WO2009085826A2 - Transhydrogenation processes - Google Patents
Transhydrogenation processes Download PDFInfo
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- WO2009085826A2 WO2009085826A2 PCT/US2008/087162 US2008087162W WO2009085826A2 WO 2009085826 A2 WO2009085826 A2 WO 2009085826A2 US 2008087162 W US2008087162 W US 2008087162W WO 2009085826 A2 WO2009085826 A2 WO 2009085826A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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- 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
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/133—Preparation by dehydrogenation of hydrogenated pyridine compounds
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- 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
- This invention relates to a transhydrogenation process involving the transfer of hydrogen from one compound to another compound to form new compounds, for example, using a transhydrogenation reaction to convert cyclic aliphatic compounds into aromatic compounds.
- Hydrogenation and dehydrogenation reactions are chemical processes used to form compounds that have increased their hydrogen content (hydrogenation) or decreased it (dehydrogenation).
- Transhydrogenation processes have been previously used. See e.g. U.S. Patent Nos. 3,267,170; 4,684,755; and 5,585,530, the disclosure of which is herein incorporated by reference.
- conventional transhydrogenation reactions involve either the hydrogenation of small-chain olefins, such as propylene or ethylene, to produce alkanes, or the dehydrogenation of small- chain alkanes to produce olefins.
- the focus of these transhydrogenation reactions thus lies in small-chain linear hydrocarbons, typically having four or fewer carbon atoms.
- the reaction conditions desirable for hydrogenating small-chain olefins or dehydrogenating small-chain linear alkanes are typically too harsh and largely ineffective for transhydrogenation methods involving more complex compounds, such as cyclic compounds.
- the high reactions temperatures typically 400-500° C
- the catalyst systems manufactured of which involve chromium
- the vapor-phase conditions of the reaction all can be problematic when attempting to conduct a transhydrogenation reaction that includes a cyclic compound.
- This invention relates to a transhydrogenation process involving cyclic compounds.
- the process comprises dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and hydrogenating at least one cyclic compound or acyclic compound that contains at least one unsaturation and/or a functional group capable of undergoing hydrogenation.
- the hydrogen generated in the dehydrogenation reaction is used as the hydrogen source in the hydrogenation reaction.
- the invention also relates to a process for hydrogenating a cyclic compound comprising reacting a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation to produce a cyclic compound having a saturated cyclic ring and/or a hydrogenated functional group.
- the reaction takes place in the presence of hydrogen gas that is generated from a dehydrogenation reaction taking place at the same time or near the same time as the hydrogenation reaction.
- the invention also relates to a process for dehydrogenating a cyclic compound, comprising dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings in the presence of a catalyst to produce a cyclic compound having at least one unsaturated ring.
- the hydrogen gas liberated from the dehydrogenation reaction is used in a hydrogenation reaction that takes place in the same reaction vessel.
- the hydrogenation reactions used in this invention typically involve the saturation of a double bond in a cyclic or acyclic compound.
- the double bond being hydrogenated may be, for instance, one or more of the double bonds located in the ring of an aromatic compound.
- the hydrogenation reaction can also involve the reduction of a functional group in a cyclic or acyclic compound, for example reducing a carbonyl group to an alcohol.
- Dehydrogenation reactions used in this invention typically involve the formation of an unsaturated cyclic compound from a saturated cyclic compound, for example forming an aromatic compound from a cyclo-aliphatic compound. This process thus involves the release of hydrogen from one compound and the uptake of hydrogen by the other compound, the reaction occurring under the appropriate temperature, pressure, catalyst type, and concentration conditions.
- the process allows for the simultaneous, or near simultaneous, transfer of hydrogen from a donor cyclic compound to a receptor compound, which beneficially precludes the handling of large amounts of hydrogen gas. Further, the choice of cyclic starting materials can produce two or more products, all of which have commercial uses. This can be achieved without the use of large stoichiometric amounts of hydrogen gas.
- This invention relates to an transhydrogenation process involving cyclic compounds. The process comprises dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and hydrogenating at least one cyclic or acyclic compound that contains at least one unsaturation and/or a functional group capable of undergoing hydrogenation. The hydrogen generated in the dehydrogenation reaction is used in the hydrogenation reaction.
- the cyclic compound in the dehydrogenation step may be any cyclic compound, such as a substituted or unsubstituted cycloaikyl, or a substituted or unsubstituted heteroalkyl.
- the cycloaikyl or heteroalkyl may be substituted with one or more substituents selected from the group consisting of alkyl, aryl, alcohol, thiol, ester, ether, amine, imine, amide, nitro, carboxylic acid, carbonate, isocyanate, halogen, and combinations thereof.
