Alcohol conversion process

Abstract

This invention relates to an alcohol conversion process using a homogeneous transition metal catalyst. In this process, a molar excess of ligands is used relative to the metal center of the catalyst.

Description

[Technical Field]

[0001] This invention relates to an alcohol conversion process. [Background technology]

[0002] The commonly used industrial production of alcohols is primarily based on the oxo process. This process involves the reaction of an alkene with an oxo gas, which is a mixture of hydrogen and carbon monoxide in a 1:1 molar ratio. After the reaction, the aldehyde is hydrogenated to the desired alcohol.

[0003] An alternative process for the synthesis of alcohols is based on the Guerbet reaction, which has been known for decades (M. Guerbet, CRHebd.Seances Acad.Sci.1899, 128, pp. 511-513). The mechanism yielding Guerbet alcohols is generally accepted to involve three steps: (i) dehydrogenation of the primary alcohol to its respective aldehyde; (ii) aldol condensation of the two aldehyde molecules to an α,β-unsaturated aldehyde, with the removal of water; and (iii) hydrogenation of the unsaturated aldehyde to a dimer alcohol. An alkaline catalyst, such as sodium hydroxide or potassium hydroxide or sodium or potassium alkoxide, is required for the Guerbet reaction. Often, homogeneous or heterogeneous metal catalysts are added to accelerate the dehydrogenation and hydrogenation steps. However, the Guerbet reaction generally suffers from harsh conditions, low selectivity, separation problems, and low yields.

[0004] In the chemical industry, butanol is an important intermediate product and solvent for a wide variety of products, including paints and various plastics. Historically, butanol has been produced from petroleum-based raw materials, resulting in a significant product carbon footprint for both butanol and the resulting products. Therefore, it is crucial for the chemical industry to find and open economical and sustainable process pathways to butanol with a lower product carbon footprint.

[0005] Ethanol can be a sustainable source for manufacturing chemicals. Using ethanol in the Guerbet reaction could be a beneficial and sustainable approach for producing butanol. While the Guerbet reaction has been used to date to produce higher alcohols from higher boiling point alcohol feedstocks than ethanol, there has been no industrial use of the Guerbet reaction with ethanol as a feedstock for producing butanol. Although the Guerbet reaction itself may seem like a simple chemical reaction, using ethanol as a feedstock presents unique problems, particularly in terms of selectivity. Higher alcohols often occur as byproducts in the process, as the product n-butanol itself can also undergo dehydrogenation, and so far the reaction has not been profitable on an industrial scale.

[0006] Y. Xie et al., "Highly efficient Process for Production of Biofuel from ethanol Catalyzed by Ruthenium Pincer Complexes," Journal of the American Society, vol. 138, no. 29, 2016-07-18, pp. 9077-9080, describes a ruthenium pincer catalyst Guerbet-type process for producing biofuel from ethanol.

[0007] International Publication No. 2012 / 119928 relates to a method for producing alkanolamines containing a primary amino group and a hydroxyl group by alcohol amination of a diol containing two hydroxyl groups using ammonia and elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9, and 10 of the periodic table and at least one donor ligand.

[0008] Chidambaram Gunanathan et al., "Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia," Angew. Chem. Int. Ed., vol. 47, no. 45, 2008-10-07, pp. 8661-8664, concerns the selective synthesis of primary amines directly from alcohols and ammonia under mild conditions, eliminating the need for stoichiometric amounts of toxic reagents, high pressure, and harsh experimental conditions.

[0009] International Publication No. 2013 / 156399 is for formula R 1 A method for producing a branched alcohol using at least one alcohol of the -CH2-CH2-OH group, wherein the group R 1 At least one complex compound is used that is selected from linear or branched C2-C3 alkyl groups in a homogeneous phase, where the components are different or the same, and in the presence of at least one base, and contains Ru(ii), wherein Ru(ii) is at least one ligand L which is at least bidentate. 1 It has L 1 The present invention relates to a method characterized in that at least one coordination site is a nitrogen atom. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] International Publication No. 2012 / 119928 [Patent Document 2] International Publication No. 2013 / 156399 [Non-patent literature]

[0011] [Non-Patent Document 1] M.Guerbet,CRHebd.Seances Acad.Sci.1899,128,p.511-513 [Non-Patent Document 2] Y.Xie et al., "Highly efficient Process for Production of Biofuel from ethanol Catalyzed by Ruthenium Pincer Complexes", Journal of the American Society, vol. 138, no. 29, 2016-07-18, pp. 9077-9080 [Non-Patent Document 3] Chidambaram Gunanathan et al., "Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia", Angew.Chem.Int.Ed., vol.47, no.45, 2008-10-07, pp.8661-8664 [Overview of the project] [Problems that the invention aims to solve]

[0012] Therefore, an object of the present invention was to provide an alcohol conversion process that enables a beneficial and sustainable approach to producing alcohols, such as butanol, which leads to increased productivity.

[0013] Accordingly, the present invention relates to an alcohol conversion process based on a Guerbet reaction in which a homogeneous transition metal catalyst is used. This process is economically feasible by matching several factors, including productivity, i.e., space-time yield. The catalyst, e.g., the combination of metal and ligand, is a factor that affects these parameters. Typically, in a homogeneously catalyzed Guerbet reaction, the metal and (pincer) ligand are used in a 1:1 molar ratio. However, in the process according to the present invention, a molar excess of ligand is used relative to the metal center used, which can dramatically increase productivity to a favorable degree. The excess ligand stabilizes the active catalyst species, thus leading to increased productivity. [Means for solving the problem]

[0014] The present invention relates in particular to an alcohol conversion process, (i) providing at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor; (ii) preparing a liquid mixture M comprising at least one alcohol R-CH2-CH2-OH E where R is selected from the group consisting of H and C1-C4-alkyl, and the liquid mixture M E comprises a base, at least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor provided according to (i), and a compound of formula (L)

Chemical formula

[0015] [Figure 1] This figure shows the significantly faster reaction and better conversion rate when comparing isolated catalysts (Comparative Example 1 vs. Example 1) and catalysts formed in situ (Comparative Example 1 vs. Example 2 / Example 3). [Modes for carrying out the invention]

[0016] The process according to the present invention is preferably a continuous process. Alternatively, the process is preferably a semi-batch process or a batch process.

[0017] Preferably, the alcohol conversion conditions according to (iii) are in the reaction space S R The alcohol conversion conditions according to (iii) are 1 x 10 5 From 3.5x10 6 Range of Pa, preferably 1x10 5 From 3.1x10 6 Pa range, more comfortably 1x10 5 From 2x10 6 Pa range, more comfortably 1x10 5 From 1.5x10 6 Reaction space S in the range of Pa R It is also preferable to include internal pressure.

[0018] Preferably, the alcohol conversion conditions according to (iii) are in the range of 100 to 200°C, preferably 120 to 180°C, more preferably 120 to 160°C, and more preferably 130 to 160°C for the reaction mixture M. G This includes the temperature.

