bond. Ambrocenide® may generally comprise one,
two, three or all of the following diastereomers (formula B):
3
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):
4
Formula C: Preparation of Ambrocenide® (4, R=R’=CH3)
Depending on the reaction conditions selected during the synthesis, the crude
5 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 (Ia)
H
O
O
10 (Ia),
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
5
a starting mixture, containing or consisting essentially of alpha,alpha-cedranediol
of formula (IIIa)
(IIIa),
5 wherein the starting mixture is free or essentially free of beta,beta-cedranediol of
formula (IIIb), beta,alpha-cedranediol of formula (IIIc) and alpha,beta-cedranediol
of formula (IIId),
(IIIb) (IIIc) (IIId).
10
In the context of the studies underlying WO 2017/186973 A2, it was found by the
applicant that the compound of formula (Ia) 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
15 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®
20 obtained from synthesis, as for example described in WO 2017/186973 A2, is
challenging to handle due to its amorphous state.
6
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 (Ia) as defined
herein), which is manufactured via an effortful solvent recrystallization of the
5 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
10 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.
15 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
20 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 (Ia)
7
H
O
O
(Ia)
and 0.01 to 5 wt.-%, preferably 0.01 to 1 wt.-%, of compound of formula
(Ib)
H
O
O5
(Ib),
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
10 fully, molten mass (at a pressure of about 1 bar);
(ii) if applicable, heating the mixture provided in step (Ia) 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
15 liquid or gaseous state) having a boiling point that is lower than the boiling
8
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
5 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
10 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.
15
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
20 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 (Ia) as
25 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
9
to 98 wt.-% of the compound of formula (Ia) and a further five to seven minor
components, which are the compound of formula (Ib) and educts and sideproducts from synthesis (cf. further below for details). The high crystallinity of
the particulate product obtained in step (vi) of the method according to the
5 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,
10 when samples of Ambrocenide® Cryst. (> 99% GC area of the compound of
formula (Ia) 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
15 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
20 properties as the highly purified product Ambrocenide® Cryst. with > 99% GC
area of compound of formula (Ia) 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:
25
- The use of organic solvents is not required in the method according to
the invention,
10
- 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,
5 - 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.
10 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.
15 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 (Ia) and 0.01 to 5 wt.-% of compound of formula (Ib),
based on the total weight of the mixture.
According to another preferred embodiment of the method according to the
20 invention, the mixture provided in step (i) comprises or consists of 80 to 96 wt.-%
of compound of formula (Ia) and 0.01 to 1 wt.-% of compound of formula (Ib),
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.-%
25 of compound of formula (Ia) and 0.01 to 1 wt.-% of compound of formula (Ib),
based on the total weight of the mixture.
11
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
5 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
10 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
15 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.
20 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
25 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,
12
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
5 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.
10 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.
15 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
20 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
25 preferably 5 to 300 wt.-%, more preferably 5 to 200 wt.-%, more preferably 5 to
13
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
5 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.
10 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,
15 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).
20 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
25 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
14
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.
5 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 (Ia) and
compound of formula (Ib), in percentage terms, as defined above for the mixture
provided in step (i) of the method.
10
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 (Ia) and 0.01 to 5 wt.-% of compound of formula (Ib),
based on the total weight of the solid product.
15
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 (Ia) and 0.01 to 1 wt.-% of compound of
formula (Ib), based on the total weight of the solid product.
20
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 (Ia) and 0.01 to 1 wt.-% of compound of
formula (Ib), based on the total weight of the solid product.
25 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
15
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,
5 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
10 (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.
15 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
20 the invention comprises or consists of essentially the same amount of compound
of formula (Ia) and compound of formula (Ib), 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,
25 the particulate product obtained in step (vi) comprises or consists of 70 to 98 wt.-
16
% of compound of formula (Ia) and 0.01 to 5 wt.-% of compound of formula (Ib),
based on the total weight of the particulate product.
According to another preferred embodiment of the method according to the
5 invention, the particulate product obtained in step (vi) comprises or consists of 80
to 96 wt.-% of compound of formula (Ia) and 0.01 to 1 wt.-% of compound of
formula (Ib), based on the total weight of the particulate product.
According to another preferred embodiment of the method according to the
10 invention, the particulate product obtained in step (vi) comprises or consists of 80
to 95 wt.-% of compound of formula (Ia) and 0.01 to 1 wt.-% of compound of
formula (Ib), 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
15 further comprises one or several compound(s) of formula (II)
H
O
(II)
and/or of formula (III)
H
OH
OH
(III)
17
and/or of formula (IV)
H
O
(IV)
and/or of formula (V)
H
OH
(V)
5 and/or of formula (VI)
(VI)
H
OH
.
