WO2016128422A1 - Process of production of cyclo-dehydrolinalool (i) - Google Patents
Process of production of cyclo-dehydrolinalool (i) Download PDFInfo
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- WO2016128422A1 WO2016128422A1 PCT/EP2016/052762 EP2016052762W WO2016128422A1 WO 2016128422 A1 WO2016128422 A1 WO 2016128422A1 EP 2016052762 W EP2016052762 W EP 2016052762W WO 2016128422 A1 WO2016128422 A1 WO 2016128422A1
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- XSDYMDMXNRPZHU-UHFFFAOYSA-N CC(C)(CCC1)OC1(C)C#C Chemical compound CC(C)(CCC1)OC1(C)C#C XSDYMDMXNRPZHU-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Definitions
- the present invention relates to an improved process of producing cyclo- dehydrolinalool.
- Cyclo-dehydrolinalool (c-DLL) can be used for example as an intermediate in the production of 2-vinyl-2,6,6-trimethyl-3,4,5,6-tetrahydro-2H-pyran, which is also known as limetol ® (compound of formula (III))
- non-polymeric it is meant that the acid, which is used as catalyst does not comprise a large molecule or macromolecule, which are composed of many repeated subunits. More specifically the catalysts are no ion exchangers (ion exchange resins such as for example zeolites and montmorillonite).
- the present invention relates to a process (P) for the production of the compound of formula (I)
- non-polymeric acid containing one or more sulfur (VI) atom as a catalyst, has also -for example- the following advantages:
- the process according to the present invention is always carried in the presence of at least one non-polymeric acid containing one or more sulfur (VI) atom as a catalyst.
- the sulfur atom (or the sulfur atoms) is usually and preferably part of -SO3 " or SO 4 ⁇
- the acid has a pK a value (measured in water) of less than 3, more preferably less than 2, or even less than 1 .
- the pK a value is the well-known value of the strength of an acid.
- a strong acid is almost completely dissociated in aqueous solution, to the extent that the concentration of the undissociated acid becomes undetectable.
- pKa values for strong acids can, however, be estimated by theoretical means or by extrapolating from measurements in non-aqueous solvents in which the dissociation constant is smaller, such as acetonitrile and dimethylsulfoxide.
- the present invention also relates to a process (P1 ), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom has a pK a value (measured in water) of less than 3.
- the present invention also relates to a process ( ⁇ 1 '), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom has a pK a value (measured in water) of less than 2. Therefore the present invention also relates to a process (P1 "), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom as a catalyst has a pK a value (measured in water) of less than 1 .
- the acid which is used as a catalyst can be inorganic as well as organic (as well as mixtures of both).
- the present invention also relates to a process (P2), which is the process (P), (P1 ), ( ⁇ 1 ') or (P1 ") wherein the non-polymeric acid containing one or more sulfur (VI) atom is inorganic.
- the present invention also relates to a process ( ⁇ 2'), which is the process (P), (P1 ), ( ⁇ 1 ') or (P1 ") wherein a mixture of inorganic non-polymeric acids containing one or more sulfur (VI) atom is used.
- the present invention also relates to a process (P3), which is the process (P), (P1 ), (P1 ') or (P1 ") wherein the non-polymeric acid containing one or more sulfur (VI) atom is organic.
- the present invention also relates to a process ( ⁇ 3'), which is the process (P), (P1 ), (P1 ') or (P1 ") wherein a mixture of organic non-polymeric acids containing one or more sulfur (VI) atom is used. Therefore the present invention also relates to a process (P4), which is the process (P), (P1 ), ( ⁇ 1 ') or (P1 ") wherein a mixture of at least one organic non- polymeric acids containing one or more sulfur (VI) atom and of at least one inorganic non-polymeric acids containing one or more sulfur (VI) atom is used.
- the organic acids which are used in the process according to the present invention can aliphatic as well as aromatic.
- the present invention also relates to a process (P5), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P3), ( ⁇ 3') or (P4), wherein at least one organic acid is aliphatic.
- the present invention also relates to a process ( ⁇ 5'), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P3), ( ⁇ 3') or (P4), wherein at least one organic acid is aromatic.
