WO2007063974A1 - Procede pour hydrogener un cycle aromatique de compose cyclique aromatique - Google Patents

Procede pour hydrogener un cycle aromatique de compose cyclique aromatique Download PDF

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WO2007063974A1
WO2007063974A1 PCT/JP2006/324021 JP2006324021W WO2007063974A1 WO 2007063974 A1 WO2007063974 A1 WO 2007063974A1 JP 2006324021 W JP2006324021 W JP 2006324021W WO 2007063974 A1 WO2007063974 A1 WO 2007063974A1
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aromatic ring
catalyst
hydrogen
solvent
ring compound
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PCT/JP2006/324021
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Japanese (ja)
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Hironao Sajiki
Tomohiro Maegawa
Kosaku Hirota
Yasunari Monguchi
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Nagoya Industrial Science Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • 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
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/42—Oxygen atoms attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • 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
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a method for hydrogenating an aromatic ring compound to an aromatic ring, and particularly to an aromatic ring compound that can be advantageously used when synthesizing a compound that is difficult to synthesize directly.
  • the present invention relates to a hydrogenation method.
  • aromatic ring compound in the scope of the present specification and claims is not only a compound having a ring (benzene ring) structure composed only of carbon, but also composed of carbon and other elements. It also includes compounds having a ring (heterocyclic) structure.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-193873
  • Patent ⁇ l3 ⁇ 4 Nishimura S, ⁇ Handbook of Heterogeneous and Atalytic Hydrogenatio n for Organic Synthesis J, Wiley-Interscience, New York, 2001, p.414-574 "A practical metal catalyst and its reaction 1", JETTY, 2003, p.147-164
  • the present invention has been made in the background of vigorous circumstances, and the problem to be solved is a relatively mild condition that can be implemented even in a small-scale facility. It is an object of the present invention to provide a method for adding hydrogen to an aromatic ring of an aromatic ring compound that has a low environmental burden.
  • an aromatic ring compound and a heterogeneous platinum group catalyst are added to water or an alcohol solvent as a solvent, and the melting point of the solvent (° A method for adding hydrogen to an aromatic ring of an aromatic ring compound, characterized in that hydrogen is contacted under a temperature range from C) to a boiling point (° C) of the solvent of 60 (° C). This is the gist.
  • the melting point (° C) and boiling point (° C) of the solvent in the present specification and claims mean the melting point (° C) and the boiling point (° C), respectively, in latm.
  • the method for adding hydrogen to the aromatic ring of the aromatic ring compound according to the present invention is preferably carried out under conditions of hydrogen pressure: 0.5 to 50 atm.
  • the solvent is any one of water, isopropyl alcohol, and t-butyl alcohol.
  • the heterogeneous platinum group catalyst is supported on a carrier.
  • the carrier is made of a carbon material.
  • the heterogeneous platinum group catalyst is a Pt / C catalyst, a Rh / C catalyst, a Ru / C catalyst, Pd It is at least one selected from the group consisting of a / C catalyst and an Ir / C catalyst.
  • an aromatic ring compound and a heterogeneous platinum group catalyst are added to water or an alcohol solvent.
  • the large-scale heating device required in the conventional method is used because the suspension is brought into contact with hydrogen under a temperature range lower than that of the conventional method. It is not required and as a result can be implemented in relatively small facilities.
  • the method for adding hydrogen to the aromatic ring of the aromatic ring compound according to the present invention is a method that does not use an acidic solvent or a basic solvent generally used in conventional methods.
  • the burden on the environment is small.
  • safety at the production site can be advantageously ensured by not using an acidic solvent or the like.
  • the present invention has the advantage that the hydrogenation reaction proceeds under a relatively mild temperature condition, and therefore, the catalyst after the reaction is completed with little deterioration of the heterogeneous platinum group catalyst after the reaction. It is also possible to reuse the powerful catalyst after recovery and washing.
  • the method for adding hydrogen to the aromatic ring of the aromatic ring compound according to the present invention has a hydrogen pressure of 0.
  • aromatic ring compounds specifically, carbon having a carbocyclic ring (benzene ring) are used as the aromatic ring compound as a raw material (hereinafter referred to as substrate).