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)
18
H
O
(II)
and/or of formula (III)
H
OH
OH
(III)
and/or of formula (IV)
H
O
(IV) 5
and/or of formula (V)
H
OH
(V)
19
and/or of formula (VI)
(VI)
H
OH
.
According to another preferred embodiment, the particulate product obtained in
step (vi) of the method according to the invention further comprises one or several
5 compound(s) of formula (II)
H
O
(II)
and/or of formula (III)
H
OH
OH
(III)
and/or of formula (IV)
20
H
O
(IV)
and/or of formula (V)
H
OH
(V)
and/or of formula (VI)
(VI)
H
OH
5 .
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),
21
H
O
(II)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 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 (III),
H
OH
OH
(III)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
10 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),
22
H
O
(IV)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 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),
H
OH
(V)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
10 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),
23
(VI)
wherein the weight ratio of the total amount of compound of formula (Ia) 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.
5 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),
H
O
(II)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
10 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 solid product obtained in step (v) of the method according to the
invention further comprises one or several compound(s) of formula (III),
24
H
OH
OH
(III)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 and/or the solid product obtained in step (v) of the method according to the
invention further comprises one or several compound(s) of formula (IV),
H
O
(IV)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
total amount of compound(s) of formula (IV) in the product is at least 40 : 1,
10 preferably at least 50 : 1, particularly preferably at least 60 : 1,
and/or the solid product obtained in step (v) of the method according to the
invention further comprises one or several compound(s) of formula (V),
25
H
OH
(V)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 and/or the solid product obtained in step (v) of the method according to the
invention further comprises one or several compound(s) of formula (VI),
(VI)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
total amount of compound(s) of formula (VI) in the product is at least 4 : 1,
10 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),
26
H
O
(II)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 and/or the particulate product obtained in step (vi) of the method according to the
invention further comprises one or several compound(s) of formula (III),
H
OH
OH
(III)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
total amount of compound(s) of formula (III) in the product is at least 50 : 1,
10 preferably at least 100 : 1, particularly preferably at least 150 : 1,
and/or the particulate product obtained in step (vi) of the method according to the
invention further comprises one or several compound(s) of formula (IV),
27
H
O
(IV)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 and/or the particulate product obtained in step (vi) of the method according to the
invention further comprises one or several compound(s) of formula (V),
H
OH
(V)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
total amount of compound(s) of formula (V) in the product is at least 30 : 1,
10 preferably at least 40 : 1, more preferably at least 50 : 1,
and/or the particulate product obtained in step (vi) of the method according to the
invention further comprises one or several compound(s) of formula (VI),
28
(VI)
wherein the weight ratio of the total amount of compound of formula (Ia) 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.
5 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.
10
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
15 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
20 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
29
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,
5 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
10 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).
15
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
20 °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
25 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.
30
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
5 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.
10
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
15 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
20 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
25 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.
31
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
5 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).
10 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
15 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,
20 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
25 following step:
32
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
5 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
10 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
15 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
20 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,
25 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
33
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.
5 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
10 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).
15 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
20 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
25 step (iv) of the method, is the upper surface of a lower cooling belt that rotates
34
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
5 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
10 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
15 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
20 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).
35
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.
5 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.
10 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
15 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
20 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
25 invention has a roughness of 0.1 to 2 µm, preferably of 0.4 to 0.8 µm.
36
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 (Ia)
H
O
O5
(Ia)
and 0.01 to 5 wt.-%, preferably 0.01 to 1 wt.-%, compound of formula (Ib)
10
(Ib),
based on the total weight of the product.
H
O
O
37
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 (Ia) and 0.01 to 5 wt.-% of compound of formula (Ib), based on the total
weight of the product.
5 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 (Ia) and 0.01 to 1 wt.-% of compound of formula (Ib), based on the
total weight of the product.
According to another preferred embodiment of the particulate product according
10 to the invention, the product comprises or consists of 80 to 95 wt.-% of compound
of formula (Ia) and 0.01 to 1 wt.-% of compound of formula (Ib), 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
15 formula (II)
H
O
(II)
and/or of formula (III)
38
H
OH
OH
(III)
and/or of formula (IV)
H
O
(IV)
and/or of formula (V)
H
OH
(V) 5
and/or of formula (VI)
(VI)
H
OH
.
