Technical field
The invention relates to the field of xanthene derivatives.
More particularly, the invention relates to a family of particular xanthene
derivatives, to a process for manufacturing same and also to corresponding uses.
Prior art
Xanthene and its derivatives are known as chromophores.
Xanthene has the chemical formula:
[Chem 1]
(D)
A derivative of xanthene that is particularly known for its fluorescent properties is
fluorescein, of chemical formula:
[Chem 2]
(DI)
Fluorescein and its derivatives have been used in many fields, notably as tracers
for coloring water or as markers of biological molecules (peptides, antibodies,
O
O HO
COOH
O
WO 2021/234251 2 PCT/FR2021/050841
nucleotides, oligonucleotides, hormones, lipids, etc.). In the case of its use as a
marker of biological molecules, fluorescein or its derivatives are generally grafted
by covalent bonding to the molecule of interest usually by means of a group
reacting with the amine functions.
The synthesis of many other xanthene derivatives, according to more or less
complex reaction schemes, is known from the prior art: see, for example, the
doctoral thesis: Kotásková, Michaela. Synthesis of new xanthene derivatives.
2013.
Objects of the invention
The object of the invention is to propose a novel family of xanthene derivatives
and also several associated uses.
According to at least certain embodiments, the object is to propose compounds
which have fluorescence properties.
According to at least certain embodiments, the object is to propose compounds
which can be used as radical initiators.
According to at least certain embodiments, the object is to propose compounds
for improving the adhesion of an aromatic or semiaromatic polymeric matrix with
a substrate.
According to at least certain embodiments, the object of the invention is to propose
compounds for improving the compatibility between one aromatic or semiaromatic
polymeric matrix and another aromatic, semiaromatic, or aliphatic polymeric
matrix.
The object of the invention is also to propose a process for manufacturing this
novel family of xanthene derivatives.
The object of the invention is also to propose possible uses for this novel family
of derivatives.
Summary of the invention
The invention relates to a compound having the chemical formula:
WO 2021/234251 3 PCT/FR2021/050841
[Chem 3]
O
O
O
R
0
H H
H
R
2
j
R
1
i
R
2
j
R
1
i
R
3
k
(I) or
[Chem 4]
(II)
in which:
R0 denotes: a charge +, -H or –OH;
i is an integer having a value from 0 to 3;
j, k and l are integers independently having a value from 0 to 4;
for any i, 𝑅𝑖
1
, for any j, 𝑅𝑗
2
, for any k, 𝑅𝑘
3
, for any l, 𝑅𝑙
4 are independently chosen
from the list consisting of:
alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, notably
carboxylic ester, amide, notably primary amide, halogen, imide, nitro and
aliphatics comprising a nitro function, nitrile and aliphatics comprising a nitrile
function, carbonyl, alkali metal or alkaline-earth metal sulfonate, alkyl sulfonate,
alkali metal or alkaline-earth metal phosphonate, amine, and quaternary
ammonium.
According to certain embodiments, said i, j, k and l are all equal to 0.
O
H H
R
2
j
R
1
i
R
2
j
R
1
i
O
R
0
H
O
R
4
l
WO 2021/234251 4 PCT/FR2021/050841
According to certain embodiments, R0
is: –OH.
According to certain embodiments, R0
is: –H.
According to certain embodiments, R0
is: +.
The invention also relates to a process for notably obtaining the compound of
formulae (I) and/or (II). The process involves reacting a compound of formula (III)
with a compound of formula (IVa) or (IVb), in the presence of a Lewis acid.
Compound (III) has the chemical formula:
[Chem 5]
Compound (IVa) has the chemical formula:
[Chem 6]
Compound (IVb) has the chemical formula:
[Chem 7]
in which i, j, k, l, 𝑅𝑖
1
, 𝑅𝑗
2
, 𝑅𝑘
3 and 𝑅𝑙
4 are defined as above;
to obtain a product mixture comprising a compound as described above.
According to certain embodiments, said i, j, k and l are all equal to 0.