- the substituent is an alkyl group, such as a methyl group, or an alcohol.
- the compound in the hydrogenation step may be cyclic or acyclic. If the compound is cyclic, the cyclic compound may be any compound that contains either an unsaturation in the ring or a functional group capable of undergoing hydrogenation. Such compounds include substituted or unsubstituted aryl, heteroaryl, cycloaikyl containing at least one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compounds containing at least one unsaturation in the cyclic ring, and heterocyclic compounds containing at least one functional group capable of undergoing hydrogenation.
- the acyclic compound may be any compound that contains an unsaturation and/or a functional group capable of undergoing hydrogenation.
- Suitable acyclic compounds include linear C 3 -C 20 olefins, such as propylene, n-butene, or octene; olefinic alcohols such as prenyl alcohol; aJlylic compounds such as allylchloride or allylalcohol; ⁇ , ⁇ -unsaturated ketones such as mesityl oxide or 4-methyl-3-penten-2-one; and acrylic compounds such as acrylic acid, methacrylic acid, and esters thereof.
- the functional group in the cyclic or acyclic compound that is capable of undergoing hydrogenation is, when present, preferably a substituent selected from the group consisting of aldehyde, ketone, alkene, alkyne, amide, anhydride, aryl, azide, azo, carboxylic ester, imine, hydrazone, hydroperoxides, nitriles, nitro, oxime, and ozonide.
- the functional group may be present in the compound because it is desired in the final product, in which case it will not undergo hydrogenation; otherwise the functional group, if suitable, may be hydrogenated.
- the reactivity of the functional group can be determined, in part, by the reaction conditions and other variables appreciated by those of skill in the art.
- the ratio of compounds being hydrogenated to compounds being dehydrogenated may vary widely, as appreciated by those of skill in the art.
- the molar ratio of the cyclic compound being hydrogenating and the cyclic compound being dehydrogenated preferably ranges from about 1:10 to about 3:1, more preferably from about 1:5 to about 2:1, and most preferably from about 1:3 to about 5:4.
- the transhydrogenation reaction may take in the presence of a catalyst.
- the catalyst is a noble metal catalyst, such as platinum, palladium, gold, ruthenium, rhodium, osmium, indium, and combinations thereof that can be supported or unsupported. Suitable supports include activated charcoal or carbon, alumina, silica, magnesia and titania or mixtures thereof. More preferably the noble metal catalyst is a palladium or a platinum catalyst or a palladium or platinum catalyst on charcoal (PoVC or Pt/C).
- Noble metal catalysts are available commercially from Johnson-Matthey or BASF (Engelhard), for example, as commercial eggshell type, 1-10% Pd/C catalysts.
- the noble metal catalyst may also be combined with a nickel catalyst. In this embodiment, Pd/C + Ni catalysts and Pt/C + Ni catalysts are also preferred.
- the amount of noble metal in the catalyst typically ranges from about 1% to about 20%.
- Hydrogen is generated from the process during the dehydrogenation reaction. Depending on the amount of hydrogen generated, an external source of hydrogen for the hydrogenation reaction may not be necessary. For other embodiments, it may be desirable to add a supplemental hydrogen source, such as hydrogen gas, to accelerate the reaction or promote the yield of certain desired products. Even when supplementing the reaction with hydrogen, large stoichiometric amounts of hydrogen are generally not necessary.
- the transhydrogenation reaction may take place under reaction conditions known to those of skill in the art. For instance, the reaction may take place in a single reaction vessel, for instance a one-liter autoclave.
- the reaction takes place under heat (typically 125-300 0 C; preferably 230-270 0 C) and pressure (typically 10450 psi hydrogen; preferably about 14.5 psi hydrogen) from a time period ranging from 1-48 hours.
- pressure typically 10450 psi hydrogen; preferably about 14.5 psi hydrogen
- the transhydrogenation reaction will be conducted as a liquid-phase reaction, which is preferable.
- the above-described reaction conditions may, however, be varied and are dependent on the other process conditions, i.e. temperature, pressure, catalyst type and concentration of the catalyst, compounds used in the reaction, molar ratio of the compounds, and other variables appreciated by those of skill in the art.
- the dehydrogenation reaction and the hydrogenation reaction of the transhydrogenation reaction takes place at the same time or near the same time.
- the reaction can be considered an in situ reaction, taking place in a single reaction vessel.
- the transhydrogenation process reduces the number of steps necessary to make each product and saves the resources that are used for each individual reaction.
- the invention also relates to a process for hydrogenating a cyclic compound comprising reacting a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation to produce cyclic compound having a saturated cyclic ring and/or a hydrogenated functional group.
