EP4100385A1 - Rearrangement of dimethylphenylacylates using zeolites - Google Patents
Rearrangement of dimethylphenylacylates using zeolitesInfo
- Publication number
- EP4100385A1 EP4100385A1 EP21703197.0A EP21703197A EP4100385A1 EP 4100385 A1 EP4100385 A1 EP 4100385A1 EP 21703197 A EP21703197 A EP 21703197A EP 4100385 A1 EP4100385 A1 EP 4100385A1
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- EP
- European Patent Office
- Prior art keywords
- rearrangement
- framework structure
- formula
- zeolite
- compound
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
Definitions
- the present invention relates to the rearrangement of dimethylphenyl- acylates.
- hydroxyaryl ketones in particular hydroxyacetophenones, and their derivatives bearing methyl groups on the aromatic ring are of great interest for many industrial applications. Such compounds are useful in the fields pharmaceutical, agricultural, animal and human nutrition, and perfumery industry, and in the manufacturing of polymeric materials, either as final compounds or as key intermediates.
- hydroxyaryl ketones are important synthons and intermediates in organic synthesis. Examples of such molecules that can be derived from hydroxyaryl ketones are the fungicide Metrafenone, the anti- spasmodic agent Flopropione, the anti-arrhythmic agent Propafenone, the vasodilator Etafenone and the anti-bacterial Aspidinol and their derivatives.
- hydroxyaryl ketones having two methyl groups bound to the aromatic ring.
- the Fries rearrangement of substituted phenyl esters generally leading to the formation of o- and p-hydroxy ketones is the most common and suitable process. See, for example: R. Martin, Organic Preparations and Procedures International, vol. 24(4), pp. 369-435 (1992); R. Martin, “Flandbook of Flydroxyacetophenones”, Kluwer Academic Publishers, Dordrecht, The Netherlands, (1997).
- the Fries rearrangement can by catalyzed by the use of Lewis or Bnzsnsted acids.
- the problem to be solved by the present invention is to offer a process for the formation of specific hydroxyaryl ketones having two methyl groups bound to the aromatic ring.
- the present invention relates to a process for the manufacturing a compound of the formula (I) by a rearrangement of a compound of formula (II) wherein
- R 1 and R 2 and R 3 represent either FI or CFh; with the proviso that exactly two of the substituents R 1 or R 2 or R 3 represent CFh; and
- R represents a C 1 -3 alkyl group, preferably a linear C 1 -3 alkyl group; characterized in that the rearrangement is performed in the presence of a zeolite having either the FAU framework structure or the *BEA framework structure.
- a “C x-y -alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a C-i- 3 -alkyl group is an alkyl group comprising 1 to 3 carbon atoms.
- the alkyl group can be linear or branched.
- -CFI(CFl3)-CFl 2 -CFl3 is considered as a C 4 -alkyl group.
- a respective dimethyl phenyl acylate having the position of the methyl groups at the 3 and 5 position such as 3,5-dimethylphenyl acetate
- R represents a methyl group.
- R 1 , R 2 and R 3 are preferred are the following combination of R 1 , R 2 and R 3 :
- the compounds of the formula (II) are known to the person skilled in the art and can be easily manufactured. Typically, the compounds of the formula (II) can be synthesized by esterification of the respective phenol (formula (ll-A)) with a suitable esterification agent (EA), such as the respective acyl halide or carboxylic acid anhydride:
- the compound of the formula (II) are 2,3-dimethylphenyl acetate, 2,4-dimethylphenyl acetate or 3,4-dimethylphenyl acetate, most preferred 2,3-dimethylphenyl acetate.
- Zeolites are known to be aluminosilicate minerals than can exhibit micro-, meso- and macro-porosity arising depending on their type and form. There exists a huge variety of natural and artificial zeolites which are classified by the
- IZA International Zeolite Association
- zeolites of a different framework are not or significantly less suited for the rearrangement reactions.