O
H H
H
R
2
j
R
1
i
R
3
k
O
O
Cl
Cl
R
4
l
O
Cl
O
Cl
WO 2021/234251 5 PCT/FR2021/050841
According to certain embodiments, the reaction of the compound of formula (III)
with the compound of formula (IVa) or, respectively, of formula (IVb) is performed
in a reaction solvent. The reaction solvent is preferentially an aprotic solvent. The
reaction solvent is more preferably chosen from the group consisting of:
dichloromethane, carbon disulfide, ortho-dichlorobenzene, metadichlorobenzene, para-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-
trichlorobenzene, ortho-difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane,
1,1,2,2-tetrachloroethane, tetrachloroethylene, dichloromethane, nitrobenzene
and a mixture thereof. The reaction solvent is most preferably orthodichlorobenzene.
According to certain embodiments, the Lewis acid is chosen from the group
consisting of: aluminum trichloride, aluminum tribromide, antimony pentachloride,
antimony pentafluoride, indium trichloride, gallium trichloride, boron trichloride,
boron trifluoride, zinc chloride, ferric chloride, stannic chloride, titanium
tetrachloride and molybdenum pentachloride. Preferentially, the Lewis acid is
chosen from the group consisting of: aluminum trichloride, boron trichloride,
aluminum tribromide, titanium tetrachloride, antimony pentachloride, ferric
chloride, gallium trichloride and molybdenum pentachloride. More preferably, the
Lewis acid is aluminum trichloride.
According to certain embodiments, the molar amount of compound of formula (III)
relative to the molar amount of compound of formula (IVa) or, respectively, (IVb)
is from 2 to 6. Preferably, the molar amount of compound of formula (III) relative
to the molar amount of compound of formula (IVa) or, respectively, (IVb) is from 2
to 4.
According to certain embodiments, the molar amount of Lewis acid relative to the
sum of the molar amounts of compound of formula (III) and compound of formula
(IVa) or, respectively, (IVb) is from 0.25 to 2. Preferably, the molar amount of
compound of formula (III) relative to the molar amount of compound of formula
(IVa) or, respectively, (IVb) is from 0.3 to 1.5.
According to certain embodiments, the process comprises:
- at least one step of separating the compound of formula (I) or, respectively, of
formula (II) from at least one other species of the product mixture; and, optionally
WO 2021/234251 6 PCT/FR2021/050841
- at least one step of purifying the compound of formula (I) or, respectively, of
formula (II).
According to certain embodiments, the process comprises a solid/liquid
separation step in order to recover a liquid comprising in major amount the
compound of formula (I) or, respectively, of formula (II), and a wet cake comprising
in minor amount the compound of formula (I) or, respectively, of formula (II).
The invention also relates to a mixture of compounds comprising:
- the compound of formula (I) as described above;
- a compound of formula:
[Chem 8]
(IX-i),
[Chem 9]
(IX-ii),
or a mixture thereof, in which i, j, k, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑘
3 are defined such as those of
compound (I).
According to certain embodiments, in this mixture, the compound of formula (I)
represents from 0.01 mol% to 10 mol% relative to the total number of moles of the
compounds of formulae (I), (IX-i) and (IX-ii).
According to certain embodiments, in this mixture, the compound of formula (I)
represents from 90 mol% to 99.99 mol% relative to the total number of moles of
the compounds of formulae (I), (IX-i) and (IX-ii).
The invention also relates to a mixture of compounds comprising:
- the compound of formula (II) as described;
- a compound of formula:
O
O
O
O
R
1
i R
1
R i
2
j
R
2
R j
3
k
O
O
O
O
R
1
i R
2
R j
2
j
R
1
R i
3
k
WO 2021/234251 7 PCT/FR2021/050841
[Chem 10]
(X-i)
[Chem 11]
(X-ii)
or a mixture thereof,
in which i, j, l, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑙
4 are defined such as those of compound (II).
According to certain embodiments, in this mixture, the compound of formula (II)
represents from 0.01 mol% to 10 mol% relative to the total number of moles of the
compounds of formulae (II), (X-i) and (X-ii).
According to certain embodiments, in this mixture, the compound of formula (II)
represents from 90 mol% to 99.99 mol% relative to the total number of moles of
the compounds of formulae (II), (X-i) and (X-ii).
