Classifications

• • 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
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/46—Ruthenium, rhodium, osmium or iridium
  • B01J23/462—Ruthenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
  • B01J27/13—Platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
  • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
• • 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
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/52—Isomerisation reactions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• the present invention relates to a method for producing a cyclohexenone compound.
• Cyclohexenone compounds are useful as intermediates for the synthesis of various active pharmaceutical ingredients. For example, it is useful as a synthetic intermediate for the nervous system agent described in Patent Document 1.
• Non-Patent Document 1 As a method for producing a cyclohexenone compound and intermediates thereof, the method of Non-Patent Document 1 is known.
• Non-Patent Document 1 as shown in the following reaction scheme, 2-cyclohexenone is used as a starting material and reacted with (trimethylsilyl)trifluoromethane to produce 3-hydroxy-3-trifluoromethylcyclohexan-1-one. and further reaction with pyridinium chlorochromate (PCC) to produce 3-trifluoromethyl-2-cyclohexen-1-one.
• PCC pyridinium chlorochromate
• Non-Patent Document 2 describes a method for producing an enone ester compound as shown in the reaction formula below.
• 3-carboxy-1,1,1-trifluoroheptane-2,6-dione is produced, and this is used as a base.
• deesterification is performed under acidic conditions, followed by decarboxylation under acidic conditions.
• Non-Patent Document 3 Even if the method of Non-Patent Document 3 is applied to the compound represented by the following formula (3), which is the object of the present invention, the reaction does not proceed efficiently, and many high-boiling impurities are produced. In addition, there is a problem that the amount of by-product isomers is large.
• the present inventors isomerized the isomer represented by the formula (4), which was a by-product during the synthesis of the compound represented by the formula (3), to the target compound represented by the formula (3).
• Various methods were examined. As a result, it was found that the isomer represented by the formula (4) can be reduced and the target compound represented by the formula (3) can be efficiently recovered by performing an isomerization reaction using a specific metal catalyst. rice field.
• Non-Patent Document 4 describes a method of using rhodium (III) chloride as a catalyst for the following isomerization reaction of aromatic compounds.
• the compound represented by formula (4) which is the object of the present invention, does not undergo a favorable isomerization reaction even when a rhodium-based catalyst is used, as shown in Comparative Example 3 below.
• An object of the present invention is to provide a method for producing a cyclohexenone compound at high yield, at low cost, with reduced purification load and environmental load, and with high productivity.
• the present inventors have found that by adopting a specific production method and purification method, it is possible to produce a cyclohexenone compound with high yield and low cost, with reduced purification load and environmental load, and with high productivity.
• the gist of the present invention is as follows.
• a cyclohexenone compound comprising an isomerization step of bringing a reaction raw material containing a compound represented by the following formula (4) into contact with an isomerization catalyst in a solvent to obtain a compound represented by the following formula (3) manufacturing method.
• a cyclohexenone compound of the present invention can be produced at high yield and at low cost, with high productivity while suppressing the purification load and environmental load.
• a reaction raw material containing a compound represented by the following formula (4) is brought into contact with an isomerization catalyst in a solvent to obtain a compound represented by the following formula (3). including conversion process.
• a compound represented by the following formula (2) is reacted in a solvent in the presence of a strong acid to obtain a compound represented by the above formula (3). It is preferred to have a cyclization step to obtain the compound
• a compound represented by the following formula (1) and methyl vinyl ketone are reacted in a solvent in the presence of a base to obtain It is preferable to have an additional step of obtaining the compound represented by (2).
• 3-trifluoromethyl-2-cyclohexene-1- represented by formula (3) is obtained by sequentially performing the following addition step, cyclization step and isomerization step. It is preferred to produce ons.
