Selective semi-hydrogenation of Allene

Abstract

This invention relates to the field of catalytic hydrogenation, and more particularly to the semi-hydrogenation of allenes to corresponding alkenes in the presence of heterogeneous catalysts.

Description

[Technical Field]

[0001] This invention relates to the field of catalytic hydrogenation, and more particularly to the partial hydrogenation of allenes to corresponding alkenes in the presence of heterogeneous catalysts.

[0002] background Compounds containing alkenes, particularly ω-1 alkenes, possess highly desirable skeletons that can be used as is or as important intermediates, particularly useful for preparing more complex compounds in different fields such as cosmetics, pharmaceuticals, or agricultural chemistry. The alkene group can be obtained by reduction of the corresponding triple bond, a method suitable for promoting the formation of a double bond by cis stereochemistry. However, access to the corresponding triple bond can be cumbersome. An alternative approach is the hepihydrogenation of allenes. Despite the fact that allenes are readily available, their hepihydrogenation, especially the hepihydrogenation of terminal allenes to ω-1 alkenes, is rarely disclosed in the literature and suffers from moderate to low stereoselectivity and regioselectivity.

[0003] Therefore, there is a need today to develop novel methods that achieve high regioselectivity while controlling stereoselectivity and reaching the alkene group through the semi-hydrogenation of allenes.

[0004] The present invention enables the semi-hydrogenation of allenes to corresponding alkenes using molecule H2, and the process is carried out in the presence of a heterogeneous catalyst while promoting the formation of cis isomers and achieving high regioselectivity. To the best of the inventors' knowledge, the process of the present invention has not been reported in the prior art, and in particular, high selectivity and regioselectivity for monosubstituted allenes of formula (I) have not been reported.

[0005] Description of the Invention Surprisingly, it was discovered that heterogeneous catalysts enable the hydrogenation of allenes with high regioselectivity and stereoselectivity.

[0006] Therefore, the first object of the present invention is to use the molecule H2, formula [ka] (In the formula, R 1 C optionally contains 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom. 2~30 The formula of allenes (which are hydrocarbons) [ka] (In the formula, R 1 A process for the semi-hydrogenation of the corresponding alkene (which has the same meaning as defined above), This is a process carried out in the presence of a heterogeneous catalyst.

[0007] To clarify, the wavy bond in compounds of formula (II), etc., means in the usual sense as understood by those skilled in the art, i.e., the double bond may have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer, or a mixture thereof. In fact, the alkene of formula (II) may be in the form of its E or Z isomer or a mixture thereof, for example, the process of the present invention yields a composition of a substance consisting of one or more alkenes of formula (II) having the same chemical structure but different double bond configurations. In particular, the alkene of formula (II) may be in the form of a mixture of isomers E and Z, where isomer Z may constitute at least 50% or at least 75% of the total mixture (i.e., a mixture Z / E between 75 / 25 and 100 / 0). According to a particular embodiment, the alkene of formula (II) is in the form of its Z isomer, i.e., 100% is Z.

[0008] The term "depending on the circumstances" is understood to mean that a particular group that may or may not include a particular atom may or may not include it.

[0009] "...hydrocarbon ligand..." means that the group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e., a linear or branched saturated hydrocarbon (e.g., alkyl group), a linear or branched unsaturated hydrocarbon (e.g., alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g., cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g., cycloalkenyl or cycloalkynyl), or an aromatic hydrocarbon, i.e., an aryl group, or a mixture of such groups. For example, a particular group may include linear alkyl, branched alkenyl (e.g., having one or more carbon-carbon double bonds), (poly)cycloalkyl, and aryl moieties unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is mentioned to be in the form of two or more topologies (e.g., linear, cyclic, or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl), it also means a group that may include a moiety having any one of the topologies, or a moiety that is saturated or unsaturated, as described above. Similarly, in all embodiments of the present invention, when it is mentioned that a group is in one type of saturated or unsaturated (e.g., alkyl) form, it means that the group may be of any type of topology (e.g., linear, cyclic, or branched) or may have several parts having various topologies.