Finally, the invention relates to the use of a compound of formula (I) or (II) as a
chromophore, as a free-radical generator, or as an adhesion promoter and/or
coupling agent.
List of figures
[Fig. 1] represents a first reaction scheme for obtaining the desired compound of
formula (V) from a mixture of diphenyl ether and terephthaloyl chloride in the
presence of aluminum trichloride.
R
1
R i
2
j
O
O
R
1
i R
2
j
O
O
R
4
l
R
2
j R
1
i
O
O
R
1
R i
2
j
O
O
R
4
l
WO 2021/234251 8 PCT/FR2021/050841
[Fig. 2] represents an alternative reaction scheme to that shown in Fig. 1 for
obtaining the desired compound of formula (V) from a mixture of diphenyl ether
and terephthaloyl chloride in the presence of aluminum trichloride.
[Fig. 3] represents a reaction scheme for obtaining the compound of formula (VIII),
obtained from the predominantly competing reaction, from a mixture of diphenyl
ether and terephthaloyl chloride in the presence of aluminum trichloride.
[Fig. 4] represents the HPLC/MS chromatogram of the mixture obtained according
to Example 1, containing essentially the compound of formula (V). The x-axis
represents an elution time and is expressed in minutes (min). The y-axis
represents the ion abundance and is expressed in milli-arbitrary units (mAU).
[Fig. 5] represents the mass spectrum of the mixture obtained according to
Example 1 containing essentially the compound of formula (VI) by HPLC/MS. The
x-axis represents an elution time and is expressed in minutes (min). The y-axis
represents the ion abundance and is expressed in milli-arbitrary units (mAU).
[Fig. 6] represents the UV/IR absorbance spectrum of the compound of formula
(V). The x-axis represents the wavelengths, expressed in nanometers (nm). The
y-axis represents the absorbance (dimensionless).
[Fig. 7] represents the UV/IR absorbance spectrum of the compound in the (V)
form and/or in the (VI) form at different pH values. The x-axis represents the
wavelengths, expressed in nanometers (nm). The y-axis represents the
absorbance (dimensionless).
Detailed description of the invention
The invention will now be described in greater detail and in a nonlimiting manner
in the description that follows.
The process involves reacting a compound of formula (III) with a compound of
formula (IVa) or, respectively, of formula (IVb), in the presence of a Lewis acid;
WO 2021/234251 9 PCT/FR2021/050841
compound (III) being an aromatic ether having the chemical formula:
[Chem 12]
compound (IVa) being an aromatic acyl chloride having the chemical formula:
[Chem 13]
and the compound of formula (IVb) being an aromatic acyl chloride having the
chemical formula:
[Chem 14]
in which:
i is an integer having a value from 0 to 3;
j, k and l are integers independently having a value from 0 to 4;
for any i, 𝑅𝑖
1
, for any j, 𝑅𝑗
2
, for any k, 𝑅𝑘
3
, for any l, 𝑅𝑙
4 are independently chosen
from the list consisting of: alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic
acid, ester, notably carboxylic ester, amide, notably primary amide, halogen,
imide, nitro and aliphatics comprising a nitro function, nitrile and aliphatics
comprising a nitrile function, carbonyl, alkali or alkaline-earth metal sulfonate, alkyl
sulfonate, alkali metal or alkaline-earth metal phosphonate, amine and quaternary
ammonium.
O
H H
H
R
2
j
R
1
i
R
3
k
O
O
Cl
Cl
R
4
l
O
Cl
O
Cl
WO 2021/234251 10 PCT/FR2021/050841
Preferentially, in the preceding formulae, for any i, 𝑅𝑖
1
, for any j, 𝑅𝑗
2
, for any k, 𝑅𝑘
3
,
for any l, 𝑅𝑙
4 are independently chosen from the list consisting of: alkyl, aryl, ether,
thioether, carboxylic acid, ester, notably carboxylic ester, amide, notably primary
amide, imide, nitro and aliphatics comprising a nitro function, nitrile and aliphatics
comprising a nitrile function, carbonyl, alkali metal or alkaline-earth metal
sulfonate, alkyl sulfonate, alkali metal or alkaline-earth metal phosphonate, and
tertiary amine.