- the present invention also relates to a process (P5"), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P3), ( ⁇ 3') or (P4), wherein the organic acid is saturated as well unsaturated or unsaturated.
- Suitable inorganic acids are i.e.H 2 SO 4 and HSO3CI .
- the present invention also relates to a process (P6), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P2), ( ⁇ 2') or (P4), wherein the inorganic acid is chosen from the group consisting of H 2 SO 4 and HSO3CI .
- aromatic organic acids examples include i.e. p-toluenesulfonic acid, 4- chlorobenzenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.
- Example of a suitable aliphatic organic acid is methanesulfonic acid.
- the present invention also relates to a process (P7), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P3), ( ⁇ 3'), (P4), (P5), ( ⁇ 5') or (P5"), wherein the organic acid is chosen from the group consisting of p-toluenesulfonic acid, 4- chlorobenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid and methanesulfonic acid.
- the amount of the acid which is necessary to obtain the product in excellent yields are low (in comparison to the processes known from the prior art).
- a ratio of 20:1 of compound (II) to acid is used.
- the ratio is weight related.
- the ratio can be as low as 100:1 .
- a suitable ratio of compound (II) to acid is from 20:1 to 100:1 .
- the present invention also relates to a process (P8), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P2), ( ⁇ 2'), (P3), ( ⁇ 3'), (P4), (P5), ( ⁇ 5'), (P5"), (P6) or (P7), wherein a ratio of 20:1 to 100:1 of compound (II) to acid is used.
- a further embodiment of the present invention is that the process according to the present invention can be carried in an inert solvent or in a mixture of inert solvents.
- the present invention also relates to a process (P9), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P2), ( ⁇ 2'), (P3), ( ⁇ 3'), ( ⁇ 4), ( ⁇ 5), ( ⁇ 5'), ( ⁇ 5"), ( ⁇ 6), ( ⁇ 7) or ( ⁇ 8), wherein the process is carried out without any solvents.
- the present invention also relates to a process (P10), which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P2), ( ⁇ 2'), (P3), ( ⁇ 3'), ( ⁇ 4), ( ⁇ 5), ( ⁇ 5'), ( ⁇ 5"), ( ⁇ 6), ( ⁇ 7) or ( ⁇ 8), wherein the process is carried out in an inert solvent or a mixture of inert solvents.
- the inert solvents are usually aliphatic hydrocarbons or aromatic hydrocarbons. These aliphatic hydrocarbons or aromatic hydrocarbons need to be liquid at the reaction conditions.
- the hydrocarbons can be linear, branched and/or cyclic.
- the present invention relates to a process (P1 1 ), which is the process (P10), wherein the solvent (or solvents) is chosen from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons. Suitable solvents are for example n-hexane, cyclohexane, n-heptane, pentane and toluene. Therefore the present invention relates to a process (P12), which is the process (P10) or (P1 1 ), wherein the solvent (or more than one) is chosen from the group consisting of n-hexane, cyclohexane, n-heptane, pentane and toluene.
- the amount of the solvent (or solvent mixture) is not critical for the invention. It is used in usual amounts.
- the solvents (or solvent mixture) can be added in an equimolar amounts in regard to DLL (compound of formula (II)). But it is also possible to use more as well to use less solvent (or solvent mixture).
- a preferred range of the ratio of solvent (or solvent mixture) to DLL is 3:1 to 0.5 :1 . The ratio is weight related.
- the present invention relates to a process (P13), which is the process (P10), (P1 1 ) or (P12), wherein the range of the ratio of solvent (or solvent mixture) to compound of formula (II) is 3:1 to 0.5 :1 .
- the process according to the present invention is usually carried out at elevated temperatures. It is usually carried out at a temperature of between 30°C and 75°C (preferably 40°C - 70°C).
- the present invention relates to a process (P14), which is the process which is the process (P), (P1 ), ( ⁇ 1 '), (P1 "), (P2), ( ⁇ 2'), (P3), ( ⁇ 3'), (P4), (P5), ( ⁇ 5'), (P5"), (P6), (P7), (P8), (P9), (P10), (P1 1 ), (P12) or (P13), wherein the process according to the present invention is carried out at a temperature of between 30°C and 75°C (preferably 40°C - 70°C).