- Zeolyst International and Clariant offer commercially suitable zeolites having either the FAU framework structure or the *BEA framework structure, particularly suitable are the commercial zeolites CP814E, CBV30, CBV712, CBV720, CBV780 from Zeolyst International, and HCZB30, HCB150 from Clariant.
- zeolite having the FAU framework structure is CBV720, CBV780 from Zeolyst International.
- Preferred zeolite having the *BEA framework structure is FICZB30 from Clariant.
- the zeolites having the FAU framework structure or the *BEA framework structure have preferably a molar ratio of Si: Al in the range between 5 and 100, preferably between 6 and 60, more preferably between 10 and 45.
- zeolites having the FAU framework structure.
- the zeolites are preferably heated in air at a temperature of at least 400°C, preferably at least 500°C, for an extended time period of at least 4 hours, preferably at least 5 hours, prior to their use in the said process for manufacturing the compound of formula (I).
- the molar amount of the compound of the formula (II) is preferably in the range of 0.5 to 50 mmol, preferably 2 to 20 mmol, more preferably 5 to 10 mmol, per gram of the zeolite.
- the rearrangement reaction can be performed using the compound of formula (II) in neat or in a suitable solvent.
- the rearrangement is performed without a solvent.
- the rearrangement is performed in the presence of a solvent being selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, nitrated aliphatic hydrocarbons and nitrated aromatic hydrocarbons, preferably selected from the group consisting of C5- 12 alkanes, C6- 12 cycloalkanes and benzene carrying at least one C 1-4 alkyl group and/or at least one nitro group.
- a solvent being selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, nitrated aliphatic hydrocarbons and nitrated aromatic hydrocarbons, preferably selected from the group consisting of C5- 12 alkanes, C6- 12 cycloalkanes and benzene carrying at least one C 1-4 alkyl group and/or at least one nitro group.
- Particularly preferred as such suitable and preferred solvents are the solvents selected from the group consisting of toluene, n-decane, n-hexane, and nitrobenzene.
- the solvent is anhydrous.
- the rearrangement reaction is typically performed in a reaction capable of withstanding elevated pressures, such as a pressure tube reactor an autoclave.
- the rearrangement is performed at a temperature in the range of 80 - 300 °C, particularly of 100 - 200 °C, most preferably of 120 - 180 °C.
- the rearrangement is performed under an inert gas atmosphere, particularly under nitrogen or a noble gas atmosphere.
- the selectivity in the formation of the compound of the formula (I) is preferably higher than 44 %, more preferably higher than 60 %, most preferably higher than 70%.
- ester hydrolysis product i.e. phenol of formula (ll-A)
- the conversion is preferably at least 60%, more preferably higher than 65 %, even more preferably higher than 70 %, most preferably at least 90 %.
- the zeolite can be easily separated from the product of the above process, i.e. the compound of the formula (I) can be easily isolated.
- the invention relates to the starting mixture, i.e. the composition comprising at least
- composition particularly for compound of formula (II) as well for the zeolite have been disclosed in great detail when discussing above the process for the manufacturing a compound of the formula (I).
- This composition is suitable for the above rearrangement reaction to form compound of the formula (I).
- the invention relates also to the product mixture, i.e. the mixture after the rearrangement reaction, i. e. the composition comprising at least
- zeolite having either the FAU framework structure or the *BEA framework structure. Details for said composition, particularly for compound of formula (I) as well for the zeolite have been disclosed in great detail when discussing above the process for the manufacturing a compound of the formula (I).
- the compound of formula (I) can be easily isolated from this composition and can be used for further purposes.
- zeolite having either the FAU framework structure or the *BEA framework can be used for the chemical transformation reaction of a compound the formula (II) which leads to the formation of compound of formula (I).
- the present invention relates to the use of a zeolite having either the FAU framework structure or the *BEA framework structure in a chemical transformation reaction of a compound the formula (II).
- the present invention is further illustrated by the following experiments.
- All zeolites have a molar ratio of Si: Al of approximately 15.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a Fries rearrangement of specific dimethylphenylacylates to form the desired respective hydroxyaryl ketones having two methyl groups bound to the aromatic ring. It has been found that the process is surprisingly very specific in view of the number and position of the methyl group(s) bound to the aromatic ring.