• a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) and methyl vinyl ketone are reacted in a solvent in the presence of a base to give a compound represented by the formula (2) an additional step of obtaining the represented compound (hereinafter sometimes referred to as “compound (2)”); Cyclization step of reacting compound (2) in a solvent in the presence of a strong acid to obtain a compound represented by formula (3) (hereinafter sometimes referred to as "compound (3)”); The compound represented by the formula (4) contained as an impurity in the reaction product obtained in the cyclization step (hereinafter sometimes referred to as "compound (4)”) is contacted with an isomerization catalyst in a solvent. Isomerization step to cause;
• the addition step is a step of reacting compound (1) with methyl vinyl ketone in the presence of a base in a solvent to obtain compound (2).
• the amount of methyl vinyl ketone used should be equal to or greater than the reaction equivalent.
• the amount of methyl vinyl ketone to be used is generally 1 mol-2 mol, preferably 1 mol-1.5 mol, per 1 mol of compound (1).
• ⁇ Base> As the base, both organic bases and inorganic bases can be used.
• organic bases include aliphatic amines such as triethylamine; aromatic amines such as aniline; pyridine, lutidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3. 0]-5-nonene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene and other heterocyclic amines.
• Inorganic bases include metal hydrides, metal hydroxides, metal carbonates and the like.
• metal hydrides include lithium hydride, sodium hydride, potassium hydride and the like.
• metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like.
• metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
• These bases may be used alone or in combination of two or more.
• inorganic bases are preferred, metal hydrides are more preferred, and sodium hydride is particularly preferred.
• metal hydride By using a metal hydride, the amount of base used can be suppressed.
• the lower limit is usually 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, and the upper limit is usually 2 mol or less, preferably 1 mol, per 1 mol of compound (1). 0.5 mol or less, more preferably 0.5 mol or less. If the amount of the base used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of the base used is equal to or less than the above upper limit, it is possible to suppress the formation of by-products.
• solvent at least one selected from the group consisting of organic solvents and water is used.
• the organic solvent includes aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane and cycloheptane; aromatic hydrocarbon solvents such as toluene and xylene; methanol, ethanol, normal propanol, isopropanol, butanol, pentanol, hexanol, heptanol, Aliphatic alcohol solvents having 1 to 8 carbon atoms such as octanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; diethyl ether, di-n-butyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, cyclopentyl methyl ether , tetrahydrofuran, 2-methyltetrahydrofuran, ether solvents such as dioxane;
• the solvent is preferably an organic solvent, more preferably an aromatic hydrocarbon solvent, and particularly preferably toluene.
• the lower limit is usually 1 L or more, preferably 2 L or more, more preferably 3 L or more, and the upper limit is usually 20 L or less, preferably 15 L or less, more preferably 10 L or less, per 1 kg of compound (1). is. If the amount of solvent used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of solvent used is equal to or less than the above upper limit, it is possible to obtain the desired product with high productivity.
• the lower limit is usually 0°C or higher, preferably 10°C or higher, more preferably 20°C or higher, particularly preferably 30°C or higher
• the upper limit is usually 80°C or lower, preferably 70°C or lower, more preferably 70°C or lower. is 60° C. or lower, particularly preferably 50° C. or lower. If the reaction temperature is equal to or higher than the above lower limit, it is possible to efficiently react the reaction substrate. If the reaction temperature is equal to or lower than the above upper limit, it is possible to suppress the formation of by-products.
• the reaction time is generally 0.1 hour to 24 hours, preferably 0.5 hour to 12 hours. If the reaction time is at least the above lower limit, the reaction can be carried out efficiently. If the reaction time is equal to or less than the above upper limit, the desired product can be obtained with high productivity.
• the reaction pressure is usually normal pressure, but it may be pressurized.
• ⁇ Reaction method> When compound (1) and methyl vinyl ketone are reacted in a solvent in the presence of a base, the order of supply of these can be appropriately selected. These may be supplied to the reaction system all at once, or may be supplied in multiple batches. For example, a base, a solvent, and the liquid compound (1) are fed into a reactor to form a uniform bed liquid, and liquid methyl vinyl ketone is fed to form a uniform solution under the reaction conditions to carry out the reaction. , the compound (2) can be obtained.