39
Preferably, the particulate product further comprises one or several compound(s)
of formula (II),
H
O
(II)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
5 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),
H
OH
OH
(III)
10 wherein the weight ratio of the total amount of compound of formula (Ia) 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),
40
H
O
(IV)
wherein the weight ratio of the total amount of compound of formula (Ia) 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,
5 and/or the particulate product further comprises one or several compound(s) of
formula (V),
H
OH
(V)
wherein the weight ratio of the total amount of compound of formula (Ia) to the
total amount of compound(s) of formula (V) in the product is at least 30 : 1,
10 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),
41
(VI)
wherein the weight ratio of the total amount of compound of formula (Ia) 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.
5 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
10 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
15 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.
42
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,
5 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
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
15 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 (Ia) 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.
20 (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.
43
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
5 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
10 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
15 arbitrarily combined with each other as long as it makes technical sense.
Figures
Figure 1: Top: X-ray powder diffraction pattern 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
20 formula (Ia) as defined herein); the y-axis shows the absolute intensity and the xaxis the 2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
25 a discharge knife to obtain a particulate product (Ambrocenide® flakes) according
to the invention (cf. step (vi) of the method according to the invention)
44
This invention is explained in more detail using the following examples. Unless
otherwise stated, all specifications refer to the weight.
Examples
5 Example 1: Preparation of a mixture comprising the compound of
formula (Ia) and the compound of formula (Ib) (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
10 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
15 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
20 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
25 140 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 reused for the reaction.
45
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.
5 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.
10
8) Ethyl acetate (700 g), soda (40 g), and water (360 g) are added, which redissolves the precipitated cedranediol.
9) The mixture is brought to 55 °C and well mixed.
15
10) The aqueous phase is separated.
11) Sodium chloride (30 g) and water (270 g) are added.
20 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
25 precipitates during cooling of the organic phase. When the solvent is removed, a
starting mixture comprising 93 wt.-% of alpha,alpha-cedranediol of formula (IIIa)
(ca. 102 g) and 0.12 wt.-% of the compound of formula (IIIe) is obtained
46
(IIIa) (IIIe)
,
the starting mixture being free of beta,beta-cedranediol of formula (IIIb),
beta,alpha-cedranediol of formula (IIIc) and alpha,beta-cedranediol of formula
5 (IIId)
(IIIb) (IIIc) (IIId).
The reaction described above can be scaled up accordingly for production of the
starting mixture on a larger scale, as required.
10 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
15 at least 8 with a slurry consisting of 1.6 kg of calcined soda in 5 kg of water.
47
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
5 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
10 two-phase mixture is obtained. The aqueous phase is separated off and methyltert.-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
15 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 (Ia) and 0.13 wt.-% of compound of formula (Ib) as defined
20 herein:

25 (Ia) (Ib).
H
O
O
H
OO
48
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
5 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 (Ia) and 0.13 wt.-% of compound of formula (Ib) as defined herein ).
Example 2:
X-ray powder diffraction patterns of Ambrocenide® Cryst. (a highly pure
10 crystalline solid with > 99% GC area of the compound of formula (Ia) as defined
herein) and of the Ambrocenide® flakes obtained according to Example 1
(comprising ca. 89.2 wt.-% of compound of formula (Ia) and 0.13 wt.-% of
compound of formula (Ib)), respectively, were recorded at 22 °C with a STOE
STADI P diffractometer in transmission geometry in the area of 2.87 ° to 79.85 °
15 2 with a step width of 0.015 ° by using Co-K1 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:
2 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
49
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:
2 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
5 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%
10 GC area of the compound of formula (Ia) as defined herein) and 0.01 wt.-% of the
Ambrocenide® flakes obtained according to Example 1 (comprising ca. 89.2 wt.-
50
% of compound of formula (Ia) and 0.13 wt.-% of compound of formula (Ib)) 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
5 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.
10 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
15 - Propels musk notes to be perceived in the top note
- Gives volume and strength to floral heart notes
Example 4:
ALDEHYDIC
Aldehyde C11 Methyloctylaldehyde
10% 285
Aldehyde C11 Undecanal 10% 95
Aldehyde C12
Methylnonylaldehyde 10% 38
Farenal® 10% 76
Florazon 10% 209
Limonenal 10% 95
Mandarine Aldehyde 10TEC 10% 114
Ozonil 10% 38
51
Dipropylene Glycol 40
0.1 wt.-% of Ambrocenide® Cryst.
(> 99% GC area of the compound
of formula (Ia)) in DPG
or
0.1 wt.-% of Ambrocenide® flakes
obtained according to Example 1
in DPG
10
1000
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
5 and provide overall strength.