Description
REARRANGEMENT OF DIMETHYLPHENYLACYLATES USING ZEOLITES
Technical Field
The present invention relates to the rearrangement of dimethylphenyl- acylates.
Background of the invention
The class of hydroxyaryl ketones, in particular hydroxyacetophenones, and their derivatives bearing methyl groups on the aromatic ring are of great interest for many industrial applications. Such compounds are useful in the fields pharmaceutical, agricultural, animal and human nutrition, and perfumery industry, and in the manufacturing of polymeric materials, either as final compounds or as key intermediates. In addition, hydroxyaryl ketones are important synthons and intermediates in organic synthesis. Examples of such molecules that can be derived from hydroxyaryl ketones are the fungicide Metrafenone, the anti- spasmodic agent Flopropione, the anti-arrhythmic agent Propafenone, the vasodilator Etafenone and the anti-bacterial Aspidinol and their derivatives.
Particularly interesting are hydroxyaryl ketones having two methyl groups bound to the aromatic ring. Of the many transformations known to prepare such hydroxyaryl ketones, the Fries rearrangement of substituted phenyl esters generally leading to the formation of o- and p-hydroxy ketones is the most common and suitable process. See, for example: R. Martin, Organic Preparations and Procedures International, vol. 24(4), pp. 369-435 (1992); R. Martin, “Flandbook of Flydroxyacetophenones”, Kluwer Academic Publishers, Dordrecht, The Netherlands, (1997).
The Fries rearrangement can by catalyzed by the use of Lewis or Bnzsnsted acids.
A. Vogt et al., Applied Catalysis A: General 123 (1995), 37-45, discloses that phenyl acetate and p-tolyl acetate can be rearranged over diverse zeolitic catalysts and that a variety of side products are formed.
Zeolites are particularly used as catalysts for a range of transformations including in the petrochemical industry, for instance in fluid catalytic cracking and hydrocracking. Further details can be found in the review W. Holderich et al. , Angew. Chem. Int. Ed. Engl. 27 (1988), 226-246.
Summary of the invention
Therefore, the problem to be solved by the present invention is to offer a process for the formation of specific hydroxyaryl ketones having two methyl groups bound to the aromatic ring.
Surprisingly, it has been found that the process according to claim 1 allows the preparation of the desired compounds in a very high selectivity and at high conversion and in a particularly high yield.
It has been observed that the respective phenols, which are the hydrolysis product of the phenylic esters used as starting material for the Fries rearrangement, are formed only to a very low degree by the present process.
Particularly, it has been found that the process is surprisingly very specific in view of the number and position of the methyl group(s) bound to the aromatic ring. Further aspects of the invention are subject of further independent claims.
Particularly preferred embodiments are subject of dependent claims.
Detailed description of the invention
In a first aspect the present invention relates to a process for the manufacturing a compound of the formula (I) by a rearrangement of a compound of formula (II)
wherein
R1 and R2 and R3 represent either FI or CFh; with the proviso that exactly two of the substituents R1 or R2 or R3 represent CFh; and
R represents a C1-3 alkyl group, preferably a linear C1-3 alkyl group; characterized in that the rearrangement is performed in the presence of a zeolite having either the FAU framework structure or the *BEA framework structure.
For sake of clarity, some terms as been used in the present document are defined as follows: In the present document, a “Cx-y-alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a C-i-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example -CFI(CFl3)-CFl2-CFl3 is considered as a C4-alkyl group.
In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.
It is important to realize that the present invention relates to compounds of formula (II) resp. (I), in which exactly two methyl groups are bound to the aromatic ring. It has been observed that in the case of the compounds having 3 methyl groups (i.e. R1 = R2 = R3 = CFh), the desired rearrangement reaction does not, or at least not substantially enough, take place.
It, furthermore, is important to realize that the position of the two methyl group on the aromatic ring matters. For example, a respective dimethyl phenyl acylate having the position of the methyl groups at the 3 and 5 position, such as 3,5-dimethylphenyl acetate,
- hence not covered by formula (II) - has been observed not, or at least not substantially enough, to show the desired rearrangement reaction.