- the reaction takes place in the presence of hydrogen gas that is generated from a dehydrogenation reaction that takes place at the same time or near the same time as the hydrogenation reaction.
- the cyclic compound being hydrogenated is a substituted or unsubstituted aryl, heteroaryl, cycloalkyl containing at least one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compound containing at least one unsaturation in the cyclic ring, or heterocyclic compound containing at least one functional group capable of undergoing hydrogenation.
- the cyclic compound being hydrogenated is preferably a substituted or unsubstituted cyclohexanone containing at least one unsaturation, a substituted or unsubstituted cyclohexanone containing a saturated cyclic ring, or a phenol. More preferably, the cyclic compound is isophorone, trimethylcyclohexanone, or phenol.
- the cyclic compound having a saturated cyclic ring is preferably a substituted or unsubstituted cyclohexanone or a substituted or unsubstituted cyclohexanol. More preferably, the cyclic compound having a saturated cyclic ring is trimethylcyclohexanone, trimethylcyclohexanol, or cyclohexanol.
- the invention also relates to a process for dehydrogenating a cyclic compound, comprising dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings in the presence of a catalyst to produce a cyclic compound having at least one unsaturated ring.
- the hydrogen gas liberated from the dehydrogenation reaction is used in a hydrogenation reaction that takes place in the same reaction vessel.
- the cyclic compound that contains one or more saturated cyclic rings is preferably a substituted or unsubstituted cyclohexyl or a substituted or unsubstituted heterocyclic compound. More preferably, the cyclic compound is a substituted or unsubstituted cyclohexylphenol or a substituted or unsubstituted piperidine.
- the cyclic compound having at least one unsaturated ring is preferably a substituted or unsubstituted aryl compound or a substituted or unsubstituted heteroaryl compound. More preferably, the cyclic compound is a substituted or unsubstituted phenylphenol or a substituted or unsubstituted pyridine.
- the cyclohexyl alkyl ether may be used as a fragrance.
- the fragrance may be used as a component of a perfume composition, or used in perfume cosmetics, such as creams, lotions, toilet waters, aerosols, toilet soaps, etc.
- the fragrance comprises
- the fragrances can also be used as a component of industrial products to improve their odor. Suitable industrial products include washing and cleaning agents, disinfectants, agents for treating textiles, etc. The products can also be used in other commercial markets, as well.
- the phenyl phenols and cyclic ketones are useful as building blocks or precursors for polycarbonates and flame retardants.
Abstract
This invention relates to a transhydrogenation process involving the dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and hydrogenating at least one cyclic or acyclic compound that contains at least one unsaturation and/or a functional group capable of undergoing hydrogenation. The process can be used to produce two or more commercially desirable products, including trimethylcyclohexanone.
Description
Transhydrogenation Processes
Cross Reference to Related Applications
[0001] This application claims priority under 35 U.S.C. § 119 to U.S. provisional application serial no. 61/015,500, filed December 20, 2007, which is incorporated herein by reference.
Field of Invention
[0002] This invention relates to a transhydrogenation process involving the transfer of hydrogen from one compound to another compound to form new compounds, for example, using a transhydrogenation reaction to convert cyclic aliphatic compounds into aromatic compounds.
Background
[0003] Hydrogenation and dehydrogenation reactions, the two reactions involved in transhydrogenation, are chemical processes used to form compounds that have increased their hydrogen content (hydrogenation) or decreased it (dehydrogenation). Transhydrogenation processes have been previously used. See e.g. U.S. Patent Nos. 3,267,170; 4,684,755; and 5,585,530, the disclosure of which is herein incorporated by reference. However, conventional transhydrogenation reactions involve either the hydrogenation of small-chain olefins, such as propylene or ethylene, to produce alkanes, or the dehydrogenation of small- chain alkanes to produce olefins. The focus of these transhydrogenation reactions thus lies in small-chain linear hydrocarbons, typically having four or fewer carbon atoms. [0004J The reaction conditions desirable for hydrogenating small-chain olefins or dehydrogenating small-chain linear alkanes, however, are typically too harsh and largely ineffective for transhydrogenation methods involving more complex compounds, such as cyclic compounds. In particular, the high reactions temperatures (typically 400-500° C), the catalyst systems (many of which involve chromium), and the vapor-phase conditions of the reaction all can be problematic when attempting to conduct a transhydrogenation reaction that includes a cyclic compound. For instance, under conventional conditions used for small- chain linear hydrocarbons, many of the cyclic products would not be stable and many of the desired functional groups would either become oxidized or otherwise not survive the reaction conditions. Moreover, the conventional transhydrogenation methods focus on only either the
hydrogenation aspects or the dehydrogenation aspects for producing a single desired product: using a transhydrogenation method to produce two or more useful products is not contemplated.