[0010] The term "hydrocarbon group optionally containing..." is understood to mean that the hydrocarbon group optionally contains one, two or three oxygen atoms in the form of an alcohol, ketone, aldehyde, ether, ester, carboxylic acid, carbonate group and / or one or two nitrogen atoms in the form of an amine or amide group and / or one sulfur atom in the form of a thiol group. These groups can replace the hydrogen atoms of the hydrocarbon group and thus can be bonded laterally to the hydrocarbon or, where chemically possible, replace the carbon atoms of the hydrocarbon group and thus can be inserted into the hydrocarbon chain. For example, the -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group containing an alcohol group (substitution of a hydrogen atom), i.e., a C4 hydrocarbon containing an oxygen atom, and the -CH2-CH2-COO-CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group containing one ester group (substitution of a carbon atom / insertion into the hydrocarbon chain), i.e., a C7 hydrocarbon containing two oxygen atoms, and, similarly, the -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a C6 hydrocarbon group containing two ether groups, i.e., a C6 hydrocarbon containing two oxygen atoms.

[0011] According to any embodiment of the present invention, R 1 when it is a hydrocarbon containing one to three oxygen atoms and / or one to two nitrogen atoms and / or one sulfur atom, the heteroatom is not directly bonded to the allene functional group.

[0012] According to any one of the above embodiments of the present invention, the allene of formula (I) is a C5-C 30 compound, in particular, a C5-C 20 compound, in particular, a C5-C 15 compound, in particular, a C5-C 12 compound, and even more particularly, a C8-C 12 compound.

[0013] According to any one of the above embodiments of the present invention, R 1 is a C 2~25It is a hydrocarbon. In particular, R 1 C may contain 1 to 3 oxygen atoms. 2~20 It is a hydrocarbon. In particular, R 1 C may contain 1 to 3 oxygen atoms. 2~18 It is a hydrocarbon. In particular, R 1 C may contain 1 to 3 oxygen atoms. 3~18 It is a hydrocarbon. In particular, R 1 C may contain 1 to 3 oxygen atoms. 4~18 It is a hydrocarbon.

[0014] According to any one of the above embodiments of the present invention, R 1 The group is substituted with a hydroxyl group. In particular, the hydroxyl group is at the α-position of the allene functional group. In other words, the allene in formula (I) is in formula [ka] (In the formula, R 2 C may contain 1-2 oxygen atoms and / or 1-2 nitrogen atoms and / or 1 sulfur atom. 1~14 In hydrocarbons, R 3 is a hydrogen atom or C 1~6 It is a hydrocarbon group; or R 2 and R 3 Together, they each have 1-2 hydroxyl groups and / or 1-3 C 1~6 Alkyl, C 2~6 Alkenil, C 1~6 C, optionally substituted with an alkoxy group 5~16 Cycloalkyl or C 5~16 It is a compound that forms a cycloalkenyl group, and The alkene in equation (II) is, [ka] (In the formula, R 2 and R 3 (This has the same meaning as defined above.)

[0015] According to any embodiment of the present invention, R3 is a hydrogen atom, a phenyl group, or C 1~6 It can be an alkyl group. In particular, R 3 is a hydrogen atom or C 1~4 It can be an alkyl group. In particular, R 3 is a hydrogen atom or C 1~3 It can be an alkyl group. In particular, R 3 R can be a hydrogen atom or a methyl, ethyl, or isopropyl group. In particular, 3 R can be a hydrogen atom or a methyl group. More specifically, 3 It can be a methyl group.