[0019] The alcohol conversion conditions according to (iii) are preferably for the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 0.1 to 10% by weight, preferably in the range of 0.5 to 8% by weight, and more preferably in the range of 1 to 5% by weight. G This includes the amount of base in the mixture. The alcohol conversion conditions according to (iii) also include the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 0.001 to 2% by weight, preferably in the range of 0.001 to 1% by weight, and more preferably in the range of 0.001 to 0.5% by weight. G It is also preferable to include the amount of catalyst in the mixture. In a more preferred embodiment, according to (iii), the reaction space is the reaction mixture M G and a gas phase, the gas phase containing H2, and the alcohol conversion conditions are such that the partial pressure of H2 in the gas phase is 2x10 4 From 3.1x10 6 Range of Pa, preferably 2x10 4 from 1.1x10 6 Pa range, more preferably 2x10 4 From 6x10 5 Pa range, even more comfortably 5x10 4 From 6x10 5 Pa range, more preferably 7x10 4 From 6x10 5 This further includes maintaining the range within Pa.

[0020] Preferably, the partial pressure of H2 in the gas phase is maintained by introducing H2 into the gas phase. Alternatively, it is preferable that the partial pressure of H2 in the gas phase is maintained by the relaxation of the gas phase.

[0021] "Maintaining" the H2 partial pressure in the gas phase, as in the meaning of this invention, includes ensuring that the H2 partial pressure remains within a desired range during the reaction. If the H2 partial pressure is within a desired range, it is not necessary to force the effective steps to be performed, but the pressure may still be adjusted to different parts of the range as needed. However, in order to ensure that the H2 partial pressure is neither too high nor too low, the H2 partial pressure may preferably be adjusted, or, if it is necessary to ensure that the H2 partial pressure is maintained within a desired range, it must be adjusted, for example, by relaxing the gas phase, in which case the H2 partial pressure may be decreased, or it may be adjusted by introducing H2 into the gas phase, in which case the H2 partial pressure may be increased. In order to adjust the H2 partial pressure in accordance with the H2 partial pressure during the reaction and to maintain the H2 partial pressure within a desired pressure range at all times during the reaction, one or more of the above alternatives may be performed as needed.

[0022] Preferably, a liquid mixture M prepared according to (ii) and subjected to alcohol conversion conditions according to (iii) E In this case, the molar ratio of the compound of formula (L) to the compound of formula (A) is in the range of 0.01:1 to 10:1, preferably in the range of 0.05:1 to 10:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 0.3:1 to 10:1, more preferably in the range of 0.5:1 to 10:1, more preferably in the range of 0.7:1 to 10:1, more preferably in the range of 0.8:1 to 10:1, more preferably in the range of 1:1 to 10:1, more preferably in the range of 1.01:1 to 10:1, more preferably in the range of 1.02:1 to 8:1, more preferably in the range of 1.03:1 to 7:1, more preferably in the range of 1.03:1 to 6:1, and more preferably in the range of 1.05:1 to 5:1.

[0023] Furthermore, preferably, the compound of formula (L) is selected from the group consisting of dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridin-4-yl]methyl]phosphane, diisopropyl-[[5-(diisopropylphosphanylmethyl)acridin-4-yl]methyl]phosphane, dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)pyridin-4-yl]methyl]phosphane and diisopropyl-[[5-(diisopropylphosphanylmethyl)pyridin-4-yl]methyl]phosphane, and more preferably, the additional compound is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridin-4-yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridin-4-yl]methyl]phosphane.

[0024] Preparing the liquid mixture M in step (ii) E preferably involves at least one alcohol R-CH2-CH2-OH, a base, a solvent, and at least one of the catalyst or its precursor provided according to (i).

[0025] In formula (A), preferably, when R 1 , R 2 , R 3 and R 4 are hydrogen, n is 0.

[0026] At least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is preferably a compound of formula (B) [Chemical formula] (where M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh and Ru; L 1 and L 2 are, independently of each other, PR a R b , NR a R b , SR a , SH and S(=O)Ra and; L 3 CO, PR a R b R c , SR a R b , R a CN, R a Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R 1 , R 2 , R 3 and R 4 is either hydrogen or, together with the pyridyl unit of the catalyst of formula (A), forms an acridinyl unit; n is either 0 or 1, R 1 , R 2 , R 3 and R 4 If is hydrogen, then n is 0; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , L1 , L 2 and n are preferably R of the catalyst of formula (B). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) Includes.

[0027] Alternatively, at least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is preferably a compound of formula (C). [ka] (In the formula, M is selected from the group consisting of Ir, Ru, and Mn; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a , SH and S(=O)R a and; L 3 CO, PR a R b R C , SR a R b , R a CN, R a Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10- Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are preferably R of the catalyst of formula (C). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) Includes.

[0028] In another embodiment, at least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is preferably a compound of formula (D). [ka] (In the formula, M is selected from the group consisting of Ir, Ru, and Mn; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a , SH and S(=O)R a and; L 3 CO, PR a R b R c , SR a R b , R a CN, Ra Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are preferably R of the catalyst of formula (D). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) Includes.

[0029] M is preferably selected from the group consisting of Ir and Ru, and preferably M is Ru. Preferably M is Ru, and the alcohol conversion conditions according to (iii) are in the range of 100 to 170°C, preferably 120 to 170°C, more preferably 120 to 160°C, and more preferably 130 to 150°C for the reaction mixture MG This includes the temperature.

[0030] Preferably, L 3 It is CO.

[0031] L 1 and L 2 Preferably, each (PR a R b ) and R a and R b C1-C 10 -alkyl, more preferably R a and R b These are isopropyl or tert-butyl, respectively. Or, L 1 and L 2 Preferably, each (PR a R b ) and R a and R b C1-C 10 -It is a cycloalkyl, preferably R a and R b These are cyclohexyl, respectively. Or, L 1 and L 2 Preferably, each (PR a R b ) and R a and R b C5-C 10 - It is Ariel.

[0032] Y is preferably selected from the group consisting of F, Cl, Br, and I, preferably selected from the group consisting of Cl or Br, and more preferably Y is Cl. It is also preferable that Y is CO.

[0033] At least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is preferably a compound of formula (E). [ka] (In the formula, Cy is cyclohexyl.) Includes, The compound of formula (L) is preferably: [ka] That is the case.

[0034] Compounds whose reduced form of the catalyst is given by formula (E') [ka] (In the formula, Cy is cyclohexyl.) It is also preferable to include, The compound of formula (L) is preferably: [ka] That is the case.

[0035] Furthermore, at least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is a compound of formula (F). [ka] (In the formula, iPr is isopropyl) It is preferable to include, The compound of formula (L) is preferably: [ka] That is the case.

[0036] Preferably, the reduced form of the catalyst is a compound of formula (F'). [ka] (In the formula, iPr is isopropyl) Includes, The compound of formula (L) is preferably: [ka] That is the case.

[0037] A catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (G). [ka] (In the formula, tBu is tert-butyl.) It is even more preferable to include, The compound of formula (L) is preferably: [ka] That is the case.

[0038] Furthermore, the reduced form of the catalyst is the compound of formula (G'). [ka] (In the formula, tBu is tert-butyl.) It is preferable to include, The compound of formula (L) is preferably: [ka] That is the case.