- the c-DLL (compound of formula (I)) obtained by the process according to present invention can be purified by using commonly known processes. As stated above the c-DLL is then used to produce 2-vinyl-2,6,6-trimethyl-3,4,5,6- tetrahydro-2H-pyran via hydrogenation.
- the hydrogenation of c-DLL can be done by using commonly known hydrogenation processes. Usually it is done by catalytic hydrogenation (i.e. with Lindlar catalysts):
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to an improved process of producing cyclo-dehydrolinalool by the cyclization of the compound of formula (II).
Description
PROCESS OF PRODUCTION OF CYCLO-DEHYDROLINALOOL (I)
The present invention relates to an improved process of producing cyclo- dehydrolinalool.
Cyclo-dehydrolinalool (c-DLL) can be used for example as an intermediate in the production of 2-vinyl-2,6,6-trimethyl-3,4,5,6-tetrahydro-2H-pyran, which is also known as limetol® (compound of formula (III))
Due to the importance of 2-vinyl-2,6,6-trimethyl-3,4,5,6-tetrahydro-2H-pyran, there is always a need for improved methods for its production as well as the production of its intermediates.
A way to obtain 2-vinyl-2,6,6-trimethyl-3,4,5,6-tetrahydro-2H-pyran is the reduction of cyclo-dehydrolinalool (compound of formula (I))
by hydrogenation (for example by using a Lindlar-type catalyst).
This hydrogenation can be carried out with excellent yield and therefore, it was a goal of the present invention to find an improved method to produce cyclo- dehydrolinalool (c-DLL). It is known form the prior art to produce c-DLL from dehydrolinalool (compound of formula (II))
In BE852918 it is disclosed that the cyclisation of dehydrolinalool (DLL) is carried out in the presence of polyphosphoric acid. In the reaction mixture, the molar ratio of DLL to polyphosphoric acid is 10:1 . The yield of c-DLL is up to 67.2 %. As stated above, due to the importance of c-DLL, there is a need for improved production of c-DLL.
Surprisingly, it was found that when the cyclization of DLL is carried in the presence of
(i) at least one non-polymeric acid containing one or more sulfur (VI) atom as a catalyst and
(ii) optionally at least one inert solvent.
By the term "non-polymeric" it is meant that the acid, which is used as catalyst does not comprise a large molecule or macromolecule, which are composed of
many repeated subunits. More specifically the catalysts are no ion exchangers (ion exchange resins such as for example zeolites and montmorillonite).
Therefore the present invention relates to a process (P) for the production of the compound of formula (I)
characterized in that the reaction is carried out in the presence of
(i) at least one non-polymeric acid containing one or more sulfur (VI) atom as a catalyst. The product of process (P), which is the compound of formula (I), is obtained in excellent yields. Usually more than 90% yield is obtained. This is a surprising and significant improvement in view of the prior art.
Furthermore the use of the non-polymeric acid containing one or more sulfur (VI) atom as a catalyst, has also -for example- the following advantages:
· no activation of the catalyst is needed (in contrast to the ion exchangers)
• homogenous conditions can be chosen
• less catalyst needed (in contrast to the prior art)
• ion exchangers can suffer (they can be damaged) during the reaction (heat).
Additionally in case that at least one inert solvent is used, there is a good heat exchange (allows safe reaction conditions in industry, when produced in industrial scale) and the end product can be separated very easily. Therefore the new process has many advantages, which are important, over the known process to produce the compound of formula (I)
The process according to the present invention is always carried in the presence of at least one non-polymeric acid containing one or more sulfur (VI) atom as a catalyst.
The sulfur atom (or the sulfur atoms) is usually and preferably part of -SO3" or SO4\ Preferably the acid has a pKa value (measured in water) of less than 3, more preferably less than 2, or even less than 1 .
The pKa value is the well-known value of the strength of an acid. The larger the value of pKa, the smaller the extent of dissociation at any given pH-value that is, the weaker the acid. A strong acid is almost completely dissociated in aqueous solution, to the extent that the concentration of the undissociated acid becomes undetectable. pKa values for strong acids can, however, be estimated by theoretical means or by extrapolating from measurements in non-aqueous solvents in which the dissociation constant is smaller, such as acetonitrile and dimethylsulfoxide.