[0016] According to any embodiment of the present invention, R 2 C may contain 1-2 oxygen atoms. 1~12 It is a hydrocarbon. In particular, R 2 C may contain 1-2 oxygen atoms. 1~10 It is a hydrocarbon. In particular, R 2 These are linear, branched, or cyclic C1-C atoms, each substituted in different cases. 10 Alkyl, or linear, branched, or cyclic C2-C 10 It is an alkenyl group, or a linear or branched C1-C6 phenylalkyl group. In particular, R 2 These are, depending on the case, substituted linear, branched, or cyclic C2-C2 atoms. 10 Alkyl, or linear, branched, or cyclic C2-C 10 It is an alkenyl group, or a linear or branched C1-C4 phenylalkyl group. In particular, R 2 R is a linear, branched, or cyclic C2-C9 alkyl group, or a linear, branched, or cyclic C2-C9 alkenyl group, or a linear or branched C1-C4 phenylalkyl group, which may be substituted. 2 R is a linear, branched, or cyclic C4-C9 alkyl group, or a linear, branched, or cyclic C4-C9 alkenyl group, or a linear or branched C1-C2 phenylalkyl group, which may be substituted. 2These are, depending on the circumstances, substituted linear, branched, or cyclic C5-C9 alkyl groups, or linear, branched, or cyclic C5-C9 alkenyl groups, or linear or branched C1-C2 phenylalkyl groups.

[0017] Furthermore, according to even further embodiments, R 2 When representing an alkenyl group, the carbon-carbon double bond is not terminal and is not conjugated to the allene.

[0018] R 2 The possible substituents are one, two, or three OR h , one or two NR h 2, or one S(=O)R h or one SO2R h (In the formula, R h This refers to a hydrogen atom, a C1-C2 halogen group, or a C1-C2 halogen group. 10 The group is a cyclic, linear, or branched alkyl or alkenyl group, preferably a C1-C4 linear or branched alkyl or alkenyl group. Other possible substituents include the COOR group. h You could also list these.

[0019] According to any embodiment of the present invention, R 2 and R 3 Together, they each have 1-2 hydroxyl atoms and / or 1-3 C atoms. 1~6 Alkyl, C 2~6 Alkenil, C 1~6 C, optionally substituted with an alkoxy group 5~14 Cycloalkyl or C 5~14 It forms a cycloalkenyl group. In particular, R 2 and R 3 Together, they each have 1-2 hydroxyl groups and / or 1-3 C atoms. 1~6 Alkyl, C 2~6 Alkenil, C 1~6 C, optionally substituted with an alkoxy group 5~12 Cycloalkyl or C 5~12 It forms a cycloalkenyl group. In particular, R 2 and R3 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 1~6 alkyl, C 2~6 alkenyl, C 1~6 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 5~10 and R 5~10 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 2 alkyl, C 3 alkenyl, C 1~6 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 2~6 and R 1~6 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 5~8 alkyl, C 5~8 alkenyl, C 2 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 3 and R 1~6 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 2~6 alkyl, C 1~6 alkenyl, C 5~6 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 5~6 and R 2 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 3 alkyl, C 1~4 alkenyl, C 2~4 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 1~4 and R 5~6 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 5~6 alkyl, C 2 alkenyl, C 3 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 1~3 and R 2~3 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 1~3 alkyl, C 5~6 cycloalkyl or C cycloalkenyl group substituted by an alkoxy group in some cases. In particular, R 5~6 and R 2 together form a C that is optionally substituted with one or two hydroxy groups and / or one to three C 3Together, they each have 1-2 hydroxyl groups and / or 1-3 C atoms. 1~2 Alkyl, C 2~3 Alkenil, C 1~2 C, optionally substituted with an alkoxy group 5~6 Cycloalkyl or C 5~6 It forms a cycloalkenyl group. More specifically, R 2 and R 3 These are, together, C, each optionally substituted with one or two methyl groups. 5~6 Cycloalkyl or C 5~6 It forms a cycloalkenyl group.

[0020] Non-limiting examples of compounds in (I) include 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, These are 4-methyldeca-1,2-dien-4-ol, 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol, and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

[0021] According to any embodiment of the present invention, the terminal allene of formula (I) can be prepared according to general methods described in the literature.