According to this notation, 𝑅0
𝑖 means that the benzene group on which the latter
is positioned has no substituent; 𝑅1
𝑖 means that the benzene group on which the
latter is positioned comprises exactly one substituent; 𝑅2
𝑖 means that the benzene
group on which the latter is positioned comprises exactly two substituents, each
of the two substituents possibly being chosen independently of each other, etc.
In certain embodiments, the process involves reacting diphenyl ether with
terephthaloyl chloride or isophthaloyl chloride in the presence of a Lewis acid, for
example aluminum trichloride (AlCl3).
Without wishing to be bound by theory, the inventors believe that the reaction for
obtaining compounds according to the invention takes place according to the
reaction scheme in Figure 1 and/or according to the reaction scheme in Figure 2.
For simplicity, the reaction schemes in Figures 1 and 2 represent the example of
a mixture of diphenyl ether and terephthaloyl chloride in the presence of aluminum
trichloride, but are not intended to be limiting to these compounds alone. The ortho
and para positions of the phenyl groups of diphenyl ether are particularly activated
by the mesomeric effect, which would explain why the electrophilic substitutions
take place mainly in the para and ortho positions. The reaction according to
Figures 1 and 2 involves two intermolecular electrophilic substitutions and one
intramolecular electrophilic substitution (cyclization). More specifically, the
reaction involves an intermolecular electrophilic substitution of a hydrogen of a
phenyl group of a diphenyl ether molecule in the ortho position, followed by an
intramolecular, 6-atom cyclization, of a hydrogen of the other phenyl group of this
diphenyl ether molecule also in the ortho position, and also another intermolecular
electrophilic substitution of a hydrogen of a phenyl group of another diphenyl ether
molecule in the ortho position. The compound below is then obtained, of formula:
WO 2021/234251 11 PCT/FR2021/050841
[Chem 15]
(V)
Since the -OH group of the compound of formula (V) is labile under acidic
conditions, the carbocation below may be formed, of formula:
[Chem 16]
(VI)
The reduced form of the carbocation of formula (VI) is the compound below, of
formula:
[Chem 17]
(VII)
The main competing reaction to those shown in Figures 1 and 2 is that according
to the reaction scheme in Figure 3. As for Figures 1 and 2, Figure 3 also illustrates
the example of a mixture of diphenyl ether and terephthaloyl chloride in the
presence of aluminum trichloride. The reaction according to Figure 3 involves two
intermolecular electrophilic substitutions of the hydrogen atom of a phenyl group
in the para position of a diphenyl ether molecule. The compound below is thus
also obtained, of formula:
O
O HO
O
O
O
O
O
O
O
WO 2021/234251 12 PCT/FR2021/050841
[Chem 18]
(VIII)
It is essential, in order for the 6-atom cyclization to take place, that the aromatic
ether of formula (III) have a hydrogen atom in the ortho position of each phenyl
group. Furthermore, it is also essential that the aromatic ether of formula (III) have
a hydrogen atom in the para position of at least one phenyl group. The other
positions of the phenyl groups of the aromatic ether of formula (III) may or may
not be substituted.
Certain parameters may further favor the reaction for synthesizing the compound
according to the invention (such as the reaction scheme according to Figure 1 or
Figure 2) relative to competing reactions (mainly such as the reaction scheme
according to Figure 3).
These parameters may be intrinsic features of the reagents: the ortho and para
positions of the aromatic ether (III) may be more or less activated depending on
the nature and position of its possible substituents, due to their electron-donating
or electron-withdrawing effect.
For example, for an aromatic ether of formula:
[Chem 19]
(III-x)
in which X is an electron-donating group, the electron-donating group X enables
the activation of the phenyl bearing this group X (in bold), which promotes multiple
substitutions on the aromatic rings.
These parameters may also be certain reaction variables as explained below in
certain preferential embodiments.
In one embodiment, the reaction is performed without solvent. The reaction is then
referred to as a bulk reaction.