Therefore the present invention also relates to a process (P1 ), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom has a pKa value (measured in water) of less than 3.
Therefore the present invention also relates to a process (Ρ1 '), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom has a pKa value (measured in water) of less than 2.
Therefore the present invention also relates to a process (P1 "), which is the process (P), wherein the non-polymeric acid containing one or more sulfur (VI) atom as a catalyst has a pKa value (measured in water) of less than 1 .
The acid, which is used as a catalyst can be inorganic as well as organic (as well as mixtures of both).
Therefore the present invention also relates to a process (P2), which is the process (P), (P1 ), (Ρ1 ') or (P1 ") wherein the non-polymeric acid containing one or more sulfur (VI) atom is inorganic.
Therefore the present invention also relates to a process (Ρ2'), which is the process (P), (P1 ), (Ρ1 ') or (P1 ") wherein a mixture of inorganic non-polymeric acids containing one or more sulfur (VI) atom is used.
Therefore the present invention also relates to a process (P3), which is the process (P), (P1 ), (P1 ') or (P1 ") wherein the non-polymeric acid containing one or more sulfur (VI) atom is organic.
Therefore the present invention also relates to a process (Ρ3'), which is the process (P), (P1 ), (P1 ') or (P1 ") wherein a mixture of organic non-polymeric acids containing one or more sulfur (VI) atom is used. Therefore the present invention also relates to a process (P4), which is the process (P), (P1 ), (Ρ1 ') or (P1 ") wherein a mixture of at least one organic non- polymeric acids containing one or more sulfur (VI) atom and of at least one inorganic non-polymeric acids containing one or more sulfur (VI) atom is used.
The organic acids which are used in the process according to the present invention can aliphatic as well as aromatic. Furthermore the acid can be saturated as well unsaturated. Therefore the present invention also relates to a process (P5), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P3), (Ρ3') or (P4), wherein at least one organic acid is aliphatic.
Therefore the present invention also relates to a process (Ρ5'), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P3), (Ρ3') or (P4), wherein at least one organic acid is aromatic.
Therefore the present invention also relates to a process (P5"), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P3), (Ρ3') or (P4), wherein the organic acid is saturated as well unsaturated or unsaturated.
Examples of suitable inorganic acids are i.e.H2SO4 and HSO3CI .
Therefore the present invention also relates to a process (P6), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P2), (Ρ2') or (P4), wherein the inorganic acid is chosen from the group consisting of H2SO4 and HSO3CI .
Examples of suitable aromatic organic acids are i.e. p-toluenesulfonic acid, 4- chlorobenzenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.
Example of a suitable aliphatic organic acid is methanesulfonic acid.
Therefore the present invention also relates to a process (P7), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P3), (Ρ3'), (P4), (P5), (Ρ5') or (P5"), wherein the organic acid is chosen from the group consisting of p-toluenesulfonic acid, 4- chlorobenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid and methanesulfonic acid.
As stated above the amount of the acid which is necessary to obtain the product in excellent yields are low (in comparison to the processes known from the prior art). Usually a ratio of 20:1 of compound (II) to acid is used. The ratio is weight related. Preferably the ratio can be as low as 100:1 . This means that a suitable ratio of compound (II) to acid is from 20:1 to 100:1 .
Therefore the present invention also relates to a process (P8), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P2), (Ρ2'), (P3), (Ρ3'), (P4), (P5), (Ρ5'), (P5"), (P6) or (P7), wherein a ratio of 20:1 to 100:1 of compound (II) to acid is used.
A further embodiment of the present invention is that the process according to the present invention can be carried in an inert solvent or in a mixture of inert solvents.