As a consequence, it has been surprisingly found that not only the type of zeolite but also the specific substrate, i.e. compound of formula (II), used is essential for the present invention.
It is particularly preferred that R represents a methyl group.
Particuarly, preferred are the following combination of R1, R2 and R3:
- R1 = R2 = CFhand R3 = H - R1 = R3 = CFhand R2 = H - R2 = R3 = CFhand R1 = H.
In a preferred embodiment, R1 = R2 = CFhand R3 = FI. It is mostly preferred that R1 = R2 = CFhand R3 = FI, and that R is a methyl group.
The compounds of the formula (II) are known to the person skilled in the art and can be easily manufactured. Typically, the compounds of the formula (II) can be synthesized by esterification of the respective phenol (formula (ll-A)) with a suitable esterification agent (EA), such as the respective acyl halide or carboxylic acid anhydride:
Preferably, the compound of the formula (II) are 2,3-dimethylphenyl acetate, 2,4-dimethylphenyl acetate or 3,4-dimethylphenyl acetate, most preferred 2,3-dimethylphenyl acetate.
Zeolites
Zeolites are known to be aluminosilicate minerals than can exhibit micro-, meso- and macro-porosity arising depending on their type and form. There exists a huge variety of natural and artificial zeolites which are classified by the
International Zeolite Association (IZA) according to their framework structure by a defined three letter designation which are compiled and described in detail in Ch. Baerlocher et al. 'Atlas of Zeolite Framework Types", 5th edition, Elsevier, Amsterdam 2001.
The above rearrangement reaction takes place in the presence of a zeolite having either the FAU framework structure or the *BEA framework structure. It has been surprisingly observed that zeolites of a different framework are not or significantly less suited for the rearrangement reactions.
Zeolyst International and Clariant offer commercially suitable zeolites having either the FAU framework structure or the *BEA framework structure, particularly suitable are the commercial zeolites CP814E, CBV30, CBV712, CBV720, CBV780 from Zeolyst International, and HCZB30, HCB150 from Clariant. Preferred as zeolite having the FAU framework structure is CBV720, CBV780 from Zeolyst International. Preferred zeolite having the *BEA framework structure is FICZB30 from Clariant.
The zeolites having the FAU framework structure or the *BEA framework structure have preferably a molar ratio of Si: Al in the range between 5 and 100, preferably between 6 and 60, more preferably between 10 and 45.
Particularly preferred are zeolites having the FAU framework structure.
The zeolites are preferably heated in air at a temperature of at least 400°C, preferably at least 500°C, for an extended time period of at least 4 hours, preferably at least 5 hours, prior to their use in the said process for manufacturing the compound of formula (I).
The molar amount of the compound of the formula (II) is preferably in the range of 0.5 to 50 mmol, preferably 2 to 20 mmol, more preferably 5 to 10 mmol, per gram of the zeolite.
The rearrangement reaction can be performed using the compound of formula (II) in neat or in a suitable solvent.
Flence, in one preferred embodiment, the rearrangement is performed without a solvent.
In another, even more, preferred embodiment, the rearrangement is performed in the presence of a solvent being selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, nitrated aliphatic hydrocarbons and nitrated aromatic hydrocarbons, preferably selected from the group consisting
of C5-12 alkanes, C6-12 cycloalkanes and benzene carrying at least one C1-4 alkyl group and/or at least one nitro group.
Particularly preferred as such suitable and preferred solvents are the solvents selected from the group consisting of toluene, n-decane, n-hexane, and nitrobenzene.
Preferably, the solvent is anhydrous.
The rearrangement reaction is typically performed in a reaction capable of withstanding elevated pressures, such as a pressure tube reactor an autoclave.
It is further preferred that the rearrangement is performed at a temperature in the range of 80 - 300 °C, particularly of 100 - 200 °C, most preferably of 120 - 180 °C.