[0022] Non-limiting examples of compounds of formula (II) include (Z)-4,8-dimethylnonano-2,7-dien-4-ol, (Z)-2-phenylpenta-3-en-2-ol, (Z)-3-phenylhexa-4-en-3-ol, (Z)-2-methyl-3-phenylhexa-4-en-3-ol, 4-methyldeca-1,2-dien-4-ol, (Z)-3-methyl-1-phenylhexa-4-en-3-ol, (Z)-4,4-dimethyl-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclopentan-1-ol, (Z)-1-(propa-1-en-1-yl)cycloheptan-1-ol, (Z)-2-(propa-1-e These are (n-1-yl)decahydronaphthalen-2-ol, (4aS,8aS)-2-((Z)-propa-1-en-1-yl)decahydronaphthalen-2-ol, (Z)-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclooctan-1-ol, (Z)-1-(p-tolyl)buta-2-en-1-ol, (Z)-1-cyclohexylbuta-2-en-1-ol, (2Z,5E)-5-methylocta-2,5-dien-4-ol, (Z)-1-phenylhexa-4-en-3-ol, (6R,Z)-6,10-dimethylundeca-2,9-dien-4-ol, and (Z)-undeca-2-en-4-ol.

[0023] The terms “alkyl,” “alkenyl,” and “alkoxy” are understood to include branched and linear alkyl and alkenyl groups unless otherwise specified. The terms “alkenyl,” “cycloalkenyl,” and “heterocycloalkenyl” are understood to include one, two, or three olefinic double bonds, preferably one or two. The terms “cycloalkyl,” “cycloalkenyl,” “heterocycloalkyl,” “heterocycloalkenyl,” and “saturated or unsaturated ring” are understood to include monocyclic or condensed, spiro and / or bridged bicyclic or tricyclic cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl groups and saturated or unsaturated rings, preferably monocyclic cycloalkyl, cycloalkenyl, heterocycloalkyl, and heterocycloalkenyl groups.

[0024] According to any embodiment of the present invention, the heterogeneous catalyst comprises palladium (Pd) metal or nickel (Ni) metal. In particular, the heterogeneous catalyst comprises supported palladium (Pd) metal or supported nickel (Ni) metal.

[0025] According to any one of the above embodiments of the present invention, the palladium (Pd) or nickel (Ni) heterogeneous catalyst is supported on a support material.

[0026] To clarify, the supporting material is intended to be a material on which such metals can be deposited and which is inert to the hydrogen source and substrate.

[0027] According to any one of the above embodiments of the present invention, specific and non-limiting examples of the support material are carbon, silica, calcium carbonate, barium sulfate, titanium oxide, or aluminum oxide. Such supports are well known to those skilled in the art.

[0028] Supported or unsupported palladium (Pd) or nickel (Ni) are known compounds and are commercially available. Those skilled in the art can select preferred types of metals as a method of deposition on the carrier, as a percentage of the metal on the carrier material, as a form (powder, granules, pellets, extruded material, mousse, etc.), and as a surface area of ​​the carrier. The amount of metal relative to the carrier can range from 0.05% to 25% w / w, or even 1% to 6%, relative to the weight on the carrier used. Examples of suitable heterogeneous catalysts include, but are not limited to, Lindler catalysts (Pd-Pb / CaCO3), or Raney nickel or Pd / C; in particular, Lindler catalysts, or Raney nickel or sulfur-modified supported Pd catalysts as described in D. Albani, M. Shahrokhi, Z. Chen, S. Mitchell, R. Hauert, N. Lopez, J. Perez-Ramirez in Nat. Commun. 2018, 1-11, or polyamine-modified supported Pd catalysts as described in Q. Luo, Z. Wang, Y. Chen, S. Mao, K. Wu, K. Zhang, Q. Li, G. Lv, G. Huang, H. Li, Y. Wang in ACS Appl. Mater. Interfaces 2021, 13, 27, 31775-31784.

[0029] Heterogeneous catalysts can be added to the reaction medium of the process of the present invention at a wide range of concentrations. Non-limiting examples include metal concentrations ranging from 0.01 mol% to 10 mol% relative to the total amount of substrate. Preferably, the metal concentration is in the range of 0.02 mol% to 5 mol%, or even 0.04 mol% to 2 mol%. As is well known to those skilled in the art, the optimal metal concentration depends on the properties of the metal, the properties of the substrate, whether the process is performed in batches or continuously, the temperature and pressure of the H2 used during the process, and the desired reaction time.