In another embodiment, the reaction is performed in a reaction solvent. The
reaction solvent is preferably a nonprotic solvent.
O
O
O
O
O
H H
X H
WO 2021/234251 13 PCT/FR2021/050841
A protic solvent is a solvent containing at least one hydrogen atom bonded to an
oxygen atom or to a nitrogen atom, and which is capable of donating protons to
the reagents. Conversely, a nonprotic solvent is a solvent that is not a protic
solvent.
The nonprotic solvent used herein may notably be chosen from methylene
chloride, carbon disulfide, ortho-dichlorobenzene, meta-dichlorobenzene, paradichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, orthodifluorobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane,
tetrachloroethylene, dichloromethane, nitrobenzene, and mixtures thereof.
ortho-Dichlorobenzene is the solvent that is the most preferred.
The Lewis acids that may be used comprise, for example, aluminum trichloride,
aluminum tribromide, antimony pentachloride, antimony pentafluoride, indium
trichloride, gallium trichloride, boron trichloride, boron trifluoride, zinc chloride,
ferric chloride, stannic chloride, titanium tetrachloride and molybdenum
pentachloride. Aluminum trichloride, boron trichloride, aluminum tribromide,
titanium tetrachloride, antimony pentachloride, ferric chloride, gallium trichloride
and molybdenum pentachloride are preferred. Aluminum trichloride is particularly
preferred.
The reaction between the compound of formula (III) and the compound of formula
(IVa) or of formula (IVb) in the presence of a Lewis acid to manufacture a
compound of formula (I) or (II) may be performed in a reactor. The reaction may
be performed in a reactor. The reactor may be, for example, a glass reactor, a
reactor with a glass inner wall or a reactor made of stainless metal materials, or
lined with PTFE.
According to certain variants, the materials introduced into the reactor in the
process of the invention are essentially, or consist of, the compound of formula
(III), the compound of formula (IVa) or, respectively, of formula (IVb), the reaction
solvent and the Lewis acid.
Preferentially, the reaction may be performed in a reaction mixture that
substantially does not comprise any water.
Preferentially, the reaction may be performed in an atmosphere that substantially
does not comprise any water or dioxygen, for example under a nitrogen or argon
atmosphere.
WO 2021/234251 14 PCT/FR2021/050841
The reaction mixture may be prepared by mixing together the components
(compound of formula (III), compound of formula (IVa) or, respectively, of formula
(IVb), Lewis acid and reaction solvent) in any order.
According to a first embodiment, an initial mixture is first prepared, comprising
(and preferably consisting of) the compound of formula (III) and the compound of
formula (IVa) or, respectively, of formula (IVb), in the reaction solvent. The initial
mixture may notably be prepared by mixing together the three compounds, in any
order. By way of example, the reaction solvent may be introduced into the reactor
first, and the compounds of formula (III) and of formula (IVa) or, respectively, of
formula (IVb) may then be added in turn. The Lewis acid is then added to the initial
mixture.
Preferably, the Lewis acid is added in solid form. Alternatively, the Lewis acid may
also be added in the form of a suspension or colloid, namely in the form of a
heterogeneous mixture of solid Lewis acid particles in a solvent. The solvent for
the suspension/colloid is advantageously the abovementioned reaction solvent.
The Lewis acid may also be added in the form of a solution, namely in the form of
a homogeneous mixture of Lewis acid in a solvent. The solvent of the solution is
preferably the abovementioned reaction solvent.
According to a second embodiment, an initial mixture is first prepared, comprising
(and preferably consisting of) the compound of formula (IVa) or, respectively, of
formula (IVb), and the Lewis acid in the reaction solvent. The initial mixture may
be prepared by mixing together the three compounds, in any order. The
compound of formula (III) is then added to the initial mixture. It may be added in
its liquid form or in the form of a solution, preferably in the abovementioned
reaction solvent.
In a third embodiment, an initial mixture is first prepared comprising (and
preferably consisting of) the compound of formula (III) and the Lewis acid in the
reaction solvent. The initial mixture may be prepared by mixing together the three
compounds, in any order. The compound of formula (IVa) or, respectively, of
formula (IVb), is then added to the initial mixture. It may be added in solid or liquid
form. Alternatively, it may be added in the form of a suspension, a colloid, or a
solution, preferably in the abovementioned reaction solvent.