[0039] Preferably, at least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is IrCl3xH2O, [Ir(COD)Cl]2, [Ir(COE)2Cl]2, [Ir(C2H4)2Cl]2, [Ir(COD)OH]2, [Ir(COD)MeO]2, [IrCp*Cl2], [IrCpCl2], Ir4(CO) 12 The compound comprises a metal M selected from the group consisting of [Ir(PPh3)2(CO)Cl], [Ir(acetylacetonate)3], and [Ir(acetylacetonate)(COD)], where Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, COE is cyclooctenyl, and methylally is 2-methylallyl. The catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2] y [Ru(CO)2Cl2] y(In the formulas, y is in the range of 1 to 1000 in each case), [Ru(CO)3Cl2]2, [Ru(COD)(allyl)], RuCl3xH2O, [Ru(acetylacetonate)3], [Ru(DMSO)4Cl2], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2Cl], [Ru(Cp*)(CO)2H], [Ru(Cp*)(CO)2]2, [Ru(indenyl)(CO)2Cl], [Ru(indenyl)(CO)2H], [Ru(indenyl)(CO)2]2, lutenocene, [Ru(COD)Cl2]2, [Ru(Cp*)(COD)Cl], [Ru3(CO) 12 It is also preferable to include a compound containing a metal M selected from the group consisting of , [Ru(PPh3)4(H)2], [Ru(PPh3)3(Cl)2], [Ru(PPh3)3(CO)(Cl)2], [Ru(PPh3)3(CO)(Cl)(H)], [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], where Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, and methylallyl is 2-methylallyl.

[0040] Preferably, the reduced form of the precursor is a compound of formula (PI) or (P-II): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is either hydrogen or, together with an N-containing ring, forms a tetrahydroquinoline unit, a decahydroquinoline unit, a tetrahydroacridine unit, or a tetradecahydroacridine unit; L 1 and L 2 They are independent of each other, as defined above. [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; L 1 and L 2 (These are independent of each other, as defined above.) Includes.

[0041] Compounds whose precursor is the reduced form of formula (PI): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 (It is either hydrogen, or together with an N-containing ring, it forms a tetrahydroacridine unit or a tetradecahydroacridine unit.) It is more preferable to include it.

[0042] In another, more preferred embodiment, the reduced form of the precursor is a compound of formula (P-II): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; L 1 and L 2 (These are independent of each other, as defined above.) Includes.

[0043] Preferably, the integer x is 1 or 2, and more preferably, the integer x is 1.

[0044] R is preferably selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably selected from the group consisting of H, methyl, ethyl, propyl and isopropyl, more preferably selected from the group consisting of H, ethyl and propyl, and more preferably R is H.

[0045] The base is preferably selected from the group consisting of alkali hydroxides, alkali alkoxides, and mixtures thereof. Preferably, the alkali hydroxide is selected from the group consisting of NaOH, KOH, and mixtures thereof, and preferably the alkali hydroxide is KOH. It is also preferable that the alkali alkoxide is selected from the group consisting of sodium alkoxides, potassium alkoxides, and mixtures thereof, preferably from the group consisting of sodium ethoxides, potassium ethoxides, and mixtures thereof.

[0046] At least one alcohol R-CH2-CH2-OH is preferably a bio-based alcohol and can be obtained from, or is obtained from, a sugar-containing crop, preferably from one or more of sugarcane and maize.

[0047] The process according to the present invention preferably yields mixture M according to (iv). C The method further includes recycling at least one portion of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor contained in (ii) or (iii).

[0048] Preferably, a liquid mixture M prepared according to (ii) EThe solvent further comprises a solvent. The solvent preferably has a boiling point of 110°C or higher, more preferably 140°C or higher, more preferably 160°C or higher, more preferably 180°C or higher, and more preferably 190°C or higher. The solvent also preferably has a solubility in water at 25°C of 0 to 0.5% by weight, preferably 0 to 0.1% by weight, more preferably 0 to 0.05% by weight, and more preferably 0 to 0.01% by weight, based on 100% by weight of water. Furthermore, the partition coefficient of the catalyst in the solvent and water system is preferably 0 to 0.01, preferably 0 to 0.005, and more preferably 0 to 0.005, based on 1 kg of catalyst. Preferably, the solvent is a mixture of at least two aromatic hydrocarbons having a boiling point of 180°C or higher.

[0049] In preferred embodiments, the solvent does not contain any of benzene, toluene, xylene, or mesitylene.

[0050] Preferably, the solvent does not form an azeotrope with water. An azeotropic mixture, or constant-boiling-point mixture, is a mixture of two or more components in a fluid state whose proportions cannot be changed or altered by simple distillation. This occurs because when an azeotropic mixture boils, the vapor has the same proportions of its components as the unboiled mixture. Each azeotropic mixture has a characteristic boiling point. It is impossible to separate the components by fractional distillation.

[0051] The solvent is preferably selected from the group consisting of biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decalin, n-butyl butyrate, n-hexylhexylate, n-octyloctyrate, texanol, di-n-butyl ether, di-iso-butyl ether, di-sec-butyl ether, and mixtures of two or more thereof, preferably selected from the group consisting of biphenyl, diphenyl ether, and mixtures thereof, and more preferably the solvent is a mixture of biphenyl and diphenyl ether. The solvent is a mixture of biphenyl and diphenyl ether, and preferably the solvent is a mixture of biphenyl and diphenyl ether in which the molar ratio of biphenyl to diphenyl ether is in the range of 1:2 to 1:6, preferably in the range of 1:2.5 to 1:4.

[0052] Preferably, the alcohol conversion conditions according to (iii) are for the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 5 to 50% by weight, more preferably in the range of 5 to 30% by weight, and more preferably in the range of 5 to 10% by weight. G This includes the amount of solvent inside.

[0053] Preferably, a liquid mixture M prepared according to (ii) E 90 to 100% by weight, more preferably 95 to 100% by weight, more preferably 98 to 100% by weight, and more preferably 99 to 100% by weight, consist of at least one alcohol R-CH2-CH2-OH, a base, a solvent, and a catalyst.

[0054] (iv) The mixture M obtained according to (iv) C Preferably, the solution comprises at least one of a catalyst, its precursor, a reduced form of the catalyst, or a reduced form of the precursor, and further comprises a solvent.

[0055] This process preferably yields mixture M according to (iv). CThe further method includes recirculating at least a portion of the solvent contained in (ii) or (iii) to (ii).

[0056] Preferably, the liquid reaction mixture M obtained according to (iii) G The process further includes at least one unreacted alcohol R-CH2-CH2-OH, and the liquid reaction mixture M G The further step is to separate at least a portion of the unreacted alcohol R-CH2-CH2-OH from the M G It is more preferable to separate at least a portion of the unreacted alcohol R-CH2-CH2-OH from the mixture by distillation, extraction, flushing, or by using a membrane. G It is also preferable that at least a portion of the at least one unreacted alcohol R-CH2-CH2-OH separated from (ii) be recycled to (iii).

[0057] Reaction space S R Preferably, the reaction vessel is contained within a reaction vessel, which is preferably a complete mixing reaction vessel.

[0058] The present invention is further described by the following set of embodiments and combinations of embodiments arising from the dependencies and backreferences shown. In particular, it should be noted that in each example in which the scope of an embodiment is referred to, for example in the context of the term, for example, “any one process of Embodiments 1 to 4,” all embodiments within this scope are expressly disclosed to those skilled in the art; that is, the wording of this term should be understood by those skilled in the art as synonymous with “any one process of Embodiments 1, 2, 3, and 4.” Furthermore, it should be explicitly noted that the following set of embodiments represents a well-structured portion of a general description directed toward preferred aspects of the present invention and therefore adequately supports, but does not represent, the claims of the present invention.