[0030] The heterogeneous catalyst can be recycled at the end of the process of the present invention. In other words, the heterogeneous catalyst is recovered at the end of the process of the present invention and can be used several times in the process of the present invention.

[0031] According to any embodiment of the present invention, the process of the present invention is carried out in the absence of a base or additive.

[0032] Hydrogenation reactions can be carried out in or without a solvent. Where a solvent is required or used for practical reasons, the current solvents in hydrogenation reactions can be used for the purposes of the present invention. Non-limiting examples include aromatic solvents such as toluene, fluorobenzene, trifluorotoluene, ortho-difluorobenzene, ortho-dichlorobenzene, chlorobenzene, or xylene; hydrocarbon solvents such as hexane or cyclohexane; polar solvents such as ethers such as tetrahydrofuran, methyltetrahydrofuran, or MTBE; primary or secondary alcohols such as isopropanol or ethanol; or mixtures thereof. The choice of solvent is a function of the properties of the complex, and those skilled in the art can readily select the most convenient solvent in each case to optimize the hydrogenation reaction.

[0033] In the hydrogenation process of the present invention, the reaction is 2 5 Pa~100×10 5 The H2 pressure can be within the range of Pa (1 to 100 bar), or even higher if desired. Here again, those skilled in the art can adjust the pressure sufficiently as a function of the catalytic load and the dilution of the substrate in the solvent. For example, 2 × 10 5 Pa~10×10 5 Typical pressures in Pa (2-10 bar) can be listed.

[0034] The temperature range in which hydrogenation can be carried out is 0°C to 80°C, more preferably 20°C to 50°C. Naturally, those skilled in the art can also select a preferred temperature as a function of the melting and boiling points of the starting and final products, as well as the desired time for the reaction or conversion.

[0035] The process of the present invention can be carried out under batch or continuous conditions.

[0036] Another aspect of the present invention is 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 4-methyldeca-1,2-dien-4-ol, The use of compounds selected from the group consisting of 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctane-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol, and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol in the semi-hydrogenation process defined above.

[0037] Some compounds of formula (IV) are novel compounds and exhibit several advantages, as described above and shown in the examples. Therefore, another object of the present invention is a compound for use in the semi-hydrogenation process of the present invention, the compound being selected from the group consisting of 4,8-dimethylnonano-1,2,7trien-4-ol, (E)-5-methylocta-1,2,5trien-4-ol, (6R)-6,10-dimethylundeca-1,2,9trien-4-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol and (4AS,8AS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

[0038] A typical method for carrying out the process of the present invention is described below in the examples. [Examples]

[0039] The present invention will now be described in more detail by the following examples, where abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). The pre-catalyst and ligand solutions were prepared under an inert atmosphere (argon) using the standard Schlenk technique. The solvents were dried by conventional procedures and distilled under an argon atmosphere. NMR spectra were recorded at 20°C using a Bruker AV300, AV400, or AV500 MHz spectrometer. Chemical shifts are reported in ppm relative to the solvent signal (chloroform, δH=7.26 ppm, δC=77.0 ppm). The signal assignments are as follows: 1 H, 1 H-COSY, -NOESY, 13 C, 1This was confirmed by recording H-HSQC and HMBC experiments. Gas chromatography was performed using an Agilent 6850 series with DB-1 or DB-Wax columns (10 m × 0.1 mm inner diameter, 0.1 μm film). The cobalt complex was prepared according to the following literature: a) SC Meier, A. Holz, J. Kulenkampff, A. Schmidt, D. Kratzert, D. Himmel, D. Schmitz, E.-W. Scheidd, W. Scherer, C. Bulow, M. Timm, R. Lindblad, STAkin, V. Zamudio-Bayer, B. von Issendorff, MADuncan, J. TLau, and I. Krossing Angew. Chem. Int. Ed. 2018, 57, 9310-9314. b) C.S. MacNeil, H. Zhong, T.P. Abst, M. Shevlin, P.J. Chirik ACS Catalysis 2022, 12, 4680-4687. c) M.R. Friedfeld, H. Zhong, R.R. Track, M. Shevlin, P.J. Chirik Science 2018,360,888-893. (R,R)-iPr-Duphos represents (R,R)-1,2-bis(2,5-diisopropylphosphoran-1-yl)benzene.