  • Any conventionally known compounds such as ring compounds and heterocyclic compounds having a ring (heterocycle) composed of carbon and other elements can be used.
  • an aromatic ring compound for example, at least a part of the carbocyclic ring is an electron-withdrawing functional group (for example, acetyl group, carboxynole group (including esterified product), nitro group, cyano group, etc.).
  • Substituted phenylacetophenone, benzoic acid, methyl p-hydroxybenzoate, biphenyl, etc., or diphenylmethane substituted with an electron-donating functional group for example, an alkoxy group, a hydroxyl group, an alkyl group, etc.
  • Carbocyclic aromatic compounds such as 1 to 20 and the number of substituted alkyl groups is preferably about 1 to 4
  • heterocyclic compounds such as pyridine derivatives or furan derivatives
  • phenylalanine derivatives For example, aromatic amino acid derivatives represented by N_acetylyl vinylanalanyl ester
  • a heterogeneous platinum group catalyst is used as a catalyst for hydrogenating the aromatic ring of such an aromatic ring compound.
  • a heterogeneous platinum group catalyst any conventionally known catalyst can be used.
  • those supported by a carrier are advantageously used.
  • Such carriers include carbon materials such as activated carbon, alumina, silica, diatomaceous earth, molecular sieves, silk, and polymers.
  • a heterogeneous platinum group catalyst supported on a carbon material can be advantageously used, in particular, a Pt / C catalyst, Rh At least one selected from the group consisting of / C catalyst, Ru / C catalyst, Pd / C catalyst and Ir / C catalyst, among which Rh / C catalyst is preferably used.
  • Pt / C catalyst Rh / C catalyst, Ru / C catalyst, Pd / C catalyst, Ir / C catalyst
  • the supported amount of Pt is Of these, those accounting for :! to 30% by weight, preferably 3 to 20% by weight, are advantageously used.
  • the amount of the heterogeneous platinum group catalyst used is such that the ratio is about 1 to 100 parts by weight with respect to 100 parts by weight of the aromatic ring compound as the substrate. And used.
  • water or an alcohol solvent is used as a solvent together with the heterogeneous platinum group catalyst as described above.
  • any solvent can be used as long as it has been used in the past in methods for adding hydrogen to an aromatic ring of an aromatic ring compound.
  • isopropyl alcohol or t-butyl alcohol is advantageously used.
  • water is also advantageously used.
  • Water and alcohol solvents can be used as a mixture of two or more. However, water alone or a single anhydrous alcohol solvent S or a solvent is preferably used.
  • a predetermined amount of an aromatic ring compound and a predetermined amount of a heterogeneous platinum group catalyst are added to the water or alcohol solvent described above to prepare a suspension as a reaction solution.
  • the preparation is performed according to the same method as in the prior art.
  • the contact of hydrogen with the prepared suspension is based on the melting point (° C) of the solvent constituting the suspension. It is carried out under conditions within a temperature range in which the boiling point (° C) of the solvent is 60 (° C).
  • the present inventors have Within the temperature range of the present invention, the suspension is in a state where the fine particles of the aromatic ring compound are aggregated in the vicinity of the heterogeneous platinum group catalyst. It is thought that the reaction proceeds efficiently between the fine particles of the aromatic ring compound existing in the vicinity of the catalyst and hydrogen.
  • an acidic solvent or a basic solvent is used from the viewpoint of improving the reaction activity, and the product is filtered after completion of the reaction.
  • a neutralization step or the like for separation is required, and the treatment of the solvent removed by filtration has been a problem.
  • water or an alcohol solvent is used. Special treatment such as neutralization of the product is not required, and the treatment of the solvent (solvent) filtered off is much easier than in the case of the conventional method using an acidic solvent, In addition, the burden on the environment is small.
  • an aromatic ring compound and a heterogeneous platinum group catalyst are added to water or an alcohol solvent, and the mixture is stirred and mixed.
  • Hydrogen is within a temperature range from the melting point (° C) of the solvent constituting the suspension to the boiling point (° C) of the solvent plus 60 (° C), preferably the solvent.
  • the boiling point (° C) of the solvent is within the temperature range below the boiling point (° C) of the solvent, and more preferably from the boiling point (° C) of the solvent to 30 ( It can be contacted under the conditions within the temperature range (° C) above the temperature (° C) subtracted from the boiling point (° C) and below the temperature (° C) subtracted by 10 (° C).