[0059] 1. The alcohol conversion process, (i) providing a catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced form of the precursor; (ii) A liquid mixture M containing at least one alcohol R-CH2-CH2-OH E A step of preparing a liquid mixture M in which R is selected from the group consisting of H and C1-C4-alkyl. E However, the base, the catalyst provided according to (i), its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor, and the compound of formula (L). [ka] Further steps include; (iii)(ii) Liquid mixture M E reaction space S R The alcohol is subjected to alcohol conversion conditions within the reaction space, and at least one alcohol R-CH2-CH2-(CHR-CH2) x - Reaction mixture M containing OH G A step to obtain, where x is an integer in the range of 1 to 4, and the reaction space is the reaction mixture M G A reaction mixture M comprising a gas phase and alcohol conversion conditions in the range of 100 to 250°C. E Temperature and 1x10 5 Pa to 4x10 6 Reaction space S in the range of Pa R Steps, including internal pressure; (iv)(iii) The reaction mixture M obtained according to (iv)(iii) G From at least one alcohol R-CH2-CH2-(CHR-CH2) x -OH is separated, and at least one alcohol R-CH2-CH2-(CHR-CH2) x A mixture M comprising at least one of -OH and a catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor. C Steps to obtain Includes, The base is selected from the group consisting of ammonium hydroxide, alkali hydroxides, alkaline earth hydroxides, ammonium carbonate, ammonium bicarbonate, alkali carbonates, alkali bicarbonates, alkaline earth carbonates, alkali bicarbonates, alkali alkoxides, alkaline earth alkoxides, alkali metal amides, alkaline earth metal amides, secondary amino acids, and mixtures of two or more of these; The catalyst is a compound of formula (A). [ka] (In the formula, M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a SH, S(=O)R a , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR a R b SbR a R b , and structure: [ka] or [ka] It is an N-heterocyclic carbene represented by; L 3 CO, PR a R b R c AsR a R b R c SbR a R b R c , SR a R b , R d CN, R d Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R 1 , R 2 , R 3 and R 4 is either hydrogen, or together with the pyridyl unit of the catalyst of formula (A) to form an acridinyl unit, or R 1 and R 2 Or R 3 and R 4 It combines with the pyridyl unit of the catalyst in formula (A) to form a quinolinyl unit; n is either 0 or 1; Y is H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, OH, OR, NR d 2, NH3, NR d 3 and R d 2NSO2R d Selected from the group consisting of; R a , R b , R c , R d , R 5 , R 6 and R 7 These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); Unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 - Heterocyclyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C5-C 10 -aryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups; and unsubstituted or substituted C5-C containing at least one heteroatom selected from the group consisting of N, O, and S.10 - Heteroaryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on an acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on a quinolinyl unit, or 1 substituent located on a carbon atom on a pyridyl unit, where the substituents are F, Cl, Br, OH, CN, NH2, and C1-C 10 - Selected from the group consisting of alkyl groups; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 is either hydrogen, or together with the pyridyl unit of the catalyst of formula (L) to form an acridinyl unit, or R 1 and R 2 Or R 3 and R 4 It combines with the pyridyl unit of the catalyst of formula (L) to form a quinolinyl unit; n is either 0 or 1; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on an acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on a quinolinyl unit, or 1 substituent located on a carbon atom on a pyridyl unit, where the substituents are F, Cl, Br, OH, CN, NH2, and C1-C 10 - Selected from the group consisting of alkyl groups; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a SH, S(=O)R a , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR a R b SbR a Rb , and structure: [ka] or [ka] It is an N-heterocyclic carbene represented by; R a , R b , R c , R d , R 5 , R 6 and R 7 These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); Unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 - Heterocyclyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C5-C 10 -aryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups; and unsubstituted or substituted C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , X, L 1 , L 2and n are preferably R of the catalyst of formula (A). 1 , R 2 , R 3 and R 4 , X, L 1 , L 2 (and is identical to n) Includes; The catalyst precursor containing the compound of formula (A) is a compound containing metal M, CO, PR a R b R c , SR a R b , R a CN, R a NC, N2, PF3, Organic Carbonyl Compound, C1-C 10 -alkyl, C1-C 12 -Cycloalkyl, C2-C 12 -Alkenyl, C3-C 15 -Cycloalkenyl, C5-C 20 A mixture comprising at least one component selected from the group consisting of -aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridine, halides, hydroxides, and thiophenes, as well as compounds of formula (H). [ka] (In the formula, M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a SH, S(=O)R a , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR a R b SbR a R b , and structure: [ka] or [ka] It is an N-heterocyclic carbene represented by; R 1 , R 2 , R 3 and R 4 is either hydrogen, or together with the pyridyl unit of the catalyst of formula (A) to form an acridinyl unit, or R 1 and R 2 Or R 3 and R 4 It combines with the pyridyl unit of the catalyst in formula (A) to form a quinolinyl unit; n is either 0 or 1; R a , R b , R c , R d , R 5 , R 6 and R 7 These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); Unsubstituted or substituted C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 - Heterocyclyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C5-C 10 -aryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups; and unsubstituted or substituted C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Heteroaryl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10- Selected from the group consisting of alkyl groups; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on an acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on a quinolinyl unit, or 1 substituent located on a carbon atom on a pyridyl unit, where the substituents are F, Cl, Br, OH, CN, NH2, and C1-C 10 (Selected from the group consisting of alkyl groups) The alcohol conversion process, including the alcohol conversion process.

[0060] 2. The process according to Embodiment 1, wherein the process is a continuous process.

[0061] 3. The process according to Embodiment 1, wherein the process is a semi-batch process or a batch process.

[0062] 4.(iii) The alcohol conversion conditions are in reaction space S R The process according to any one of Embodiments 1 to 3, comprising the presence of at least one inert gas, wherein the at least one inert gas is preferably selected from the group consisting of nitrogen, argon and mixtures thereof.

[0063] 5.(iii) The alcohol conversion conditions are 1 x 10 5 From 3.5x10 6 Range of Pa, preferably 1x10 5 From 3.1x10 6 Pa range, more comfortably 1x10 5 From 2x10 6 Pa range, more comfortably 1x10 5 From 1.5x10 6 Reaction space S in the range of Pa R A process according to any one of embodiments 1 to 4, including internal pressure.

[0064] 6.(iii) The alcohol conversion conditions are in the range of 100 to 200°C, preferably 120 to 180°C, more preferably 120 to 160°C, and more preferably 130 to 160°C. G The process according to any one of embodiments 1 to 5, including the temperature.

[0065] The alcohol conversion conditions according to 7.(iii) are for the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 0.1 to 10% by weight, preferably in the range of 0.5 to 8% by weight, and more preferably in the range of 1 to 5% by weight. G The process according to any one of Embodiments 1 to 6, including the amount of base in it.