[0040] Example 1 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using a palladium Rindler-type catalyst in various solvents

[0041] In a 100 ml stainless steel autoclave, (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (20 g, 120.3 mmol), Lindler catalyst (19 mg on CaCO3, 5% Pd, 5% Pb), and the desired solvent (20 ml) shown in Table 1 were added. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred at 60°C under hydrogen (5 bar) for the indicated time. The autoclave was then cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The results are shown in Table 1.

[0042] Table 1. Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using palladium Rindler-type catalysts in various solvents. [Table 1] 1) Conversion rate: 100% - the percentage of the starting material measured by GC. 3) Amount of (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol measured by GC.

[0043] Example 2 Hydrogenation of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol using a Raney nickel catalyst (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (20 g, 120.3 mmol), Raney nickel catalyst (64 mg, washed 3 times with iPrOH), and EtOH (20 ml) were placed in a 100 ml stainless steel autoclave. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred at 60°C under hydrogen (5 bar) for 26 hours. The autoclave was then cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The analysis showed a conversion rate of 99.5% and a production rate of 72% of (rac)-(Z)-4,8-dimethyl-2,7-nonatrien-4-ol.

[0044] Example 3 Hydrogenation of (rac)-4,8-dimethyl-2,7-nonadien-4-ol using various poisoned palladium catalysts A solution of (rac)-4,8-dimethyl-1,2,7-nonatrien-4-ol (20 g, 120 mmol), poisoned palladium catalyst (40 mg for 5% Pd or 20 mg for 10% Pd), and ethanol (20 ml) was placed in a 100 ml autoclave with a glass liner, as shown in Table 2. The autoclave was closed, purged with hydrogen (3 × 5 bar), and the solution was mechanically stirred at 60°C under hydrogen (5 bar). After the indicated time, the autoclave was cooled to room temperature, evacuated, purged with nitrogen, and the reaction mixture was analyzed by GC (DB-Wax). The results are shown in Table 2.

[0045] Table 2. Hydrogenation of (rac)-4,8-dimethyl-2,7-nonadien-4-ol using various poisoned palladium catalysts. [Table 2] 1) Conversion rate: 100% - the percentage of the starting material measured by GC. 2) Amount of (rac)-(Z)-4,8-dimethyl-2,7-nonadien-4-ol measured by GC.

Claims

1. Molecule H ２ A method for the semi-hydrogenation of an allene of formula (I) to a corresponding alkene of formula (II), using a heterogeneous catalyst. 【Chemistry 1】 【Chemistry 2】 (In each formula, R １ C may contain 1 to 3 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom. ２～３０ It is a hydrocarbon.

2. Allen in the above formula (I) is C ５ ~C １５ The method according to claim 1, wherein the compound is a compound.

3. R １ C may contain 1 to 3 oxygen atoms. ４～１８ The method according to claim 1, wherein the hydrocarbon is used.

4. The method according to any one of claims 1 to 3, wherein the allene in formula (I) is of formula (III), and the alkene in formula (II) is of formula (IV). 【Transformation 3】 【Chemistry 4】 (In each formula, R ２ is a C １～１４ hydrocarbon which may contain 1 to 2 oxygen atoms and / or 1 to 2 nitrogen atoms and / or 1 sulfur atom, and R ３ is a hydrogen atom or a C １～６ hydrocarbon group; or R ２ and R ３ together form a C １～６ cycloalkyl or C ２～６ cycloalkenyl group, each of which may be substituted with 1 to 2 hydroxy groups and / or 1 to 3 C １～６ alkyl, C ５～１６ alkenyl, C ５～１６ alkoxy groups. )

5. R ３ is a hydrogen atom or C １～３ The method according to claim 4, wherein the alkyl group is preferably a hydrogen atom or a methyl, ethyl, or isopropyl group.