[0005] When more complex cyclic compounds are hydrogenated or dehydrogenated, these reactions are typically performed independently. The hydrogenation reactions involve the use of molecular hydrogen in combination with a metal catalyst, and the dehydrogenation reactions involve the use of a metal catalyst and mechanism for removing liberated hydrogen from the system. However, a separate hydrogenation reaction involves the handling of large volumes of hazardous hydrogen gas, and a separate dehydrogenation generates hydrogen which is usually disregarded as waste. Both of these features are undesirable. [0006] Accordingly, there is a need in the art for a transhydrogenation method that can be applied to cyclic compounds to produce one or more useful products through the reaction. This invention answers that need.
Summary of the Invention
[0007] This invention relates to a transhydrogenation process involving cyclic compounds. The process comprises dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and hydrogenating at least one cyclic compound or acyclic compound that contains at least one unsaturation and/or a functional group capable of undergoing hydrogenation. The hydrogen generated in the dehydrogenation reaction is used as the hydrogen source in the hydrogenation reaction.
[0008] The invention also relates to a process for hydrogenating a cyclic compound comprising reacting a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation to produce a cyclic compound having a saturated cyclic ring and/or a hydrogenated functional group. The reaction takes place in the presence of hydrogen gas that is generated from a dehydrogenation reaction taking place at the same time or near the same time as the hydrogenation reaction. [0009] The invention also relates to a process for dehydrogenating a cyclic compound, comprising dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings in the presence of a catalyst to produce a cyclic compound having at least one unsaturated ring. The hydrogen gas liberated from the dehydrogenation reaction is used in a hydrogenation reaction that takes place in the same reaction vessel.
Detailed Description
[001QJ The hydrogenation reactions used in this invention typically involve the saturation of a double bond in a cyclic or acyclic compound. The double bond being hydrogenated may be, for instance, one or more of the double bonds located in the ring of an aromatic compound. The hydrogenation reaction can also involve the reduction of a functional group in a cyclic or acyclic compound, for example reducing a carbonyl group to an alcohol. Dehydrogenation reactions used in this invention typically involve the formation of an unsaturated cyclic compound from a saturated cyclic compound, for example forming an aromatic compound from a cyclo-aliphatic compound. This process thus involves the release of hydrogen from one compound and the uptake of hydrogen by the other compound, the reaction occurring under the appropriate temperature, pressure, catalyst type, and concentration conditions.
[0011] The process allows for the simultaneous, or near simultaneous, transfer of hydrogen from a donor cyclic compound to a receptor compound, which beneficially precludes the handling of large amounts of hydrogen gas. Further, the choice of cyclic starting materials can produce two or more products, all of which have commercial uses. This can be achieved without the use of large stoichiometric amounts of hydrogen gas. [0012] This invention relates to an transhydrogenation process involving cyclic compounds. The process comprises dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and hydrogenating at least one cyclic or acyclic compound that contains at least one unsaturation and/or a functional group capable of undergoing hydrogenation. The hydrogen generated in the dehydrogenation reaction is used in the hydrogenation reaction.
[0013] The cyclic compound in the dehydrogenation step may be any cyclic compound, such as a substituted or unsubstituted cycloaikyl, or a substituted or unsubstituted heteroalkyl. When the cycloaikyl or heteroalkyl is substituted, it may be substituted with one or more substituents selected from the group consisting of alkyl, aryl, alcohol, thiol, ester, ether, amine, imine, amide, nitro, carboxylic acid, carbonate, isocyanate, halogen, and combinations thereof. Preferably the substituent is an alkyl group, such as a methyl group, or an alcohol. [0014] The compound in the hydrogenation step may be cyclic or acyclic. If the compound is cyclic, the cyclic compound may be any compound that contains either an unsaturation in the ring or a functional group capable of undergoing hydrogenation. Such compounds include substituted or unsubstituted aryl, heteroaryl, cycloaikyl containing at least
one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compounds containing at least one unsaturation in the cyclic ring, and heterocyclic compounds containing at least one functional group capable of undergoing hydrogenation.