[0066] The alcohol conversion conditions according to 8.(iii) are for the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 0.001 to 2% by weight, preferably in the range of 0.001 to 1% by weight, and more preferably in the range of 0.001 to 0.5% by weight. G The process according to any one of Embodiments 1 to 7, including the amount of catalyst contained therein.

[0067] 9.(iii) The reaction space is the reaction mixture M G and a gas phase, wherein the gas phase contains H2, and the alcohol conversion conditions are such that the partial pressure of H2 in the gas phase is 2x10 4 From 3.1x10 6 Range of Pa, preferably 2x10 4 from 1.1x10 6 Pa range, more preferably 2x10 4 From 6x10 5 Pa range, even more comfortably 5x10 4 From 6x10 5 Pa range, more preferably 7x10 4 From 6x10 5 The process according to any one of embodiments 1 to 8, further comprising maintaining within the range of Pa.

[0068] 10. The process according to Embodiment 9, wherein the partial pressure of H2 in the gas phase is maintained by introducing H2 into the gas phase.

[0069] 11. The process according to Embodiment 9, wherein the partial pressure of H2 in the gas phase is maintained by relaxation of the gas phase.

[0070] Liquid mixture M prepared according to 12.(ii) and subjected to alcohol conversion conditions according to (iii) E The process according to any one of Embodiments 1 to 11, wherein the molar ratio of the compound of formula (L) to the compound of formula (A) is in the range of 0.01:1 to 10:1, preferably in the range of 0.05:1 to 10:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 0.3:1 to 10:1, more preferably in the range of 0.5:1 to 10:1, more preferably in the range of 0.7:1 to 10:1, more preferably in the range of 0.8:1 to 10:1, more preferably in the range of 1:1 to 10:1, more preferably in the range of 1.01:1 to 10:1, more preferably in the range of 1.02:1 to 8:1, more preferably in the range of 1.03:1 to 7:1, more preferably in the range of 1.03:1 to 6:1, and more preferably in the range of 1.05:1 to 5:1.

[0071] 13. The process according to any one of Embodiments 1 to 12, wherein the compound of formula (L) is selected from the group consisting of dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane, diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane, dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)pyridine-4-yl]methyl]phosphane, and more preferably the additional compound is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane.

[0072] 14. Step (ii) Liquid mixture M E The process according to any one of Embodiments 1 to 13 comprises at least one alcohol R-CH2-CH2-OH, a base, a solvent, and at least one catalyst or precursor provided according to (i).

[0073] 15. In equation (A), R 1 , R 2 , R 3 and R 4 The process according to any one of Embodiments 1 to 14, wherein n is 0 when is hydrogen.

[0074] 16. At least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is a compound of formula (B). [ka] (In the formula, M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru; L 1 and L 2 They operate independently of each other, PR a R b , NRa R b , SR a , SH and S(=O)R a and; L 3 CO, PR a R b R c , SR a R b , R a CN, R a Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R 1 , R 2 , R 3 and R 4 is either hydrogen or, together with the pyridyl unit of the catalyst of formula (A), forms an acridinyl unit; n is either 0 or 1, R 1 , R 2 , R 3 and R 4 If is hydrogen, then n is 0; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are preferably R of the catalyst of formula (B). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) A process according to any one of embodiments 1 to 14, including the process described above.

[0075] 17. A catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (C). [ka] (In the formula, M is selected from the group consisting of Ir, Ru, and Mn; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a , SH and S(=O)R a and; L 3 CO, PR a R b R c , SR a R b , R a CN, R a Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10-Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are preferably R of the catalyst of formula (C). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) A process according to any one of embodiments 1 to 14, including the process described above.

[0076] 18. At least one of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor is a compound of formula (D). [ka] (In the formula, M is selected from the group consisting of Ir, Ru, and Mn; L 1 and L 2 They operate independently of each other, PR a R b , NR a R b , SR a , SH and S(=O)R a and; L 3 CO, PR a R b Rc , SR a R b , R a CN, R a Selected from the group consisting of NC, N2, PF3, pyridine, and thiophene; R a , R b , R c and R d These are H, unsubstituted or substituted C1-C, independently of each other. 10 -alkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); unsubstituted or substituted C1-C 10 -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH2 and C1-C) 10 - Selected from the group consisting of alkyl groups); C3-C containing at least one heteroatom selected from the group consisting of N, O, and S 10 -Heterocyclyl;C5-C 10 -aryl; and C5-C containing at least one heteroatom selected from the group consisting of N, O, and S. 10 - Selected from the group consisting of heteroaryls; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; For the compound of formula (L), R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are preferably R of the catalyst of formula (D). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) A process according to any one of embodiments 1 to 14, including the process described above.

[0077] 19. The process according to any one of Embodiments 1 to 18, wherein M is selected from the group consisting of Ir and Ru, and preferably M is Ru.

[0078] 20. A reaction mixture M in which M is Ru and the alcohol conversion conditions according to (iii) are in the range of 100 to 170°C, preferably 120 to 170°C, more preferably 120 to 160°C, and more preferably 130 to 150°C. G The process according to any one of embodiments 1 to 19, including the temperature.

[0079] 21.L 3 The process according to any one of Embodiments 1 to 20, wherein CO is

[0080] 22.L 1 and L 2 (PR) a R b ) and R a and R b C1-C 10 -It is alkyl, preferably R a and R b The process according to any one of Embodiments 1 to 21, wherein the respective isopropyl or tert-butyl.

[0081] 23.L 1 and L 2 (PR) a R b ) and R a and R b C1-C 10 -It is a cycloalkyl, preferably R a and R b The process according to any one of Embodiments 1 to 21, wherein each of the elements is cyclohexyl.

[0082] 24.L 1 and L 2 (PR) a R b ) and R a and R b C5-C 10 - The process according to any one of embodiments 1 to 21, wherein the process is aryl.

[0083] 25. The process according to any one of Embodiments 1 to 24, wherein Y is selected from the group consisting of F, Cl, Br, and I, preferably Y is selected from the group consisting of Cl or Br, and more preferably Y is Cl.

[0084] 26. The process according to any one of Embodiments 1 to 24, wherein Y is CO.

[0085] 27. A catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (E). [ka] (In the formula, Cy is cyclohexyl.) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0086] 28. The reduced form of the catalyst is a compound of formula (E'). [ka] (In the formula, Cy is cyclohexyl.) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0087] 29. A catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (F). [ka] (In the formula, iPr is isopropyl) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0088] 30. The reduced form of the catalyst is a compound of formula (F'). [ka] (In the formula, iPr is isopropyl) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0089] 31. A catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (G). [ka] (tBu is tert-butyl) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0090] 32. The reduced form of the catalyst is a compound of formula (G'). [ka] (tBu is tert-butyl) Includes, A compound of formula (L) is preferably: [ka] The process described in any one of Embodiments 1 to 14.

[0091] 33. A catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor is IrCl3xH2O, [Ir(COD)Cl]2, [Ir(COE)2Cl]2, [Ir(C2H4)2Cl]2, [Ir(COD)OH]2, [Ir(COD)MeO]2, [IrCp*Cl2], [IrCpCl2], Ir4(CO) 12 The process according to any one of Embodiments 1 to 14, comprising a compound containing a metal M selected from the group consisting of [Ir(PPh3)2(CO)Cl], [Ir(acetylacetonate)3], and [Ir(acetylacetonate)(COD)], wherein Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, COE is cyclooctenyl, and methylally is 2-methylally.