It is further preferred that the rearrangement is performed under an inert gas atmosphere, particularly under nitrogen or a noble gas atmosphere.
It has been shown that the above process is very efficient and specific, i.e. it has been shown that it is possible to get very high conversion and a very high selectivity.
Particularly, it has been shown that the selectivity in the formation of the compound of the formula (I) is preferably higher than 44 %, more preferably higher than 60 %, most preferably higher than 70%.
Particularly it has been shown that the formation of the ester hydrolysis product, i.e. phenol of formula (ll-A), is strongly reduced as compared with reactions used other types of zeolite or other substrates. Particularly, it has been shown also shown that the conversion is preferably at least 60%, more preferably higher than 65 %, even more preferably higher than 70 %, most preferably at least 90 %.
The zeolite can be easily separated from the product of the above process, i.e. the compound of the formula (I) can be easily isolated.
In a further aspect, the invention relates to the starting mixture, i.e. the composition comprising at least
- a compound of the formula (II)
and - a zeolite having either the FAU framework structure or the *BEA framework structure.
Details for said composition, particularly for compound of formula (II) as well for the zeolite have been disclosed in great detail when discussing above the process for the manufacturing a compound of the formula (I). This composition is suitable for the above rearrangement reaction to form compound of the formula (I).
In a further aspect, the invention relates also to the product mixture, i.e. the mixture after the rearrangement reaction, i. e. the composition comprising at least
- a compound of the formula (I)
and
- a zeolite having either the FAU framework structure or the *BEA framework structure.
Details for said composition, particularly for compound of formula (I) as well for the zeolite have been disclosed in great detail when discussing above the process for the manufacturing a compound of the formula (I). The compound of formula (I) can be easily isolated from this composition and can be used for further purposes.
As shown above, an essential aspect of the present invention is that zeolite having either the FAU framework structure or the *BEA framework can be used for the chemical transformation reaction of a compound the formula (II) which leads to the formation of compound of formula (I).
Hence, the present invention relates to the use of a zeolite having either the FAU framework structure or the *BEA framework structure in a chemical transformation reaction of a compound the formula (II).
Examples
The present invention is further illustrated by the following experiments.
Zeolites
The following zeolites have been used for the experiments:
MFI: CBV30241, Zeolyst International: MFI framework structure FAU: CBV720, Zeolyst International: FAU framework structure *BEA: HCZB30, Clariant: *BEA framework structure
All zeolites have a molar ratio of Si: Al of approximately 15.
All zeolites were calcined in static air at 823 K (heating rate = 5 K min-1) for 5 h prior to the catalytic tests.
General procedure for the following rearrangement reactions
The following rearrangement reactions were all carried out in an identical manner:
The rearrangement was carried out in pressure tube reactors (V = 21 cm3, Ace Glass) equipped with a magnetic stirrer and oil bath. The pre-dried catalyst (340 mg, 573 K, 0.1 mbar, 12 h), and substrate (2.5 mmol) in 10 cm3 anhydrous toluene were added into the reactor. After replacing air with Ar three times (PanGas, purity 5.0), the reactor was heated to T = 423 K at autogenous pressure for 6 h. The reaction mixture was quenched with ice-water, and 0.01 cm3 of the reaction mixture was added into 1 cm3 acetonitrile (99.9%, AcroSeal) for further analysis. Samples were analyzed using an Agilent 1260 Infinity HPLC equipped with an Agilent Zorbax C18 column and both DAD and RID detectors. The concentrations of substrates and products were calibrated with reference to the respective pure standards. The conversion (X,) and the product selectivity (S,) were calculated according to equations (1) and (2), respectively. Equation (1) Equation (2)
where n°s and n\ are the moles of substrate before and after the reaction, respectively, while n) is the mole of product i. The yield is calculated as the product of conversion and selectivity of the desired product.
Rearrangement of 2, 3-dimethyl phenylacetate ((II): R1=R2=CH3and 2,3-dimethyl phenylacetate has been used as substrate for the rearrangement reaction as described above.