  • the solvent may not function as a solvent (it does not exist as a liquid).
  • the temperature (° C) of the boiling point of the solvent exceeds 60 (° C)
  • hydrogen may be added to a site other than the aromatic ring in the aromatic ring compound, and the target compound may not be generated. Because there is.
  • the hydrogen brought into contact with the strong suspension is gaseous (hydrogen gas), and if the pressure is too low, the hydrogenation reaction of the aromatic ring compound to the aromatic ring will not occur.
  • hydrogen pressure is also the substrate as a substrate because there is a possibility that the same problem as when the temperature is too high may occur even if the pressure is too high.
  • 0.5 to 50 atm preferably 0.5 to 20 atm, more preferably 0. It is adjusted to about 5-5atm and implemented.
  • the hydrogen pressure is not necessarily required to be constant from the start of the reaction to the end of the reaction, and the hydrogen pressure from the start of the reaction to the end of the reaction is sufficient if it is within the above range.
  • the time for bringing the suspension into contact with hydrogen is appropriately set according to the amount of the aromatic ring compound serving as a substrate in addition to the above-described temperature and hydrogen pressure.
  • an aromatic ring compound as a substrate for example, having a phenolic hydroxyl group or an unsaturated hydrocarbon group
  • a suspension containing such an aromatic ring compound is used.
  • hydrogen is brought into contact with hydrogen, in addition to the compound in which hydrogen is added only to the aromatic ring of the aromatic ring compound, not only the aromatic ring but also a hydrogenated part of the original aromatic ring compound other than the aromatic ring is produced. There is a case.
  • a predetermined aromatic ring compound and a heterogeneous platinum group catalyst are added to a solvent (water or an alcohol solvent), and the mixture is stirred and mixed to prepare a suspension.
  • a separately prepared reaction tank with a heating device is sealed and filled with hydrogen gas at a predetermined pressure, and then the obtained suspension is put into the reaction tank and heated to a predetermined temperature.
  • the reaction solution is taken out from the reaction vessel, various organic solvents and the like are added to the reaction solution, and the catalyst is filtered off.
  • the obtained filtrate is separated, the organic phase is dried, and the solvent is removed to obtain the desired product (hydride).
  • a supply device that can supply hydrogen into the reaction tank at all times, and to keep the hydrogen pressure in the reaction tank constant from the start of the reaction to the end of the reaction. is there.
  • a hydrogen gas introduction pipe is introduced into a suspension of an aromatic ring compound or the like prepared in advance, and hydrogen gas is introduced into the suspension from a powerful hydrogen gas introduction pipe. Time, blowing techniques, etc. can also be used.
  • 10% RhZC catalyst means that the proportion of Rh loading (weight) in the total weight of the catalyst is 10% (weight%)
  • PtZC catalyst, IrZC catalyst, Pd / C catalyst, RuZC catalyst the same applies to other heterogeneous platinum group catalysts.
  • gas chromatograph or NMR measurement was performed after the reaction was completed, and the aromatic ring compound as the substrate was completely lost. I confirmed that Further, when the catalyst was filtered off, a membrane filter (Millex-LH, filter pore size: 0.45 xm) manufactured by Millipore was used, and the reaction product was confirmed by NMR.
  • the obtained filtrate was extracted with water and ether, and the ether layer was washed with saturated Japanese saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain biphenyl, cyclohexylbenzene and A mixture consisting of cyclohexylcyclohexane was obtained [Experimental example la].
  • the obtained mixture was subjected to ifi-NMR measurement, and the ratio (molar ratio) of biphenyl, cyclohexylbenzene and cyclohexylcyclohexane in the mixture was calculated. The results are shown in Table 1 below.
  • the aromatic ring compound (biphenyl) has an aromatic ring (benzene ring) according to the method for hydrogenation of the aromatic ring compound to the aromatic ring according to the present invention.
  • the reaction temperature is 80 ° C, that is, the boiling point (100 ° C) to 20 ( It was confirmed that the hydrogenation reaction proceeded most efficiently when the temperature was reduced (° C) (Experimental Example lc).