[0015] If the compound is acyclic, the acyclic compound may be any compound that contains an unsaturation and/or a functional group capable of undergoing hydrogenation. Suitable acyclic compounds include linear C3-C20 olefins, such as propylene, n-butene, or octene; olefinic alcohols such as prenyl alcohol; aJlylic compounds such as allylchloride or allylalcohol; α,β-unsaturated ketones such as mesityl oxide or 4-methyl-3-penten-2-one; and acrylic compounds such as acrylic acid, methacrylic acid, and esters thereof. [0016] The functional group in the cyclic or acyclic compound that is capable of undergoing hydrogenation is, when present, preferably a substituent selected from the group consisting of aldehyde, ketone, alkene, alkyne, amide, anhydride, aryl, azide, azo, carboxylic ester, imine, hydrazone, hydroperoxides, nitriles, nitro, oxime, and ozonide. The functional group may be present in the compound because it is desired in the final product, in which case it will not undergo hydrogenation; otherwise the functional group, if suitable, may be hydrogenated. The reactivity of the functional group can be determined, in part, by the reaction conditions and other variables appreciated by those of skill in the art. [0017] The ratio of compounds being hydrogenated to compounds being dehydrogenated may vary widely, as appreciated by those of skill in the art. The molar ratio of the cyclic compound being hydrogenating and the cyclic compound being dehydrogenated preferably ranges from about 1:10 to about 3:1, more preferably from about 1:5 to about 2:1, and most preferably from about 1:3 to about 5:4.
[0018] The transhydrogenation reaction may take in the presence of a catalyst. Preferably, the catalyst is a noble metal catalyst, such as platinum, palladium, gold, ruthenium, rhodium, osmium, indium, and combinations thereof that can be supported or unsupported. Suitable supports include activated charcoal or carbon, alumina, silica, magnesia and titania or mixtures thereof. More preferably the noble metal catalyst is a palladium or a platinum catalyst or a palladium or platinum catalyst on charcoal (PoVC or Pt/C). Noble metal catalysts are available commercially from Johnson-Matthey or BASF (Engelhard), for example, as commercial eggshell type, 1-10% Pd/C catalysts. The noble metal catalyst may also be combined with a nickel catalyst. In this embodiment, Pd/C + Ni
catalysts and Pt/C + Ni catalysts are also preferred. The amount of noble metal in the catalyst typically ranges from about 1% to about 20%.
[0019] Hydrogen is generated from the process during the dehydrogenation reaction. Depending on the amount of hydrogen generated, an external source of hydrogen for the hydrogenation reaction may not be necessary. For other embodiments, it may be desirable to add a supplemental hydrogen source, such as hydrogen gas, to accelerate the reaction or promote the yield of certain desired products. Even when supplementing the reaction with hydrogen, large stoichiometric amounts of hydrogen are generally not necessary. [0020] The transhydrogenation reaction may take place under reaction conditions known to those of skill in the art. For instance, the reaction may take place in a single reaction vessel, for instance a one-liter autoclave. Typically, the reaction takes place under heat (typically 125-300 0C; preferably 230-2700C) and pressure (typically 10450 psi hydrogen; preferably about 14.5 psi hydrogen) from a time period ranging from 1-48 hours. Under these conditions, the transhydrogenation reaction will be conducted as a liquid-phase reaction, which is preferable. The above-described reaction conditions may, however, be varied and are dependent on the other process conditions, i.e. temperature, pressure, catalyst type and concentration of the catalyst, compounds used in the reaction, molar ratio of the compounds, and other variables appreciated by those of skill in the art. [0021] In a preferred embodiment, the dehydrogenation reaction and the hydrogenation reaction of the transhydrogenation reaction takes place at the same time or near the same time. The reaction can be considered an in situ reaction, taking place in a single reaction vessel. The transhydrogenation process reduces the number of steps necessary to make each product and saves the resources that are used for each individual reaction. [0022] The invention also relates to a process for hydrogenating a cyclic compound comprising reacting a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation to produce cyclic compound having a saturated cyclic ring and/or a hydrogenated functional group. The reaction takes place in the presence of hydrogen gas that is generated from a dehydrogenation reaction that takes place at the same time or near the same time as the hydrogenation reaction. [0023] The cyclic compound being hydrogenated is a substituted or unsubstituted aryl, heteroaryl, cycloalkyl containing at least one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compound containing at least one unsaturation in the cyclic ring, or heterocyclic compound
containing at least one functional group capable of undergoing hydrogenation. The cyclic compound being hydrogenated is preferably a substituted or unsubstituted cyclohexanone containing at least one unsaturation, a substituted or unsubstituted cyclohexanone containing a saturated cyclic ring, or a phenol. More preferably, the cyclic compound is isophorone, trimethylcyclohexanone, or phenol.