In certain embodiments:
WO 2021/234251 15 PCT/FR2021/050841
- the molar amount of compound of formula (IVa) or, respectively, of formula (IVb),
relative to the sum of the molar amounts of reaction solvent, compound of formula
(III), compound of formula (IVa) or, respectively, of formula (IVb), and Lewis acid
introduced into the reactor, is from 2% to 11%, and preferably 3% to 8%;
- the molar amount of compound of formula (III), relative to the sum of the molar
amounts of reaction solvent, compound of formula (III), compound of formula (IVa)
or, respectively, of formula (IVb), and Lewis acid introduced into the reactor, is
from 5% to 40%, and preferably from 8% to 25%;
- the molar amount of Lewis acid, relative to the sum of the molar amounts of
reaction solvent, compound of formula (III), compound of formula (IVa) or,
respectively, of formula (IVb), and Lewis acid introduced into the reactor, is from
4% to 45%, and preferably from 8% to 30%;
- the molar amount of compound of formula (III) relative to the molar amount of
compound of formula (IVa) or, respectively, of formula (IVb), introduced into the
reactor is from 2 to 6, and preferably from 2 to 4; and
- the molar amount of Lewis acid relative to the sum of the molar amounts of
compound of formula (III) and of compound of formula (IVa) or, respectively, of
formula (IVb), introduced into the reactor is from 0.25 to 2, and preferably from
0.3 to 1.5.
Preferably, the reaction mixture is stirred during at least part of the reaction step.
Thus, the reactor is preferably equipped with a stirring device such as a
mechanical stirrer (which may comprise, for example, one or more blades) or a
recirculation loop comprising a pump.
The reaction step between the compound of formula (III) and the compound of
formula (IVa) or, respectively, of formula (IVb), can be maintained, preferably with
stirring, for a certain period of time, in order to complete the reaction to the desired
extent.
Once the reaction is completed to the desired extent, the reaction mixture is
referred to as the “product mixture”. The product mixture comprises the desired
product of formula:
WO 2021/234251 16 PCT/FR2021/050841
[Chem 20]
O
O
O
R
0
H H
H
R
2
j
R
1
i
R
2
j
R
1
i
R
3
k
(I)
or, respectively, of formula:
[Chem 21]
(II)
in which i, j, k, l, 𝑅𝑖
1
, 𝑅𝑗
2
, 𝑅𝑘
3 and 𝑅𝑙
4 are defined as described above for the
compounds of formulae (III), (IVa) and (IVb).
Preferably, the temperature of the reaction mixture is less than or equal to 79°C
during at least a portion of the reaction. According to certain variants, the
temperature of the reaction mixture is less than or equal to 55°C, or less than or
equal to 50°C, or less than or equal to 40°C, or less than or equal to 30°C, or less
than or equal to 20°C, or less than or equal to 10°C, or less than or equal to 5°C,
or less than or equal to 0°C, or less than or equal to -5°C, or less than or equal to
-10°C.
The temperature must notably remain below the boiling point of the reaction
solvent. For this purpose, the reactor can, where appropriate, be operated under
pressure, so that the temperature in the reactor can reach a higher value without
O
H H
R
2
j
R
1
i
R
2
j
R
1
i
O
R
0
H
O
R
4
l
WO 2021/234251 17 PCT/FR2021/050841
boiling the solvent. In this case, the pressure in the reactor may range from 1 bar
(atmospheric pressure) to 6 bar, preferably from 1.5 bar to 3 bar.
As a variant and preferably, the reaction may be performed at atmospheric
pressure.
The temperature of the reaction mixture can remain almost constant during the
reaction. Alternatively, it may vary during the reaction.
Once the reaction has been completed to the desired extent, the process
according to the invention may comprise steps for recovering and purifying the
compound of formula (I) or, respectively, of formula (II) from the product mixture.