  • N-heptylbenzene lmmol (176.3 mg) and a predetermined amount of each catalyst listed in Table 2 below are added to water in lipped test tubes: lmL, stirred, and 9 types of suspensions are added. A liquid was prepared. Next, a Dimroth cooler and a hydrogen balloon were attached to each test tube, and after filling the test tube with hydrogen gas (hydrogen pressure: latm) with a hydrogen balloon, the test was conducted with the hydrogen balloon still attached. The tube was heated to the temperature listed in Table 2 below (80 ° C or 60 ° C), and vigorously stirred for a predetermined time (24 hours or 3 hours) to react n_heptylbenzene with hydrogen.
  • the method for adding hydrogen to an aromatic ring according to the present invention is used.
  • a Pd / C catalyst, Ir / C catalyst, Pt / C catalyst, Ru / C catalyst or RhZC catalyst as a heterogeneous platinum group catalyst. It is recognized that hydrogenation of the aromatic ring (benzene ring) proceeds effectively, and PtZC catalyst, RuZC catalyst or Rh / C catalyst is used especially under the conditions of these experimental examples 2a to 2i. It was confirmed that a high hydrogenation rate was achieved when using Rh / C catalyst among them.
  • the obtained filtrate was extracted with water and ether, and the ether layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 53.6 mg of product ( 1, 3, 5-trimethylcyclohexane, boiling point: 148 ° C) .
  • the isolated yield was as low as 42%. This is because the reaction progressed quantitatively, but the boiling point of the product was low. Is also assumed to have distilled off.
  • the obtained filtrate was extracted with water and ether, the ether layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 109.7 mg of product ( t-butylcyclohexane, boiling point: 171.5 ° C.).
  • the isolation yield was relatively low at 78%. This was because the reaction proceeded quantitatively, but the product had a low boiling point. It is estimated that a part of the water was also distilled off.
  • 4-Cyclohexylphenol as an aromatic ring compound 4-Cyclohexylphenol and hydrogen according to the same procedure as in Example 6 except that 1 mmol (176. 25 mg) and 17.6 mg of 10% RhZC catalyst were used. And reacted. Note that the hydrogen pressure in the sealed tube is constant. 3 hours after hydrogen filling. Then, according to the same procedure as in Experimental Example 6, the catalyst was filtered off to obtain 173.4 mg of product (4-cyclohexyl — 1-cyclohexanol).
  • 3-Hydroxypyridine as an aromatic ring compound 3-hydroxypyridine and hydrogen according to the same procedure as in Experimental Example 6 except that lmmol (95.04 mg) and 9.5 mg of 10% Rh / C catalyst were used. And reacted. The hydrogen pressure in the sealed tube became constant after 2 hours had passed since the hydrogen was filled. After this reaction, water is added to dissolve the product, the catalyst is filtered off with a membrane filter, and the resulting filtrate is distilled off under reduced pressure to give 101.2 mg of the product (3-hydroxypiperidine). ) The isolation yield was 100%.
  • Nicotinamide as an aromatic ring compound Nicotinamide and hydrogen were reacted according to the same procedure as in Experimental Example 6 except that 1 mmol (122. 05 mg) and 12.2 mg of 10% Rh / C catalyst were used. The hydrogen pressure in the sealed tube became constant after 1.5 hours had passed since hydrogen filling. After this reaction, water is added to dissolve the product, the catalyst is filtered off with a membrane filter, and the resulting filtrate is distilled off under reduced pressure to give 127.02 mg of product (3_carboxamidopiperidine. ) The isolation yield is 100. /. Met.
  • 2_pentylfuran as an aromatic ring compound 1mmol (138.21mg) and 1_pentylfuran were reacted with hydrogen according to the same procedure as Example 6 except that 13.8mg of 10% RhZC catalyst was used. I let you. The hydrogen pressure in the sealed tube became constant after 1 hour had passed since hydrogen filling. Then, 97.6 mg of the product (2-pentyltetrahydrofuran, boiling point: 174.5 ° C) was obtained by filtering the catalyst according to the same procedure as in Experimental Example 6. The isolation yield was 69%, which was relatively low. This is because the reaction progressed quantitatively, but the boiling point of the product was low. The part is also assumed to have distilled off.