• the reaction solution containing compound (2) may be directly subjected to the next step, but the remaining base is neutralized with an acid, and after liquid separation, the obtained organic layer is subjected to a treatment such as filtration. You may use for a process. Further, the concentrate obtained by concentrating the obtained organic layer may be subjected to the next step, or the product may be subjected to the next step after further purification by purification means such as column chromatography.
• the cyclization step is a step of reacting compound (2) obtained in the addition step in the presence of a strong acid in a solvent to obtain compound (3).
• a strong acid is an acid with an acid dissociation constant of less than 0 in water at 25°C.
• strong acids that can be used include strong inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and strong organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. Only one of these strong acids may be used, or two or more may be mixed and used, but from the viewpoint of productivity, it is preferable to use only one.
• inorganic strong acids, particularly sulfuric acid are preferably used from the viewpoint of cost and reactivity. Sulfuric acid having a concentration of 30% by mass or more and less than 90% by mass is usually used.
• the amount of the strong acid to be used has a lower limit of usually 0.1 mol or more, preferably 0.2 mol or more, more preferably 0.3 mol or more, and an upper limit of usually 20 mol or less, preferably 10 mol or less, relative to 1 mol of compound (2). More preferably, it is 5 mol or less. If the amount of the strong acid used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of strong acid used is equal to or less than the above upper limit, it is possible to suppress the generation of by-products.
• Solvents used in the cyclization step include the same solvents as those used in the addition step described above. From the viewpoint of reactivity, organic solvents are preferred, alcohol solvents and ether solvents are more preferred, and isopropanol and methyl tert-butyl ether are particularly preferred. Only one solvent may be used, or a mixture of two or more solvents may be used, but from the viewpoint of productivity, it is preferable to use only one solvent.
• the lower limit is usually 1 L or more, preferably 2 L or more, more preferably 3 L or more, and the upper limit is usually 20 L or less, preferably 15 L or less, more preferably 10 L or less, per 1 kg of compound (2). is. If the amount of solvent used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of solvent used is equal to or less than the above upper limit, it is possible to obtain the desired product with high productivity.
• the lower limit is usually 50° C. or higher, preferably 60° C. or higher, more preferably 70° C. or higher, and the upper limit is usually 120° C. or lower, preferably 110° C. or lower, more preferably 100° C. or lower. . If the reaction temperature is equal to or higher than the above lower limit, the reaction can be efficiently carried out. If the reaction temperature is equal to or lower than the above upper limit, it is possible to suppress the formation of by-products.
• the reaction time is generally 0.1 to 72 hours, preferably 12 to 36 hours. If the reaction time is at least the above lower limit, the reaction can be carried out efficiently. If the reaction time is equal to or less than the above upper limit, the desired product can be obtained with high productivity.
• reaction method When the compound (2) is reacted with a strong acid, the order of supplying these compounds can be appropriately selected. These compounds may be supplied to the reaction system all at once, or may be supplied in multiple batches. For example, the reaction can be carried out by supplying compound (2) together with a solvent into a reactor, using this as a bed solution, and supplying a strong acid under the reaction conditions. Conversely, a solution of compound (2) may be added dropwise to a bed solution containing a strong acid.
• the reaction solution containing the compound (3) and the compound (4) is generally neutralized with a strong acid with a base, subjected to liquid separation, filtration and other treatments, and then an organic layer containing the compound (3) and the compound (4).
• the solvent is distilled off, and the isolated compound (3) and compound (4) may be subjected to the next isomerization step, or the organic layer containing compound (3) and compound (4) may be separated from compound (3 ) and the compound (4) may be distilled off and the distillate obtained may be supplied to the next isomerization step. Further, these may be further purified by purification means such as column chromatography, and then subjected to the next isomerization step.
• the isomerization step is a step of isomerizing compound (4) in a solvent in the presence of an isomerization catalyst.
• reaction substrate> As the starting material compound (4) for the isomerization step, a highly pure product of 3-trifluoromethyl-3-cyclohexen-1-one can be used, but the compound (3) obtained in the cyclization step and compound (4) is preferably used as an industrial process.