DP1. Desired product: Formula (I): R1=R2=CH3and R3=H, R=CH3) USP1. Undesired Side Product: Formula (ll-A): R1=R2=CH3 and R3=H)
The results show that the zeolites having the FAU and *BEA framework structure show excellent conversions combined with high selectivity in the desired product of rearrangement reaction whereas the undesired products are formed only in significantly lower amounts as compared when used the zeolite having the MFI type.
Rearrangement of 3, 4-dimethyl phenylacetate ((II): R1=H, R=CFI3)
3,4-dimethyl phenylacetate has been used as substrate for the rearrangement reaction as described above. DP2: Desired product: Formula (I): R2=R3=CH3and R1=H, R=CH3)
USP2. Undesired Side Product: Formula (ll-A): R2=R3=CH3 and R1=H)
The results show that the zeolites having the FAU and *BEA framework structure show excellent conversions combined with high selectivity in the desired product of rearrangement reaction whereas the undesired products are formed only in significantly lower amounts as compared when used the zeolite having the MFI type.
Rearrangement of 2, 4-dimethyl phenylacetate ((II): R1=R3=CH3and R2=H, R=CH3)
2,4-dimethyl phenylacetate has been used as substrate for the rearrangement reaction as described above. DP3. Desired product: Formula (I): R1=R3=CH3and R2=H, R=CH3)
USP3. Undesired Side Product: Formula (ll-A): R1=R3=CFl3and R2=FI)
The results show that the zeolites having the FAU and *BEA framework structure show excellent conversions combined with high selectivity in the desired product of rearrangement reaction whereas the undesired products are formed only in significantly lower amounts as compared when used the zeolite having the MFI type.
Rearrangement of 3,5-dimethyl phenylacetate (Comparison)
3,5-dimethyl phenylacetate has been used as substrate for the rearrangement reaction as described above.
3,5-dimethyl phenylacetate
DP3. Desired product:
USP3. Undesired Side Product:
The results show that for this substrate (having two methyl groups on the benzene ring, but in a different substitution pattern as compounds of formula (II) resp. (I)), all the zeolites have a very low conversion and a high amounts of undesired products are formed.
Rearrangement of 2,3,5-trimethylphenyl acetate (comparison) 2,3,5-trimethylphenyl acetate has been used as substrate for the rearrangement reaction as described above.
2,3,5-trimethylphenyl acetate
DP4. Desired product:
USP4. Undesired Side Product:
The results show that for this substrate (having three methyl groups on the benzene ring), all the zeolites tested gave low conversions and formation of large amounts of the undesired product. No formation of the desired product has been found.
Rearrangement of 4-methyl phenylacetate (comparison)
4-methyl phenylacetate (=p-tolyl acetophenone) has been used as substrate for the rearrangement reaction as described above.
4-methyl phenylacetate
DP5. Desired product:
USP5. Undesired Side Product:
OH
The results show that for this substrate (having one methyl group on the benzene ring), zeolites of the FAU and *BEA framework structure show a moderate to good conversion, however, the respective selectivity in the desired product at a respective conversion is less than when using the substrate of formula (II).
Claims
1 . A process for the manufacturing a compound of the formula (I) by a rearrangement of a compound of formula (II)
wherein
R1 and R2 and R3 represent either H or CFh; with the proviso that exactly two of the substituents R1 or R2 or R3 represent Chh; and
R represents a C1-3 alkyl group, preferably a linear C1-3 alkyl group; characterized in that the rearrangement is performed in the presence of a zeolite having either the FAU framework structure or the *BEA framework structure.
2. The process according to claim 1 , characterized in that R= CH3.
3. The process according to anyone of the preceding claims characterized in that molar ratio of Si: Al of the zeolite is in the range between 5 and 100, preferably between 6 and 60, more preferably between 10 and 45.
4. The process according to anyone of the preceding claims characterized in that the molar amount of the compound of the formula (II) is in the range of 0.5 to 50 mmol, preferably 2 to 20 mmol, more preferably 5 to 10 mmol, per gram of the zeolite.