  • a Dimroth cooler and a hydrogen balloon were attached to a test tube with a force rub.
  • the test tube was filled with hydrogen gas with a hydrogen balloon (hydrogen pressure: latm) and stirred vigorously for 24 hours at room temperature (20 ° C) with the hydrogen balloon attached.
  • diphenylmethane and hydrogen were reacted.
  • ether is added to dissolve the substrate and product, the catalyst is filtered off with a membrane filter, and the resulting filtrate is distilled off under reduced pressure to form diphenylmethane, fuelcyclohexylmethane, and dicyclohexylhexylmethane.
  • a mixture was obtained [Experimental Example 15a]. About the resulting mixture
  • the aromatic ring compound (diphenylmethane) has an aromatic ring (benzene ring) according to the method for hydrogenation of the aromatic ring compound to the aromatic ring according to the present invention.
  • the reaction temperature was 60 ° C, that is, the boiling point (82.4 ° C).
  • the hydrogenation reaction proceeded most efficiently when the temperature was reduced by about 20 (° C) (° C) (Experimental Example 15c).
  • Example 16a to 16f were obtained.
  • the obtained mixture was subjected to ifi-NMR measurement, and the proportion (molar ratio) of diphenylmethane, phenylcyclohexylmethane and dicyclohexylmethane in the mixture was calculated. The results are shown in Table 4 below.
  • Example 17 2 1 was performed using isopropyl alcohol as a solvent and appropriately changing the substrate (aromatic ring compound), the type of catalyst, the hydrogen pressure, the reaction temperature, or the reaction time. .
  • Isopropyl alcohol in a rubbed test tube Add lmmol (176.3 mg) of n-p-tylbenzene and 17.6 mg of 10% Rh / C catalyst to 1 mL, suspend, and then rub A Dimroth cooler and a hydrogen balloon were attached to the test tube. Next, the test tube was filled with hydrogen with a hydrogen balloon (hydrogen pressure: latm), and with vigorous stirring for 24 hours at room temperature (20 ° C) with the hydrogen balloon attached. n-Heptylbenzene was reacted with hydrogen. Thereafter, ether was added to dissolve the product, and the catalyst was filtered off with a membrane filter.
  • T_Butylbenzene 1 mmol (134. 22 mg) was used as the aromatic ring compound, and 13.4 mg of 10% RhZC was used as the catalyst. After reacting t_butylbenzene with hydrogen, the catalyst was filtered off to obtain 57.49 mg of product (t-butylcyclohexane). Although the isolation yield was as low as 41%, this was because the reaction proceeded quantitatively, but the product had a low boiling point. It is estimated that a part of was also distilled off.
  • Isopropyl alcohol in a rubbed test tube Add 1 mL of biphenyl Immo (154.21 mg) and 10% Rh / C hornworm medium (15.4 mg) and add it to the suspension. A Dimroth cooler and a hydrogen balloon were attached to a test tube with rubbing. Next, the test tube was filled with hydrogen in a hydrogen balloon (hydrogen pressure: latm), heated to 60 ° C with the hydrogen balloon attached, and stirred vigorously for 24 hours under such temperature conditions. By doing so, biphenyl and hydrogen were reacted. Thereafter, ether was added to dissolve the product, and the catalyst was filtered off with a membrane filter. The filtrate was distilled off under reduced pressure to obtain 161.22 mg of product (bicyclohexyl). The isolation yield was 97%.
  • 1,3,5-Tri-1_butylbenzene as an aromatic ring compound According to the same conditions as in Experimental Example 20, except that 1mmol (246.43mg) and 24.6mg of 10% Rh / C catalyst were used. 1,3,5-tri-t-butylbenzene was reacted with hydrogen. The hydrogen pressure in the sealed tube became constant after 5 hours had passed since hydrogen filling. Then, according to the same procedure as in Experimental Example 20, the catalyst was filtered off to obtain 252.43 mg of product (1, 3, 5_tri_t-butylcyclohexane). The isolation yield was 100%.
  • a Dimroth cooler and a hydrogen balloon were attached to a test tube with a force rub.
  • the inside of the test tube is filled with hydrogen gas with a hydrogen balloon (hydrogen pressure: latm), and the test tube is heated to 40 ° C. with the hydrogen balloon attached, and under such temperature conditions.