• the mixture containing compound (3) and compound (4) obtained in the cyclization step usually contains 5 mol% to 50 mol% of compound (4) relative to compound (3).
• compound (4) is isomerized and converted to compound (3), so that the content of compound (3) increases and the content of compound (4) increases. is reduced.
• the content of compound (4) in the reaction product liquid obtained after the isomerization reaction is usually less than 5 mol%, preferably 4 mol% or less, and particularly preferably 3 mol% or less relative to compound (3). , a higher purity compound (3) can be obtained in a high yield.
• the isomerization catalyst is not particularly limited as long as it can isomerize compound (4) to compound (3).
• a ruthenium-containing catalyst is preferable, and a ruthenium-based catalyst or a ruthenium-containing composite metal catalyst is particularly preferable.
• a ruthenium-based catalyst is particularly preferable from the viewpoint of reactivity and cost.
• Ruthenium-based catalysts include ruthenium-supported carbon catalysts (hereinafter sometimes referred to as "Ru/C"), ruthenium chloride (III), tris(acetylacetonato)ruthenium (III), tris(2,2' -bipyridyl)ruthenium (II) chloride, dichloro(p-cymene)ruthenium (II) (dimer) and the like.
• Ru/C ruthenium-supported carbon catalysts
• ruthenium chloride (III) tris(acetylacetonato)ruthenium (III), tris(2,2' -bipyridyl)ruthenium (II) chloride, dichloro(p-cymene)ruthenium (II) (dimer) and the like.
• Ru/C ruthenium-supported carbon catalysts
• III ruthenium chloride
• III tris(acetylacetonato)ruthenium
• II tris
• ruthenium chloride (III) and ruthenium-supported carbon catalysts are preferred from the viewpoint of reactivity and cost.
• the amount of ruthenium supported is preferably about 5 to 10% by mass based on carbon, from the viewpoint of availability and cost.
• the lower limit is usually 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, relative to 1 mol of compound (4), as the amount used in terms of metal in the catalyst.
• the upper limit is usually 2 mol or less, preferably 1 mol or less, more preferably 0.5 mol. If the amount of the isomerization catalyst used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of the isomerization catalyst used is equal to or less than the above upper limit, it is possible to suppress the formation of by-products.
• solvent used in the isomerization step examples include the same solvents as those used in the addition step described above. From the viewpoint of reactivity and productivity, the ether solvent is preferred, and methyl tert-butyl ether is particularly preferred. These solvents can efficiently carry out the reaction without inhibiting the isomerization reaction. Only one kind of solvent may be used, or two or more kinds may be mixed and used, but from the viewpoint of productivity, it is preferable to use only one kind.
• the amount of the solvent used has a lower limit of usually 1 L or more, preferably 2 L or more, more preferably 3 L or more, and an upper limit of 1 kg of compound (4) or a mixture containing compound (3) and compound (4). 20 L or less, preferably 15 L or less, more preferably 10 L or less. If the amount of solvent used is at least the above lower limit, the reaction can be carried out efficiently. If the amount of solvent used is equal to or less than the above upper limit, it is possible to obtain the desired product with high productivity.
• the lower limit of the reaction temperature in the isomerization step (the temperature at which the reaction raw material containing the compound represented by formula (4) is brought into contact with the isomerization catalyst) is usually 10°C or higher, preferably 20°C or higher, and more preferably 30°C or higher.
• the upper limit is usually 100°C or lower, preferably 80°C or lower, more preferably 60°C or lower. If the reaction temperature is equal to or higher than the above lower limit, the reaction can be efficiently carried out. If the reaction temperature is equal to or lower than the above upper limit, it is possible to suppress the formation of by-products.
• the reaction time is generally 0.1 hour to 72 hours, preferably 1 hour to 24 hours. If the reaction time is at least the above lower limit, the reaction can be carried out efficiently. If the reaction time is equal to or less than the above upper limit, the desired product can be obtained with high productivity.
• the reaction pressure is usually normal pressure, but it may be pressurized.
• reaction method When reacting compound (4) or a mixture containing compound (3) and compound (4) with an isomerization catalyst, the order of supplying these compounds can be appropriately selected. These compounds may be supplied to the reaction system all at once, or may be supplied in multiple batches. For example, the reaction can be carried out by supplying a mixture containing the compound (3) and the compound (4) together with a solvent into a reactor, using this as a bed liquid, and supplying an isomerization catalyst under the reaction conditions.