6. R ２ Each of these may be a linear, branched, or cyclic C12. １ ~C １０ Alkyl, or linear, branched, or cyclic carbon atoms. ２ ~C １０ Alkenyl group, or linear or branched carbon group １ ~C ６ The method according to any one of claims 4 to 5, wherein the material is a phenylalkyl group.

7. R ２ and R ３ Together, they each have 1-2 hydroxyl groups and / or 1-3 C groups. １～３ Alkyl, C ２～３ Alkenil, C １～３ C may be substituted with an alkoxy group. ５～６ Cycloalkyl or C ５～６ The method according to claim 4, wherein a cycloalkenyl group is formed.

8. The compound of formula (I) is 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 4-methyldeca-1,2-dien-4- The method according to any one of claims 1 to 7, selected from the group consisting of ol, 3-methyl-1-phenylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

9. The compounds of formula (II) are (Z)-4,8-dimethylnonano-2,7-dien-4-ol, (Z)-2-phenylpenta-3-en-2-ol, (Z)-3-phenylhexa-4-en-3-ol, (Z)-2-methyl-3-phenylhexa-4-en-3-ol, 4-methyldeca-1,2-dien-4-ol, (Z)-3-methyl-1-phenylhexa-4-en-3-ol, (Z)-4,4-dimethyl-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclopentan-1-ol, (Z)-1-(propa-1-en-1-yl)cycloheptan-1-ol, (Z)-2-(propa-1-en-1-yl)decahydronaphthalene-2 The method according to any one of claims 1 to 8, selected from the group consisting of -ol, (4aS,8aS)-2-((Z)-propa-1-en-1-yl)decahydronaphthalene-2-ol, (Z)-1-(propa-1-en-1-yl)cyclohexane-1-ol, (Z)-1-(propa-1-en-1-yl)cyclooctan-1-ol, (Z)-1-(p-tolyl)buta-2-en-1-ol, (Z)-1-cyclohexylbuta-2-en-1-ol, (2Z,5E)-5-methylocta-2,5-dien-4-ol, (Z)-1-phenylhexa-4-en-3-ol, (6R,Z)-6,10-dimethylundeca-2,9-dien-4-ol and (Z)-undeca-2-en-4-ol.

10. The method according to any one of claims 1 to 9, wherein the heterogeneous catalyst is a Lindler catalyst, or a Raney nickel or sulfur-modified supported Pd catalyst, or a polyamine-modified supported Pd catalyst.

11. The method according to any one of claims 1 to 10, wherein the heterogeneous catalyst is a Lindler catalyst or Raney nickel.

12. The method according to any one of claims 1 to 11, carried out in the absence of a base or additive.

13. 4,8-dimethylnonano-1,2,7-trien-4-ol, 1-(p-tolyl)buta-2,3-dien-1-ol, 1-cyclohexylbuta-2,3-dien-1-ol, undeca-1,2-dien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, 1-phenylhexa-4,5-dien-3-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-phenylpenta-3,4-dien-2-ol, 3-phenylhexa-4,5-dien-3-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 4-methyldeca-1,2-dien-4-ol, 3-methyl-1-phenyl Use of a compound selected from the group consisting of ylhexa-4,5-dien-3-ol, 4,4-dimethyl-1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclopentan-1-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol in the hemihydrogenation method according to any one of claims 1 to 12.

14. Compounds selected from the group consisting of 4,8-dimethylnonano-1,2,7-trien-4-ol, (E)-5-methylocta-1,2,5-trien-4-ol, (6R)-6,10-dimethylundeca-1,2,9-trien-4-ol, 2-methyl-3-phenylhexa-4,5-dien-3-ol, 1-(propa-1,2-dien-1-yl)cyclohexane-1-ol, 1-(propa-1,2-dien-1-yl)cyclooctan-1-ol, 2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol, and (4aS,8aS)-2-(propa-1,2-dien-1-yl)decahydronaphthalene-2-ol.

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