5. The process according to anyone of the preceding claims characterized in that the rearrangement is performed in the presence of a solvent being selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, nitrated aliphatic hydrocarbons and nitrated aromatic hydrocarbons, preferably selected from the group consisting of C5-12 alkanes,
Ce-12 cycloalkanes and benzene carrying at least one C1-4 alkyl group and/or at least one nitro group.
6. The process according to anyone of the preceding claims 1 to 4 characterized in that the rearrangement is performed without a solvent.
7. The process according to anyone of the preceding claims characterized in that the rearrangement is performed at a temperature in the range of 80 - 300 °C, particularly of 100 - 200 °C, most preferably of 120 - 180 °C.
8. The process according to anyone of the preceding claims characterized in that the rearrangement is performed under an inert gas atmosphere, particularly under nitrogen or a noble gas atmosphere.
9. The process according to anyone of the preceding claims characterized in that R1 = R2 = Chhand R3 = H, and that R is particularly a methyl group.
10. The process according to anyone of the preceding claims characterized in that the rearrangement is performed in the presence of a zeolite having the FAU framework structure.
11. Composition comprising at least
- a compound of the formula (II)
and
- a zeolite having either the FAU framework structure or the *BEA framework structure; wherein
R1 and R2 and R3 represent either FI or CFh; with the proviso that exactly two of the substituents R1 or R2 or R3 represent CFh; and R represents a C1-3 alkyl group, preferably a linear C1-3 alkyl group.
12. Composition comprising at least - a compound of the formula (I)
and
- a zeolite having either the FAU framework structure or the *BEA framework structure; wherein
R1 and R2 and R3 represent either FI or CFI3; with the proviso that exactly two of the substituents R1 or R2 or R3 represent CFI3; and
R represents a C1-3 alkyl group, preferably a linear C1-3 alkyl group.
13. The composition according to claim 11 or 12, characterized in that R = CFI3.
14. The composition according to anyone of the preceding claims 11-13, characterized in that the zeolite has the FAU framework structure.
15. Use of a zeolite having either the FAU framework structure or the *BEA framework structure in a chemical transformation reaction of a compound the formula (II) into the compound of formula (I)
wherein
R1 and R2 and R3 represent either FI or CFh; with the proviso that exactly two of the substituents R1 or R2 or R3 represent CFh; and
R represents a C1-3 alkyl group, preferably a linear C1-3 alkyl group.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20155082 | 2020-02-03 | ||
| PCT/EP2021/052341 WO2021156214A1 (en) | 2020-02-03 | 2021-02-01 | Rearrangement of dimethylphenylacylates using zeolites |
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| EP4100385A1 true EP4100385A1 (en) | 2022-12-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1128549A (en) * | 1978-12-14 | 1982-07-27 | Lewis B. Young | Production of 3-methylphenol |
| US5679865A (en) * | 1992-05-06 | 1997-10-21 | Technische Universiteit Delft | Process for the preparation of polyhydroxybenzophenones |
| DE19637976A1 (en) * | 1996-09-18 | 1998-03-19 | Wolfgang Prof Dr Hoelderich | Acylated phenol preparation by Fries rearrangement |
| KR100618367B1 (en) * | 2002-09-12 | 2006-08-30 | 가부시키가이샤 구라레 | Process for production of 4-alkylphenols |
| DE102004005318A1 (en) * | 2004-02-04 | 2005-08-25 | Bayer Cropscience Ag | Process for the preparation of 2,5-dimethylphenylacetic acid |
| JP6782597B2 (en) * | 2016-09-28 | 2020-11-11 | 上野製薬株式会社 | Method for Producing 2-Ethyl-4'-Hydroxyhexanophenone |
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- 2021-02-01 CN CN202180011736.7A patent/CN115023413B/en active Active
- 2021-02-01 WO PCT/EP2021/052341 patent/WO2021156214A1/en not_active Ceased
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| Publication number | Publication date |
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| CN115023413A (en) | 2022-09-06 |
| WO2021156214A1 (en) | 2021-08-12 |
| CN115023413B (en) | 2024-11-15 |
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