In addition to the desired product (I) or (II), the product mixture may notably
contain the Lewis acid, possibly unreacted reagents and possibly product(s)
derived from the competing reaction of the type shown in the reaction scheme
according to Figure 3.
In the embodiments in which the reagent of formula (IVa) is used, products derived
from the competing reaction have the formula:
[Chem 22]
(IX-i),
and/or
[Chem 23]
O
O
O
O
R
1
i R
2
R j
2
j
R
1
R i
3
k
(IX-ii)
in which i, j, k, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑘
3 are defined as described above for the compounds
of formulae (III) and (IVa).
In the embodiments in which the reagent of formula (IVb) is used, products derived
from the competing reaction have the formula:
O
O
O
O
R
1
i R
1
R i
2
j
R
2
R j
3
k
WO 2021/234251 18 PCT/FR2021/050841
[Chem 24]
(X-i),
and/or
[Chem 25]
(X-ii)
in which i, j, l, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑙
4 are defined as described above for the compounds
of formulae (III) and (IVb).
The competing reaction products of formulae (IX-i) and/or (IX-ii) or, respectively,
of formula (X-i) and/or (X-ii) are generally less soluble in the reaction solvent than
is the desired product of formula (I) or, respectively, of formula (II). Thus, whereas
the desired reaction product is generally totally or virtually totally dissolved in the
reaction solvent, the products derived from the competing reaction are generally
at least partially in the form of a precipitate.
Claims
1. A compound having the chemical formula:
[Chem 26]
O
O
O
R
0
H H
H
R
2
j
R
1
i
R
2
j
R
1
i
R
3
k
(I) or
[Chem 27]
(II)
in which:
R0 denotes: a charge +, -H or –OH;
i is an integer having a value from 0 to 3;
j, k and l are integers independently having a value from 0 to 4;
for any i, 𝑅𝑖
1
, for any j, 𝑅𝑗
2
, for any k, 𝑅𝑘
3
, for any l, 𝑅𝑙
4 are
independently chosen from the list consisting of:
alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester,
notably carboxylic ester, amide, notably primary amide, halogen,
imide, nitro and aliphatics comprising a nitro function, nitrile and
aliphatics comprising a nitrile function, carbonyl, alkali metal or
O
H H
R
2
j
R
1
i
R
2
j
R
1
i
O
R
0
H
O
R
4
l
WO 2021/234251 28 PCT/FR2021/050841
alkaline-earth metal sulfonate, alkyl sulfonate, alkali metal or
alkaline-earth metal phosphonate, amine, and quaternary
ammonium.
2. The compound as claimed in claim 1, in which said i, j, k and l are all equal to 0.
3. The compound as claimed in either of claims 1 and 2, in which R0
is: –OH.
4. The compound as claimed in either of claims 1 and 2, in which R0
is: –H.
5. The compound as claimed in either of claims 1 and 2, in which R0
is: +.
6. A process involving reacting a compound of formula (III) with a compound of
formula (IVa) or (IVb), in the presence of a Lewis acid;
compound (III) having the chemical formula:
[Chem 28]
compound (IVa) having the chemical formula:
[Chem 29]
and compound (IVb) having the chemical formula:
O
H H
H
R
2
j
R
1
i
R
3
k
O
O
Cl
Cl
WO 2021/234251 29 PCT/FR2021/050841
[Chem 30]
in which i, j, k, l, 𝑅𝑖
1
, 𝑅𝑗
2
, 𝑅𝑘
3 and 𝑅𝑙
4 are defined as in claim 1;
to obtain a mixture of products comprising a compound as claimed
in any one of claims 1 to 5.
7. The process as claimed in claim 6, in which said i, j, k and l are all equal to 0.
8. The process as claimed in either of claims 6 and 7, in which the reaction of the
compound of formula (III) with the compound of formula (IVa) or, respectively, of
formula (IVb) is performed in a reaction solvent;
said reaction solvent preferentially being an aprotic solvent;
said reaction solvent more preferably being chosen from the group consisting of:
dichloromethane, carbon disulfide, ortho-dichlorobenzene, metadichlorobenzene, para-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-
trichlorobenzene, ortho-difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane,
1,1,2,2-tetrachloroethane, tetrachloroethylene, dichloromethane, nitrobenzene
and a mixture thereof; and
said reaction solvent most preferably being ortho-dichlorobenzene.