[0024] The cyclic compound having a saturated cyclic ring is preferably a substituted or unsubstituted cyclohexanone or a substituted or unsubstituted cyclohexanol. More preferably, the cyclic compound having a saturated cyclic ring is trimethylcyclohexanone, trimethylcyclohexanol, or cyclohexanol.
[0025] The invention also relates to a process for dehydrogenating a cyclic compound, comprising dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings in the presence of a catalyst to produce a cyclic compound having at least one unsaturated ring. The hydrogen gas liberated from the dehydrogenation reaction is used in a hydrogenation reaction that takes place in the same reaction vessel.
[0026] The cyclic compound that contains one or more saturated cyclic rings is preferably a substituted or unsubstituted cyclohexyl or a substituted or unsubstituted heterocyclic compound. More preferably, the cyclic compound is a substituted or unsubstituted cyclohexylphenol or a substituted or unsubstituted piperidine.
[0027] The cyclic compound having at least one unsaturated ring is preferably a substituted or unsubstituted aryl compound or a substituted or unsubstituted heteroaryl compound. More preferably, the cyclic compound is a substituted or unsubstituted phenylphenol or a substituted or unsubstituted pyridine.
[0028] Products produced from the processes of this invention have various commercial uses. For instance, the cyclohexyl alkyl ether may be used as a fragrance. The fragrance may be used as a component of a perfume composition, or used in perfume cosmetics, such as creams, lotions, toilet waters, aerosols, toilet soaps, etc. Typically, the fragrance comprises
0.05% to 2% by weight of the product. The fragrances can also be used as a component of industrial products to improve their odor. Suitable industrial products include washing and cleaning agents, disinfectants, agents for treating textiles, etc. The products can also be used in other commercial markets, as well. For example, the phenyl phenols and cyclic ketones are useful as building blocks or precursors for polycarbonates and flame retardants.
[0029] The following examples are intended to illustrate the invention. These examples should not be used to limit the scope of the invention, which is defined by the claims.
[0030] EXAMPLE 1
[0031] 84g (0.85 mole) 2-methylpiperidine, 41Og (2.97 mole) isophorone and 1Og of a
5% palladium on carbon catalyst were charged to a 1 -litre autoclave. After purging with nitrogen, the mixture was heated to 150 0C. After about 4 hours the reaction mixture was cooled. The residue on analysis showed complete conversion of the 2-methylpiperidine to 2- picoline together with stoichiometric conversion of isophorone to 3,3,5- trimethylcyclohexanone.
[0032] EXAMPLE 2
[0033] 133.5g cyclohexylphenol (1.0 mole) and 366.4g of isophorone (3.5 mole) together with 1Og of a 5% palladium on carbon catalyst (Johnson-Matthey 87L) were charged to a 1- Htre autoclave. After purging with nitrogen, the autoclave was sealed under a pressure of 50 psi hydrogen. The contents were then heated to 225 0C for a period of 22 hours. The residue, after filtration from the catalyst was found to contain the following:
Trimethylcyclohexanone - 67.26%
Isophorone - 1.97%
2-Phenylphenol - 28.74%
2-Cyclohexylρhenol - 0.06%
Unknowns - 1.97%
[0034] EXAMPLE 3
[0035] 10.0g 2 -cyclohexylphenol (0.057 mole) and 150g 3,3,5-trimethylcyclohexanone (1.071 mole) together with 0.75g of a Ni and 4.5g of a 10% palladium on carbon catalyst were charged to a 1 -litre autoclave. After purging with helium, the autoclave was sealed under a pressure of 14.5 psi hydrogen. The contents were then heated to 220 0C for a period of 5 hours. The residue, after filtration from the catalyst was found to contain the following:
Trimethylcyclohexanone - 83.10%
Trimethylcyclohexanol - 9.10% (mix of cis and trans)
2-Phenylphenol - 1.82%
2-Cyclohexylphenol - 1.83%
Others - 2.18%
[0036] EXAMPLE 4
[0037] 52.9g 4-cyclohexylphenol (0.30 mole) and 165.8g isophorone (1.20 mole) together with 8.3g of a 10% palladium on carbon catalyst were charged to a 1 -litre autoclave. After purging with helium, the autoclave was sealed under a pressure of 14.5 psi hydrogen. The contents were then heated to 220 0C for a period of όhours. The residue, after filtration from the catalyst was found to contain the following:
Trimethylcyclohexanone - 59.97%
Isophorone - 16.56%
4-Phenylρhenol - 22.79%
Others - 1.68%
[0038] EXAMPLE 5
[0039] 35.27g 2-cyclohexylphenol (0.20 mole), 17.6Og 4-cyclohexylphenol (0.1 mole) and 165.8g isophorone (1.20 mole) together with 8.3g of a 10% palladium on carbon catalyst were charged to a 1 -litre autoclave. After purging with helium, the autoclave was sealed under a pressure of 14.5 psi hydrogen. The contents were then heated to 220 0C for a period of 6 hours. The residue, after filtration from the catalyst was found to contain the following:
Trimethylcyclohexanone - 54.64%
Isophorone - 21.47%
2-PhenyIphenol - 13.21%
2-Cyclohexylphenol - 2.36%
4-Phenylphenol - 7.27%
Others - 1.05%
[0040] EXAMPLE 6
[0041] 94.1 g phenol (1.0 mole) and 141.Og 2-cyclohexylphenol (0.8 mole) together with 2.82g of a 10% palladium on carbon catalyst were charged to a 1 -litre autoclave. After purging with helium, the autoclave was sealed under a pressure of 14.5 psi hydrogen. The contents were then heated to 220 0C for a period of 5.2 hours. The residue, after filtration from the catalyst was found to contain the following:
Cyclohexanol - 0.48%
Cyclohexanone - 18.12%
Phenol - 19.97%
2-Phenylphenol - 22.92 2-Cyciohexylphenol - 31.60% Others - 6.91%
Claims
1. A transhydrogenation process, comprising: a. dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings, and b. hydrogenating at least one cyclic or acyclic compound that contains at least one unsaturatkm and/or a functional group capable of undergoing hydrogenation, wherein the hydrogen generated in the dehydrogenation reaction is used in the hydrogenation reaction.
2. The process of claim 1, wherein the cyclic compound in the dehydrogenation step is a substituted or unsubstituted cycloalkyL or a substituted or unsubstituted heteroalkyl.
3. The process of claim 2, wherein the cycloalkyl or heteroalkyl is substituted with one or more substituents selected from the group consisting of alkyl, aryl, alcohol, thiol, ester, ether, amine, imine, amide, nitro, carboxylic acid, carbonate, isocyanate, halogen, and combinations thereof.
4. The process of claim 2, wherein the substituent is an alkyl group or an alcohol.
5. The process of claim 1 , wherein the hydrogenation step involves a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation.
6. The process of claim 5, wherein the cyclic compound is a substituted or unsubstituted aryl, heteroaryl, cycloalkyl containing at least one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compound containing at least one unsaturation in the cyclic ring, or heterocyclic compound containing at least one functional group capable of undergoing hydrogenation.
7. The process of claim 1, wherein the functional group capable of undergoing hydrogenation is a substituent selected from the group consisting of aldehyde, ketone, alkene, alkyne, amide, anhydride, aryl, azide, azo, carboxylic ester, imine, hydrazone, hydroperoxides, nitriles, nitro, oxime, and ozonide.
8. The process of claim 1, wherein the process takes place in the presence of a catalyst selected from the group consisting of a noble metal catalyst, a noble metal catalyst on. a support, a copper catalyst, and combinations thereof.
9. The process of claim 1, wherein the dehydrogenation reaction and the hydrogenation reaction take place at the same time or near the same time.
10. The process of claim 1, wherein the reactions take place in a single reaction vessel.
11. The process of claim 1, wherein the reaction is conducted as a liquid-phase reaction.
12. A process for hydrogenating a cyclic compound, comprising reacting a cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation in the presence of hydrogen gas that is generated from a dehydrogenation reaction that takes place at the same time or near the same time as the hydrogenation reaction, to produce a cyclic compound having a saturated cyclic ring and/or a hydrogenated functional group.
13. The process of claim 12, wherein the cyclic compound that contains at least one unsaturation in the cyclic ring and/or a functional group capable of undergoing hydrogenation is a substituted or unsubstituted aryl, heteroaryl, cycloalkyl containing at least one unsaturation in the cyclic ring, cycloalkyl containing at least one functional group capable of undergoing hydrogenation, heterocyclic compound containing at least one unsaturation in the cyclic ring, or heterocyclic compound containing at least one functional group capable of undergoing hydrogenation.
14. The process of claim 13, wherein the cyclic compound is a substituted or unsubstituted cyclohexanone containing at least one unsaturation, a substituted or unsubstituted cyclohexanone containing a saturated cyclic ring, or a phenol
15. The process of claim 14, wherein the cyclic compound is isophorone, trimethylcyclohexanone, or phenol.
16. The process of claim 12, wherein the cyclic compound having a saturated cyclic ring is a substituted or unsubstituted cyclohexanone or a substituted or unsubstituted cyclohexanol.
17. The process of claim 16, wherein the cyclic compound having a saturated cyclic ring is trimethylcyclohexanone, trimethylcyclohexanol, or cyclohexanol.