• the reaction solution is generally subjected to liquid separation, filtration, or the like, and then the target product may be isolated from the organic layer by means of isolation such as concentration or distillation. After isolation, it may be further purified by purification means such as column chromatography.
• the isopropanol solution of compound (3) and compound (4) obtained in the cyclization step was cooled to 25° C., 900 g of water and 335.7 g of MTBE were added, stirred, and allowed to stand to obtain an organic layer 1. . 335.7 g of MTBE was added to the remaining aqueous layer, and the mixture was stirred and allowed to stand.
• the obtained organic layer 2 was mixed with the organic layer 1, 450 g of water was added, the mixture was stirred, and left to stand still to remove the aqueous layer. 450 g of 5% by mass aqueous sodium bicarbonate solution was added to the obtained organic layer, and the mixture was stirred and allowed to stand to remove the aqueous layer.
• reaction solution was cooled to 25° C. and concentrated to a liquid volume of about 450 ml at a reduced pressure of 100 hPa. %, compound (4): 21.6 area %).
• the obtained distillate mixture (3-2) is heated from 25° C. to 100° C. at 10 stages, a reflux ratio of 4, and a degree of reduced pressure of 10 hPa, and batch rectification is performed to obtain the mixture (3-2) as an oily compound.
• 3) (Compound (3): 83.5 area %, Compound (4): 14.2 area %) were obtained.
• the resulting mixture (3-3) was heated from 25° C. to 100° C. at 10 stages, a reflux ratio of 4, and a degree of reduced pressure of 10 hPa, and batch rectification was performed. Consistent yield from (1): 18%, chemical purity: 98.8 area %, content: 98.2 mass %, compound (4): 1.2 area %).
• Example 1 the same procedure as in Example 1 was performed except that 6 mg of ruthenium chloride (III) (0.01 mol equivalent to the substrate) was changed to 86 mg of 5% by mass ruthenium/carbon (0.01 mol equivalent to the substrate). isomerization was performed.
• the compound (3) was found to be 94.0 area % and the compound (4) was found to be 2.3 area %.
• Example 1 In Example 1, except that 6 mg of ruthenium chloride (III) (0.01 mol equivalent to the substrate) was changed to 9 mg of tris(acetylacetonato)ruthenium (III) (0.01 mol equivalent to the substrate). Isomerization was carried out in the same manner as in 1. As a result of analyzing the obtained reaction liquid under the above-described GC analysis conditions, the compound (3) was found to be 93.0 area % and the compound (4) was found to be 3.1 area %.
• Example 1 Isomerization catalyst: Isomerization of compound (4) using palladium (II) chloride] Same as Example 1 except that 6 mg of ruthenium (III) chloride (0.01 mol equivalent to the substrate) was changed to 1.6 mg of palladium (II) chloride (0.01 mol equivalent to the substrate) in Example 1. and isomerization was performed. As a result of analyzing the obtained reaction liquid under the above-described GC analysis conditions, the compound (3) was 89.4 area % and the compound (4) was 6.5 area %. In Comparative Example 1, the isomerization efficiency of compound (4) was lower than in Example 1 using ruthenium (III) chloride.
• Example 2 Isomerization catalyst: Isomerization of compound (4) using nickel (II) chloride] Same as Example 1 except that 6 mg of ruthenium (III) chloride (0.01 mol equivalent to the substrate) was changed to 1.2 mg of nickel (II) chloride (0.01 mol equivalent to the substrate) in Example 1. and isomerization was performed. As a result of analyzing the obtained reaction liquid under the above-described GC analysis conditions, the compound (3) was 86.1 area % and the compound (4) was 7.9 area %.
• Example 3 Isomerization of mixture (4) using isomerization catalyst: rhodium (III) chloride
• the mixture (3-3) obtained in Example 1 was allowed to stand at room temperature for 2 weeks and analyzed under the GC analysis conditions described above. , compound (4) 9.4 area %, and other impurities 3.4 area %.
• the mixture (3-3) was added to the mixture (3-3A), 6 mg of ruthenium (III) chloride (0.01 mol equivalent to the substrate) was added to 9 mg of rhodium (III) chloride (0.01 mol equivalent to the substrate).
• Isomerization was carried out in the same manner as in Example 1, except that each was changed to 01 mol equivalent).
• the compound (3) was 87.6 area % and the impurity (4) was 8.6 area %.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=82931767

Family Applications (1)

Country Status (5)

Citations (3)

Family Cites Families (6)

• 2022
  • 2022-02-15 US US18/277,158 patent/US20240158328A1/en active Pending
  • 2022-02-15 JP JP2023500845A patent/JPWO2022176837A1/ja not_active Ceased
  • 2022-02-15 WO PCT/JP2022/005854 patent/WO2022176837A1/ja not_active Ceased
  • 2022-02-15 EP EP22756155.2A patent/EP4296254A4/en not_active Withdrawn
  • 2022-02-15 CN CN202280014372.2A patent/CN116867762A/zh active Pending

Patent Citations (3)

Non-Patent Citations (9)

Also Published As

Similar Documents

Legal Events