9. The process as claimed in any one of claims 6 to 8, in which the Lewis acid is
chosen from the group consisting of: aluminum trichloride, aluminum tribromide,
antimony pentachloride, antimony pentafluoride, indium trichloride, gallium
trichloride, boron trichloride, boron trifluoride, zinc chloride, ferric chloride, stannic
chloride, titanium tetrachloride and molybdenum pentachloride;
preferentially in which the Lewis acid is chosen from the group consisting
of: aluminum trichloride, boron trichloride, aluminum tribromide, titanium
R
4
l
O
Cl
O
Cl
WO 2021/234251 30 PCT/FR2021/050841
tetrachloride, antimony pentachloride, ferric chloride, gallium trichloride
and molybdenum pentachloride; and
more preferably in which the Lewis acid is aluminum trichloride.
10. The process as claimed in any one of claims 6 to 9, in which the molar amount
of compound of formula (III) relative to the molar amount of compound of formula
(IVa) or, respectively, (IVb) is from 2 to 6, and preferably from 2 to 4.
11. The process as claimed in any one of claims 6 to 10, in which the molar
amount of Lewis acid relative to the sum of the molar amounts of compound of
formula (III) and of compound of formula (IVa) or, respectively, of formula (IVb) is
from 0.25 to 2, and preferably from 0.3 to 1.5.
12. The process as claimed in any one of claims 6 to 11, comprising
- at least one step of separating the compound of formula (I) or,
respectively, of formula (II) from at least one other species of the
product mixture; and, optionally
- at least one step of purifying the compound of formula (I) or,
respectively, of formula (II).
13. The process as claimed in claim 12, comprising a solid/liquid separation step
in order to recover a liquid comprising in major amount the compound of formula
(I) or, respectively, of formula (II), and a wet cake comprising in minor amount the
compound of formula (I) or, respectively, of formula (II).
14. A mixture of compounds comprising:
- the compound of formula (I) as claimed in any one of claims 1 to 5;
- a compound of formula:
[Chem 31]
(IX-i)
O
O
O
O
R
1
i R
1
R i
2
j
R
2
R j
3
k
WO 2021/234251 31 PCT/FR2021/050841
[Chem 32]
(IX-ii)
or a mixture thereof, in which i, j, k, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑘
3 are defined such as those
of compound (I); or
a mixture of compounds comprising:
- the compound of formula (II) as claimed in any one of claims 1 to 5;
- a compound of formula:
[Chem 33]
(X-i)
[Chem 34]
(X-ii)
or a mixture thereof, in which i, j, l, 𝑅𝑖
1
, 𝑅𝑗
2 and 𝑅𝑙
4 are defined such as those
of compound (II).
15. The mixture of compounds as claimed in claim 14, in which the compound of
formula (I) or, respectively, of formula (II) represents from 0.01 mol% to 10 mol%
relative to the total number of moles of the compounds of formulae (I), (IX-i) and
(IX-ii) or, respectively, of the compounds of formulae (II), (X-i) and (X-ii).
16. The mixture of compounds as claimed in claim 14, in which the compound of
formula (I) or, respectively, of formula (II) represents from 90 mol% to 99.99 mol%
O
O
O
O
R
1
i R
2
R j
2
j
R
1
R i
3
k
R
1
R i
2
j
O
O
R
1
i R
2
j
O
O
R
4
l
R
2
j R
1
i
O
O
R
1
R i
2
j
O
O
R
4
l
WO 2021/234251 32 PCT/FR2021/050841
relative to the total number of moles of the compounds of formulae (I), (IX-i) and
(IX-ii) or, respectively, of the compounds of formulae (II), (X-i) and (X-ii).
17. The use of a compound as claimed in any one of claims 1 to 5, as a
chromophore.
18. The use of a compound as claimed in any one of claims 1 to 5, as a freeradical generator.
19. The use of a compound as claimed in any one of claims 1 to 5, as an adhesion
promoter and/or coupling agent.