18. The process of claim 12, wherein the dehydrogenation reaction comprises dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings.
19. A process for dehydrogenating a cyclic compound, comprising dehydrogenating at least one cyclic compound that contains one or more saturated cyclic rings to produce a cyclic compound having at least one unsaturated ring, wherein the hydrogen gas liberated from the dehydrogenation reaction is used in a hydrogenation reaction that takes place in the same reaction vessel.
20. The process of claim 19, wherein cyclic compound that contains one or more saturated cyclic rings is a substituted or unsubstituted cyclohexyl or a substituted or unsubstituted heterocyclic compound.
21. The process of claim 20, wherein the cyclic compound is a substituted or unsubstituted cyclohexylphenol or a substituted or unsubstituted piperidine.
22. The process of claim 19, wherein the cyclic compound having at least one unsaturated ring is a substituted or unsubstituted aryl compound or a substituted or unsubstituted heteroaryl compound.
23. The process of claim 22, wherein the cyclic compound is a substituted or unsubstituted phenylphenol or a substituted or unsubstituted pyridine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1550007P | 2007-12-20 | 2007-12-20 | |
| US61/015,500 | 2007-12-20 |
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| WO2009085826A2 true WO2009085826A2 (en) | 2009-07-09 |
| WO2009085826A3 WO2009085826A3 (en) | 2009-09-11 |
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| PCT/US2008/087162 WO2009085826A2 (en) | 2007-12-20 | 2008-12-17 | Transhydrogenation processes |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB310055A (en) * | 1928-04-22 | 1930-07-21 | Schering-Kahlbaum Aktiengesellschaft | |
| GB342010A (en) * | 1928-11-29 | 1931-01-29 | Schering Kahlbaum Ag | Process for the hydrogenation of pyridine, quinoline and homologues thereof |
| US1877203A (en) * | 1928-04-21 | 1932-09-13 | Firm Schering Kahlbaum A G | Method of simultaneous hydrogenation and dehydrogenation |
| US2560361A (en) * | 1946-06-01 | 1951-07-10 | Standard Oil Dev Co | Production of 3, 3, 5-trimethyl cyclohexanone |
| US3697606A (en) * | 1968-03-20 | 1972-10-10 | Union Carbide Corp | Para-phenylphenol preparation |
| US4322556A (en) * | 1979-03-01 | 1982-03-30 | Texaco Inc. | Method for preparing aniline by reaction of nitrobenzene and vinylcyclohexene |
| EP0195541A1 (en) * | 1985-03-18 | 1986-09-24 | Mobil Oil Corporation | Process for conversion of alicyclic compounds into aromatic compounds |
| EP0287290A1 (en) * | 1987-04-14 | 1988-10-19 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of 4,4'-biphenol, precursor of same and preparation process of precursor |
| WO2006009630A2 (en) * | 2004-06-22 | 2006-01-26 | The Regents Of Teh University Of California | Method and system for hydrogen evolution and storage |
-
2008
- 2008-12-17 WO PCT/US2008/087162 patent/WO2009085826A2/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1877203A (en) * | 1928-04-21 | 1932-09-13 | Firm Schering Kahlbaum A G | Method of simultaneous hydrogenation and dehydrogenation |
| GB310055A (en) * | 1928-04-22 | 1930-07-21 | Schering-Kahlbaum Aktiengesellschaft | |
| GB342010A (en) * | 1928-11-29 | 1931-01-29 | Schering Kahlbaum Ag | Process for the hydrogenation of pyridine, quinoline and homologues thereof |
| US2560361A (en) * | 1946-06-01 | 1951-07-10 | Standard Oil Dev Co | Production of 3, 3, 5-trimethyl cyclohexanone |
| US3697606A (en) * | 1968-03-20 | 1972-10-10 | Union Carbide Corp | Para-phenylphenol preparation |
| US4322556A (en) * | 1979-03-01 | 1982-03-30 | Texaco Inc. | Method for preparing aniline by reaction of nitrobenzene and vinylcyclohexene |
| EP0195541A1 (en) * | 1985-03-18 | 1986-09-24 | Mobil Oil Corporation | Process for conversion of alicyclic compounds into aromatic compounds |
| EP0287290A1 (en) * | 1987-04-14 | 1988-10-19 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of 4,4'-biphenol, precursor of same and preparation process of precursor |
| WO2006009630A2 (en) * | 2004-06-22 | 2006-01-26 | The Regents Of Teh University Of California | Method and system for hydrogen evolution and storage |
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| WO2009085826A3 (en) | 2009-09-11 |
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