[0092] 34. The catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2] y [Ru(CO)2Cl2] y (In the formulas, y is in the range of 1 to 1000 in each case), [Ru(CO)3Cl2]2, [Ru(COD)(allyl)], RuCl3xH2O, [Ru(acetylacetonate)3], [Ru(DMSO)4Cl2], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2Cl], [Ru(Cp*)(CO)2H], [Ru(Cp*)(CO)2]2, [Ru(indenyl)(CO)2Cl], [Ru(indenyl)(CO)2H], [Ru(indenyl)(CO)2]2, lutenocene, [Ru(COD)Cl2]2, [Ru(Cp*)(COD)Cl], [Ru3(CO) 12The process according to any one of Embodiments 1 to 14, comprising a compound containing a metal M selected from the group consisting of , [Ru(PPh3)4(H)2], [Ru(PPh3)3(Cl)2], [Ru(PPh3)3(CO)(Cl)2], [Ru(PPh3)3(CO)(Cl)(H)], [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], wherein Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1,5-cyclooctadienyl, and methylallyl is 2-methylallyl.

[0093] 35. Compounds whose precursor is a reduced form of formula (PI) or (P-II): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is either hydrogen or, together with an N-containing ring, forms a tetrahydroquinoline unit, a decahydroquinoline unit, a tetrahydroacridine unit, or a tetradecahydroacridine unit; L 1 and L 2 They are independent of each other, as defined above. [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; L 1 and L 2 (These are independent of each other, as defined above.) A process according to any one of embodiments 1 to 34, including the process described above.

[0094] 36. The reduced form of the precursor is a compound of formula (PI): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 (It is either hydrogen, or together with an N-containing ring, it forms a tetrahydroacridine unit or a tetradecahydroacridine unit.) A process according to any one of embodiments 1 to 34, including the process described above.

[0095] 37. The reduced form of the precursor is a compound of formula (P-II): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; L 1 and L 2 (These are independent of each other, as defined above.) A process according to any one of embodiments 1 to 34, including the process described above.

[0096] 38. The process according to any one of Embodiments 1 to 37, wherein the integer x is 1 or 2, preferably the integer x is 1.

[0097] 39. The process according to any one of Embodiments 1 to 38, wherein R is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, preferably from the group consisting of H, methyl, ethyl, propyl and isopropyl, more preferably from the group consisting of H, ethyl and propyl, and more preferably R is H.

[0098] 40. The process according to any one of Embodiments 1 to 39, wherein the base is selected from the group consisting of alkali hydroxides, alkali alkoxides, and mixtures thereof.

[0099] 41. The process according to Embodiment 40, wherein the alkali hydroxide is selected from the group consisting of NaOH, KOH, and mixtures thereof, and preferably the alkali hydroxide is KOH.

[0100] 42. The process according to Embodiment 40, wherein the alkali alkoxide is selected from the group consisting of sodium alkoxide, potassium alkoxide and mixtures thereof, preferably from the group consisting of sodium ethoxide, potassium ethoxide and mixtures thereof.

[0101] 43. The process according to any one of Embodiments 1 to 42, wherein at least one alcohol R-CH2-CH2-OH is a bio-based alcohol which can or can be obtained from a sugar-containing crop, preferably from one or more of sugarcane and maize.

[0102] Mixture M obtained according to 44.(iv) C The process according to any one of Embodiments 1 to 43, further comprising recirculating at least one portion of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor contained in (ii) or (iii).

[0103] Liquid mixture M prepared according to 45.(ii) E The process according to any one of Embodiments 1 to 44, further comprising a solvent.

[0104] 46. ​​The process according to Embodiment 45, wherein the solvent has a boiling point of 110°C or higher, preferably 140°C or higher, more preferably 160°C or higher, more preferably 180°C or higher, and more preferably 190°C or higher.

[0105] 47. The process according to Embodiment 45 or 46, wherein the solvent has a solubility in water at 25°C of 0 to 0.5% by weight, preferably 0 to 0.1% by weight, more preferably 0 to 0.05% by weight, based on 100% by weight of water, and more preferably 0 to 0.01% by weight, based on 100% by weight of water.

[0106] 48. The process according to any one of embodiments 45 to 47, wherein the partition coefficient of the catalyst in the solvent and water system is 0 to 0.01, preferably 0 to 0.005, and more preferably 0 to 0.005, based on 1 kg of catalyst.

[0107] 49. The process according to any one of embodiments 45 to 48, wherein the solvent is a mixture of at least two aromatic hydrocarbons having a boiling point of 180°C or higher.

[0108] 50. The process according to any one of Embodiments 45 to 49, wherein the solvent is selected from the group consisting of biphenyl, diphenyl ether, 1-tert-butyl-3,5-dimethylbenzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decalin, n-butyl butyrate, n-hexylhexylate, n-octyloctyrate, texanol, di-n-butyl ether, di-iso-butyl ether, di-sec-butyl ether and mixtures of two or more thereof, preferably selected from the group consisting of biphenyl, diphenyl ether and mixtures thereof, and more preferably the solvent is a mixture of biphenyl and diphenyl ether.

[0109] 51. The process according to any one of Embodiments 45 to 50, wherein the solvent is a mixture of biphenyl and diphenyl ether, preferably the solvent is a mixture of biphenyl and diphenyl ether in which the molar ratio of biphenyl to diphenyl ether is in the range of 1:2 to 1:6, preferably in the range of 1:2.5 to 1:4.

[0110] 52. The process according to any one of embodiments 45 to 51, wherein the solvent does not form an azeotrope with water.

[0111] 53. The process according to any one of Embodiments 45 to 52, wherein the solvent does not contain any one of benzene, toluene, xylene, or mesitylene.

[0112] The alcohol conversion conditions according to 54.(iii) are for the reaction mixture M G Based on the total weight, the reaction mixture M is in the range of 5 to 50% by weight, preferably in the range of 5 to 30% by weight, more preferably in the range of 5 to 10% by weight. G The process according to any one of embodiments 45 to 53, including the amount of solvent in the solvent.

[0113] Liquid mixture M prepared according to 55.(ii) E The process according to any one of Embodiments 45 to 54, wherein 90 to 100% by weight, preferably 95 to 100% by weight, more preferably 98 to 100% by weight, and more preferably 99 to 100% by weight of the solution consists of at least one alcohol R-CH2-CH2-OH, a base, a solvent, and a catalyst.

[0114] Mixture M obtained according to 56.(iv) C The process according to any one of Embodiments 45 to 55, further comprising a catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor, and further comprising a solvent.

[0115] Mixture M obtained according to 57.(iv) C The process according to Embodiment 56, further comprising recirculating at least a portion of the solvent contained in to (ii) or (iii).

[0116] Liquid reaction mixture M obtained according to 58.(iii) G However, the process further contains at least one unreacted alcohol R-CH2-CH2-OH, and the liquid reaction mixture M GThe process according to any one of Embodiments 1 to 57, further comprising separating at least a portion of the unreacted alcohol R-CH2-CH2-OH from the alcohol.