Therefore the present invention also relates to a process (P9), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P2), (Ρ2'), (P3), (Ρ3'), (Ρ4), (Ρ5), (Ρ5'), (Ρ5"), (Ρ6), (Ρ7) or (Ρ8), wherein the process is carried out without any solvents. Therefore the present invention also relates to a process (P10), which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P2), (Ρ2'), (P3), (Ρ3'), (Ρ4), (Ρ5), (Ρ5'), (Ρ5"), (Ρ6), (Ρ7) or (Ρ8), wherein the process is carried out in an inert solvent or a mixture of inert solvents. The inert solvents are usually aliphatic hydrocarbons or aromatic hydrocarbons. These aliphatic hydrocarbons or aromatic hydrocarbons need to be liquid at the reaction conditions. The hydrocarbons can be linear, branched and/or cyclic.
Therefore the present invention relates to a process (P1 1 ), which is the process (P10), wherein the solvent (or solvents) is chosen from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons.
Suitable solvents are for example n-hexane, cyclohexane, n-heptane, pentane and toluene. Therefore the present invention relates to a process (P12), which is the process (P10) or (P1 1 ), wherein the solvent (or more than one) is chosen from the group consisting of n-hexane, cyclohexane, n-heptane, pentane and toluene.
The amount of the solvent (or solvent mixture) is not critical for the invention. It is used in usual amounts. The solvents (or solvent mixture) can be added in an equimolar amounts in regard to DLL (compound of formula (II)). But it is also possible to use more as well to use less solvent (or solvent mixture). A preferred range of the ratio of solvent (or solvent mixture) to DLL is 3:1 to 0.5 :1 . The ratio is weight related.
Therefore the present invention relates to a process (P13), which is the process (P10), (P1 1 ) or (P12), wherein the range of the ratio of solvent (or solvent mixture) to compound of formula (II) is 3:1 to 0.5 :1 .
The process according to the present invention is usually carried out at elevated temperatures. It is usually carried out at a temperature of between 30°C and 75°C (preferably 40°C - 70°C).
Therefore the present invention relates to a process (P14), which is the process which is the process (P), (P1 ), (Ρ1 '), (P1 "), (P2), (Ρ2'), (P3), (Ρ3'), (P4), (P5), (Ρ5'), (P5"), (P6), (P7), (P8), (P9), (P10), (P1 1 ), (P12) or (P13), wherein the process according to the present invention is carried out at a temperature of between 30°C and 75°C (preferably 40°C - 70°C).
The c-DLL (compound of formula (I)) obtained by the process according to present invention can be purified by using commonly known processes.
As stated above the c-DLL is then used to produce 2-vinyl-2,6,6-trimethyl-3,4,5,6- tetrahydro-2H-pyran via hydrogenation.
The hydrogenation of c-DLL can be done by using commonly known hydrogenation processes. Usually it is done by catalytic hydrogenation (i.e. with Lindlar catalysts):
The following examples serve to illustrate the invention. All percentages and parts (if not otherwise stated) are related to the weight and the temperature is given in °C.
Example 1 :
200g of n-hexane, 300g DLL and 7.5g p-toluenesulfonic acid (65wt-% aqueous solution) were added into a 11-flask. The reaction mixture was heated up to 75°C under constant stirring. The reaction mixture was kept at 75°C for 24 hours.
Afterwards 6,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 96 %.
Example 2:
51 Og DLL were added into a 1 1-flask. Afterwards 2.12 weight-% of p- toluenesulfonic acid (65wt-% aqueous solution), based on the total weight of the reaction mixture, was added The reaction mixture was heated up to 70°C under constant stirring. The reaction mixture was kept at 70°C for 1440 minutes..
Afterwards 6,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 98.7 %.
Example 3:
50g DLL were added into a flask. Afterwards 3.32 weight-% of 4- chlorobenzenesulfonic acid, based on the total weight of the reaction mixture was added The reaction mixture was heated up to 50°C under constant stirring. The reaction mixture was kept at 50°C for 1440 minutes.
Afterwards 1 ,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 98.5 %.
Example 4:
50g DLL were added into a flask. Afterwards 3.4 weight-% of 2,5- dimethylbenzenesulfonic acid, based on the total weight of the reaction mixture was added The reaction mixture was heated up to 50°C under constant stirring. The reaction mixture was kept at 50°C for 1440 minutes.
Afterwards 1 ,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 95.9 %.