Example 5:
CITRUS
Amarocit® 60
Lemon Oil Ital. 300
Claritone® 80
Dihydromyrcenol 150
Linalool 160
Terpinylacetate 80
Vertacetal® Coeur 20
Dipropylene Glycol 120
0.1 wt.-% of Ambrocenide®
Cryst. (> 99% GC area of the
compound of formula (Ia)) in
DPG
or
0.1 wt.-% of Ambrocenide®
30
52
flakes obtained according to
Example 1 in DPG
1000
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.
5 Example 6:
53
No significant differences in the effect of the two Ambrocenide® qualities are
perceived between the two formulations by a panel comprising 6 perfumers and
5 perfume experts. Both qualities underline the warm, rooty part of the iris note and
support the substantivity.
FLORAL
Cetone Alpha 10
Evernyl 10% 20
Frambinon® 1% 40
Helional 5
Heliotropin 10
Ionon Alpha 80
Ionon Beta 40
Iraldein Beta 110
Iron Alpha 10% 20
Isoraldein 70 460
Leafovert® 10% 15
Nonadienal 0,1% 10
Parmanyl® 20
Patchouli Oil 5
Syvertal 10% 10
Violet Leaves Abs. 1% 20
Dipropylene Glycol 80
0.1 wt.-% of
Ambrocenide® Cryst. (>
99% GC area of the
compound of formula
(Ia)) in DPG
or
0.1 wt.-% of
Ambrocenide® flakes
obtained according to
Example 1 in DPG
20
1000
54
Example 7:
WOODY
Iso E Super 350
Timberol® 200
Ysamber® K 300
Dipropylene Glycol 50
0.1 wt.-% of Ambrocenide®
Cryst. (> 99% GC area of the
compound of formula (Ia)) in
DPG
or
0.1 wt.-% of Ambrocenide®
flakes obtained according to
Example 1 in DPG
100
1000
No significant differences in the effect of the two Ambrocenide® qualities are
perceived between the two formulations by a panel comprising 6 perfumers and
5 perfume experts. Both qualities underline the woody character and add ambery
elements to the formulations.
Example 8:
AMBERY
Amberwood® F 200
Cashmeran 40
Iso E Super 250
Madranol® 200
Ambrinol S 10% 20
Ambroxide Cryst. 110
55
Ysamber® K 100
Ambrarome Abs. 10% 25
Lactoscatone 5
Dipropylene Glycol 40
0.1 wt.-% of Ambrocenide® Cryst.
(> 99% GC area of the compound
of formula (Ia)) in DPG
or
0.1 wt.-% of Ambrocenide® flakes
obtained according to Example 1
in DPG
20
1000
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.
5 Example 9:
Musk
Aurelione® 100
Globalide® 300
Globanone® 200
Macrolide® Supra 300
Dipropylene Glycol 90
0.1 wt.-% of Ambrocenide® Cryst.
(> 99% GC area of the compound of
formula (Ia)) in DPG
or
0.1 wt.-% of Ambrocenide® flakes
obtained according to Example 1 in
DPG
10
1000
56
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.
5
10
15
20
25
30
35
40
57
WE CLAIM :
5 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 of formula (Ia)
10

(Ia)
15 and 0.01 to 5 wt.-% of compound of formula (Ib)

20
(Ib),
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;
H
O
OH
O
O
58
(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
5 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;
10 (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
15 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.
20
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).
25
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.
59
5. Method according to any of the preceding claims, wherein the particulate
product obtained in step (vi) is in the form of flakes.
5 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:
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
10 molten mass on at least parts of the cold surface.
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:
15 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.
20
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
25 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.
60
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.
5
12. Method according to any of the preceding claims, wherein the cold surface
has a roughness of 0.1 to 2 µm, preferably of 0.4 to 0.8 µm.
13. Particulate product, preferably obtained or obtainable by a method
10 according to any of claims 1 to 12, comprising 80 to 95 wt.-% compound of
formula (Ia)
15
20 (Ia)
and 0.01 to 1 wt.-% compound of formula (Ib)
25
(Ib),
H
O
OH
O
O
61
based on the total weight of the product, and
wherein the particulate product is in the form of flakes with an average
5 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,
or
wherein the particulate product is in the form of pastilles with an average
diameter of from 2 to 12 mm and average height of from 1 to 10 mm.
10
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
15 or more odour notes selected from the group consisting of ambery, dry
woody, and ambery-woody.