[0117] 59.M G The process according to Embodiment 58, wherein at least a portion of the unreacted alcohol R-CH2-CH2-OH is separated from the alcohol by distillation, extraction, flushing, or by using a membrane.

[0118] 60.M G The process according to embodiment 58 or 59, wherein at least a portion of the at least one unreacted alcohol R-CH2-CH2-OH separated from is recycled to (ii) or (iii).

[0119] 61. Reaction space S R The process according to any one of Embodiments 1 to 60, wherein the reaction vessel is included in the reaction vessel, and the reaction vessel is preferably a complete mixing reaction vessel.

[0120] The present invention is further illustrated by the following embodiments, which are described to illustrate specific aspects of the invention and should not be construed as limitations thereof. [Examples]

[0121] Determining the partition coefficient of a solvent in water involves the following steps: 1. The step of combining two components, for example, feed and solvent, in a predetermined solvent ratio; 2. A turbulent mixing step of the combined components for a longer period (more than 10 minutes) at the defined extraction temperature; 3. Steps to enable phase separation; 4. Step of taking samples of each phase at the extraction temperature; 5. Centrifugation of the sample and removal of a clear sample at the extraction temperature; 6. Steps to analyze the sample; and 7. Step to compare the results of the extraction calculation and the raffinate calculation of the distribution equilibrium / distribution coefficient at the selected temperature. Includes.

[0122] Comparative Example 1 70.09 g of ethanol, 3.80 g (3 mol%) of potassium ethoxide, and 172.6 mg of (Cy-Acr-PNP)RuHCl(CO) (0.015 mol%) were weighed into a screw-top bottle and stirred overnight at room temperature. The reaction suspension was poured into an autoclave using a syringe in countercurrent of the starting materials, and the screw-top bottle was rinsed with ethanol. Then, 7.71 g of diphenyl and diphenyl ether were added as solvents in a molar ratio of 1:3.

[0123] The reaction mixture was heated to 150°C for approximately 15 minutes at 85% heating power with the outlet valve closed, while stirring at 750 rpm. The pressure was maintained at approximately 10 bar during the reaction. After reaching the reaction temperature of 150°C, a "zero sample" was taken. The sample was filtered through a 2 μm syringe filter, and the internal standard 1,4-dioxane was added to the sample for analysis by GC. Further samples were taken at 1, 2, 3, 6, and 24 hours and processed / analyzed similarly. [ka]

[0124] Example 1 The procedure was carried out as disclosed in Comparative Example 1, and 135.2 mg (0.015 mol%) of dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane was further weighed into a threaded vial.

[0125] Example 2 The procedure was the same as in Comparative Example 1, but instead of 172.6 mg of (Cy-Acr-PNP)RuHCl(CO), 90.3 mg (0.015 mol%) of Ru(acac)3 (ruthenium(III) acetylacetonate) and an additional 273.1 mg of Cy-Acr-PNP (0.03 mol%) were weighed into a screw-top bottle.

[0126] Example 3 The procedure was the same as in Comparative Example 1, but instead of 172.6 mg of (Cy-Acr-PNP)RuHCl(CO), 6 g (0.015 mol%) of Ru(acac)3 (ruthenium(III) acetylacetonate) and an additional 676 mg of Cy-Acr-PNP (0.075 mol%) were weighed into a screw-top bottle.

[0127] In this series of experiments, it was found that excess ligand resulted in significantly faster reactions and better conversion. This was demonstrated using isolated catalysts (Comparative Example 1 vs. Example 1) and in-situ formed catalysts (Comparative Example 1 vs. Example 2 / Example 3), as shown in Figure 1.

[0128] Excess ligands stabilize the activated catalyst species and prevent catalytic decomposition.

[0129] References: -M.Guerbet,CRHebd.Seances Acad.Sci.1899,128,p.511-513 -Y.Xie et al., "Highly efficient Process for Production of Biofuel from ethanol Catalyzed by Ruthenium Pincer Complexes", Journal of the American Society, vol.138, no.29, 2016-07-18, pp.9077-9080 - International Publication No. 2012 / 119928 -Chidambaram Gunanathan et al., "Selective Synthesis of Primary Amines Directly from Alcohols and Ammonia", Angew.Chem.Int.Ed., vol.47, no.45, 2008-10-07, pp.8661-8664 - International Publication No. 2013 / 156399