Example 5:
50g DLL were added into a flask. Afterwards 2.24 weight-% of methanesulfonic acid, based on the total weight of the reaction mixture was added The reaction mixture was heated up to 50°C under constant stirring. The reaction mixture was kept at 50°C for 1440 minutes.
Afterwards 1 ,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 93.3 %.
Example 6:
50g DLL were added into a flask. Afterwards 1 .8 weight-% of HSO3CI, based on the total weight of the reaction mixture was added The reaction mixture was heated up to 50°C under constant stirring. The reaction mixture was kept at 50°C for 1440 minutes.
Afterwards 1 ,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 87.5 %.
Example 7:
50g DLL were added into a flask. Afterwards 2.24 weight-% of H2SO4 (65% in H2O), based on the total weight of the reaction mixture was added The reaction mixture was heated up to 50°C under constant stirring. The reaction mixture was kept at 50°C for 1440 minutes.
Afterwards 1 ,0 g Na2CO3 was added. The solvent and the side-products were removed by distillation. The c-DLL was obtained in a yield of 89.6 %.
Claims
1. A process for the production of the compound of formula (I)
characterized in that the process is carried out in the presence of (i) at least one non-polymeric acid containing one or more sulfur (VI) atom as a catalyst.
2. Process according to claim 1 , wherein the at least one non-polymeric acid containing one or more sulfur (VI) atom has a pKa value of less than 3.
3. Process according to anyone of the preceding claims, wherein the non- polymeric acid containing one or more sulfur (VI) atom is inorganic.
4. Process according to anyone of the preceding claims, wherein the non- polymeric acid containing one or more sulfur (VI) atom is organic.
5. Process according to claim 4, wherein the organic acid is aliphatic.
6. Process according to claim 4, wherein the organic acid is aromatic.
7. Process according to claim 3, wherein the inorganic acid is chosen from the group consisting of H2SO4 and HSO3CI .
8. Process according to claim 4, wherein the organic acid is chosen from the group consisting of p-toluenesulfonic acid, 4-chlorobenzenesulfonic acid, 2,5- dimethylbenzenesulfonic acid and methanesulfonic acid.
9. Process according to anyone of the preceding claims, wherein a ratio of 20:1 to 100:1 of compound (II) to acid is used.
10. Process according to anyone of the preceding claims, wherein the process is carried out without any solvents.
11. Process according to anyone of the preceding claims 1 - 9, wherein the process is carried out in an inert solvent or a mixture of inert solvents.
12. Process according to claim 1 1 , wherein the solvent (or solvents) is chosen from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons.
13. Process according to anyone of the preceding claims 1 1 - 12, wherein the solvent (or more than one) is chosen from the group consisting of chosen from the group consisting of n-hexane, cydohexane, n-heptane, pentane and toluene.
14. Process according to anyone of the preceding claims 1 1 - 13, wherein ratio of solvent (or solvent mixture) to compound of formula (II) is 3:1 to 0.5 :1 .
15. Process according to anyone of the preceding claims, wherein process according to the present invention is carried out at a temperature of between 30°C and 75°C.
Priority Applications (2)
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EP16704164.9A EP3256457A1 (en) | 2015-02-10 | 2016-02-10 | Process of production of cyclo-dehydrolinalool (i) |
MX2017010192A MX2017010192A (en) | 2015-02-10 | 2016-02-10 | Process of production of cyclo-dehydrolinalool (i). |
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EPEP15154526.6 | 2015-02-10 | ||
EP15154526 | 2015-02-10 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE852918A (en) * | 1976-03-26 | 1977-07-18 | Anic Spa | DEHYDROLINALOL CYCLING PROCESS AND PRODUCTS OBTAINED |
EP1186600A1 (en) * | 2000-09-06 | 2002-03-13 | Roche Vitamins AG | Process for the preparation of substituted pyranes |
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2016
- 2016-02-10 MX MX2017010192A patent/MX2017010192A/en unknown
- 2016-02-10 WO PCT/EP2016/052762 patent/WO2016128422A1/en active Application Filing
- 2016-02-10 EP EP16704164.9A patent/EP3256457A1/en not_active Withdrawn
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