  • Diphenylmethane and hydrogen were reacted by vigorous stirring for 24 hours.
  • ether is added to dissolve the substrate and the product, the catalyst is filtered off with a membrane filter, and the resulting filtrate is distilled off under reduced pressure to obtain a mixture of diphenylmethane, fuel cyclohexyl methane and dicyclohexyl methane. Obtained [Experimental Example 22a].
  • the obtained mixture was subjected to iH-NMR measurement, and the ratio (molar ratio) of diphenylmethane, phenylcyclohexylmethane, and dicyclohexylmethane in the mixture was calculated.
  • the results are shown in Table 5 below.
  • the reaction temperature is 60 ° C, that is, the temperature (° C) reduced by about 20 (° C) from the boiling point (82.5 ° C) (Experimental Example 22b) In addition, it was confirmed that the hydrogenation reaction proceeds most efficiently.
  • the amount of the recovered catalyst was measured after drying. Then, using the amount of diphenylmethane according to the amount of the catalyst, diphenylmethane and hydrogen are reacted according to the same method as described above (second synthesis), and after such reaction, the catalyst is recovered and dicyclohexane is added. Xylmethan was isolated. The amount of diphenylmethane used in this second synthesis, the amount of catalyst used, and the isolated yield of dicyclohexylmethane are also shown in Table 6 below.
  • the catalyst is recovered in the same manner as described above, and dicyclohexylmethane is synthesized in an amount corresponding to the recovered amount in the same manner as described above (the third synthesis of dicyclohexylmethane). Synthesis).
  • the amount of diphenylmethane used in this third synthesis, the amount of catalyst used, and the isolated yield of dicyclohexylmethane are also shown in Table 6 below.
  • the second synthesis and the third synthesis also yielded dicyclo in a yield similar to that of the first synthesis. Xylmethane was obtained, and it was confirmed that the catalyst used in carrying out the present invention can be reused advantageously.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

La présente invention concerne un procédé pour hydrogéner un cycle aromatique d'un composé cyclique aromatique qui se produit dans des conditions comparativement douces. Ce procédé pour hydrogéner un cycle aromatique d'un composé cyclique aromatique peut être conduit dans des petites installations et ne produit qu'une faible nuisance pour l'environnement. Spécifiquement, un composé cyclique aromatique et un catalyseur au platine non uniforme sont ajoutés dans un solvant, à savoir dans l'eau ou un solvant alcoolique, et de l'hydrogène est amené au contact de la suspension ainsi obtenue dans la plage de températures allant du point de fusion (°C) du solvant à une température supérieure au point d'ébullition (°C) du solvant de 60°C.
PCT/JP2006/324021 2005-12-02 2006-11-30 Procede pour hydrogener un cycle aromatique de compose cyclique aromatique WO2007063974A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009040717A (ja) * 2007-08-08 2009-02-26 Sumitomo Seika Chem Co Ltd シクロヘキサンカルボン酸の製造方法
JP2011162494A (ja) * 2010-02-12 2011-08-25 Yuki Gosei Kogyo Co Ltd ４−ホルミルピペリジンアセタール誘導体の製造方法
JP2015506333A (ja) * 2011-12-21 2015-03-02 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ 抗菌活性化合物としてのシクロヘキサノール誘導体の使用
JP2021066707A (ja) * 2019-10-25 2021-04-30 学校法人上智学院 環状化合物の製造方法

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JPS647953A (en) * 1987-03-24 1989-01-11 Tno Production of rhodium catalyst for hydrogenating unsaturated compound and hydrogenation of said compound
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JP2009040717A (ja) * 2007-08-08 2009-02-26 Sumitomo Seika Chem Co Ltd シクロヘキサンカルボン酸の製造方法
JP2011162494A (ja) * 2010-02-12 2011-08-25 Yuki Gosei Kogyo Co Ltd ４−ホルミルピペリジンアセタール誘導体の製造方法
JP2015506333A (ja) * 2011-12-21 2015-03-02 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ 抗菌活性化合物としてのシクロヘキサノール誘導体の使用
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JP2021066707A (ja) * 2019-10-25 2021-04-30 学校法人上智学院 環状化合物の製造方法

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