Claims

1. The alcohol conversion process, (i) providing a catalyst, a precursor thereof, a reduced form of the catalyst, or at least one of the reduced form of the precursor; (ii) at least one alcohol R-CH ２ -CH ２ -OH-containing liquid mixture M Ｅ A step of preparing a mixture in which R is H and C １ -C ４ - Selected from the group consisting of alkyl groups, the liquid mixture M Ｅ However, the base, the catalyst provided according to (i), its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor, and the compound of formula (L). 【Chemistry 1】 Further including steps; (iii) The liquid mixture M prepared according to (ii) Ｅ is subjected to alcohol conversion conditions in the reaction space S Ｒ to obtain a reaction mixture M containing at least one alcohol R-CH ２ -CH ２ -(CHR-CH ２ ) ｘ -OH, where x is an integer in the range from 1 to 4, the reaction space contains the reaction mixture M Ｇ and a gas phase, and the alcohol conversion conditions include a temperature of the reaction mixture M in the range from 100 to 250 °C Ｇ and a pressure in the reaction space S in the range from 1×10 Ｅ Pa to 4×10 ５ Pa, step;​​​​ The reaction mixture M obtained according to (iv)(iii) Ｇ from the at least one alcohol R-CH ２ -CH ２ - (CHR-CH ２ ) ｘ -OH is separated, and the at least one alcohol R-CH ２ -CH ２ - (CHR-CH ２ ) ｘ A mixture M comprising at least one of -OH and a catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor. Ｃ Steps to obtain; Includes, The base is selected from the group consisting of ammonium hydroxide, alkali hydroxide, alkaline earth hydroxide, ammonium carbonate, ammonium bicarbonate, alkali carbonate, alkali bicarbonate, alkaline earth carbonate, alkali bicarbonate, alkali alkoxide, alkaline earth alkoxide, alkali metal amide, alkaline earth metal amide, secondary amino acids, and mixtures of two or more thereof; The catalyst is a compound of formula (A). 【Chemistry 2】 (wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru; L １ and L ２ They operate independently of each other, PR ａ R ｂ , NR ａ R ｂ , SR ａ , SH, S(=O)R ａ , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR ａ R ｂ SbR ａ R ｂ , and structure: 【Transformation 3】 or 【Chemistry 4】 It is an N-heterocyclic carbene represented by; L ３ CO, PR ａ R ｂ R ｃ AsR ａ R ｂ R ｃ SbR ａ R ｂ R ｃ , SR ａ R ｂ , R ｄ CN, R ｄ NC, N ２ , PF ３ Selected from the group consisting of pyridine and thiophene; R １ , R ２ , R ３ and R ４ is either hydrogen, or together with the pyridyl unit of the catalyst of formula (A) to form an acridinyl unit, or R １ and R ２ Or R ３ and R ４ It combines with the pyridyl unit of the catalyst of formula (A) to form a quinolinyl unit; n is either 0 or 1; Y is H, F, Cl, Br, I, OC(=O)CF ３ OSO ２ CF ３ ,CN,CO,OH,OR,NR ｄ ２ NH ３ , NR ｄ ３ and R ｄ ２ NSO ２ R ｄ Selected from the group consisting of; R ａ 、R ｂ 、R ｃ 、R ｄ 、R ５ 、R ６ and R ７ are, independently of one another, H, unsubstituted or substituted C １ -C １０ -alkyl (the substituents being selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl); unsubstituted or substituted C １ -C １０ -cycloalkyl (the substituents being selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl); unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O and S ３ -C １０ -heterocyclyl (the substituents being selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl); unsubstituted or substituted C ５ -C １０ -aryl (the substituents being selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl); and unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O and S ５ -C １０ -heteroaryl (the substituents being selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl) and are selected from the group consisting of; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on the acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on the quinolinyl unit, or 1 substituent located on a carbon atom on the pyridyl unit, wherein the substituents are F, Cl, Br, OH, CN, NH ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; For the compound of formula (L), R １ , R ２ , R ３ and R ４ is either hydrogen, or together with the pyridyl unit of the catalyst of formula (L) to form an acridinyl unit, or R １ and R ２ Or R ３ and R ４ It combines with the pyridyl unit of the catalyst of formula (L) to form a quinolinyl unit; n is either 0 or 1; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on the acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on the quinolinyl unit, or 1 substituent located on a carbon atom on the pyridyl unit, wherein the substituents are F, Cl, Br, OH, CN, NH ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; L １ and L ２ They operate independently of each other, PR ａ R ｂ , NR ａ R ｂ , SR ａ , SH, S(=O)R ａ , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR ａ R ｂ SbR ａ R ｂ , and structure: 【Transformation 5】 or 【Transformation 6】 It is an N-heterocyclic carbene represented by; R ａ , R ｂ , R ｃ , R ｄ , R ５ , R ６ and R ７ These are H, unsubstituted, or substituted C, independently of each other. １ -C １０ - Alkyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups); unsubstituted or substituted C １ -C １０ -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O, and S ３ -C １０ - Heterocyclyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups); unsubstituted or substituted C ５ -C １０ -aryl (the substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; and unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O, and S. ５ -C １０ - Heteroaryl (the substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ Selected from the group consisting of alkyl groups; For the compound of formula (L), R １ , R ２ , R ３ and R ４ , X, L １ , L ２ and n are preferably R of the catalyst of formula (A). １ , R ２ , R ３ and R ４ , X, L １ , L ２ (and is identical to n) The precursor of the catalyst containing the compound of formula (A) is a compound containing metal M, and CO, PR ａ R ｂ R ｃ , SR ａ R ｂ , R ａ CN, R ａ NC, N ２ , PF ３ , organic carbonyl compounds, C １ -C １０ - Alkyl, C １ -C １２ - Cycloalkyl, C ２ -C １２ - Alkenil, C ３ -C １５ -Cycloalkenyl, C ５ -C ２０ -aryl, CN, CO, OH, OC(=O)CF ３ OSO ２ CF ３ A mixture comprising at least one component selected from the group consisting of hydrides, pyridines, halides, hydroxides, and thiophenes, and a compound of formula (H). 【Transformation 7】 (wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru; L １ and L ２ They operate independently of each other, PR ａ R ｂ , NR ａ R ｂ , SR ａ , SH, S(=O)R ａ , heteroaryls containing at least one heteroatom selected from nitrogen and sulfur, AsR ａ R ｂ SbR ａ R ｂ , and structure: 【Transformation 8】 or 【Chemistry 9】 It is an N-heterocyclic carbene represented by; R １ , R ２ , R ３ and R ４ is either hydrogen, or together with the pyridyl unit of the catalyst of formula (A) to form an acridinyl unit, or R １ and R ２ Or R ３ and R ４ It combines with the pyridyl unit of the catalyst of formula (A) to form a quinolinyl unit; n is either 0 or 1; R ａ , R ｂ , R ｃ , R ｄ , R ５ , R ６ and R ７ These are H, unsubstituted, or substituted C, independently of each other. １ -C １０ - Alkyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups); unsubstituted or substituted C １ -C １０ -Cycloalkyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O, and S ３ -C １０ - Heterocyclyl (substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups); unsubstituted or substituted C ５ -C １０ -aryl (the substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ - Selected from the group consisting of alkyl groups; and unsubstituted or substituted C containing at least one heteroatom selected from the group consisting of N, O, and S. ５ -C １０ - Heteroaryl (the substituents are F, Cl, Br, OH, CN, NH) ２ and C １ -C １０ (Selected from the group consisting of alkyl groups) Selected from the group consisting of; X is selected from the group consisting of 1, 2, 3, 4, 5, 6, and 7 substituents located on any carbon atom on the acridinyl unit, or 1, 2, 3, 4, and 5 substituents located on any carbon atom on the quinolinyl unit, or 1 substituent located on a carbon atom on the pyridyl unit, wherein the substituents are F, Cl, Br, OH, CN, NH ２ and C １ -C １０ (Selected from the group consisting of alkyl groups) The alcohol conversion process, including the alcohol conversion process.

2. In (iii), the reaction space is the reaction mixture M Ｇ and a gas phase, wherein the gas phase is H ２ The alcohol conversion conditions include the gas phase H ２ Partitioning the pressure by 2 x 10 ４ From 3.1 x 10 ６ The process according to claim 1, further comprising maintaining within the range of Pa.

3. The H of the gas phase ２ The partial pressure is H in the gas phase. ２ Maintained by introducing or the H of the gas phase ２ The process according to claim 2, wherein the partial pressure is maintained by the relaxation of the gas phase.

4. The liquid mixture M prepared according to (ii) and subjected to alcohol conversion conditions according to (iii) Ｅ The process according to any one of claims 1 to 3, wherein the molar ratio of the compound of formula (L) to the compound of formula (A) is in the range of 0.01:1 to 10:1, preferably in the range of 0.05:1 to 10:1, and more preferably in the range of 0.1:1 to 10:

1.

5. The process according to any one of claims 1 to 4, wherein the compound of formula (L) is selected from the group consisting of dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane, diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane, dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)pyridine-4-yl]methyl]phosphane, and diisopropyl-[[5-(diisopropylphosphanylmethyl)pyridine-4-yl]methyl]phosphane, and preferably the additional compound is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane.

6. The reaction mixture M is Ru, and the alcohol conversion conditions according to (iii) are in the range of 100 to 170°C. Ｇ The process according to any one of claims 1 to 5, including the temperature.

7. A catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (E). 【Chemistry 10】 (In the formula, Cy is cyclohexyl.) Includes, The compound of formula (L) is preferably: 【Chemistry 11】 The process according to any one of claims 1 to 6.

8. A catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (F). 【Chemistry 12】 (In the formula, iPr is isopropyl.) Includes, The compound of formula (L) is preferably: 【Chemistry 13】 The process according to any one of claims 1 to 6.

9. A catalyst, its precursor, a reduced form of the catalyst, or at least one of the reduced forms of the precursor is a compound of formula (G). 【Chemistry 14】 (tBu is tert-butyl) Includes, The compound of formula (L) is preferably: 【Chemistry 15】 The process according to any one of claims 1 to 6.

10. The process according to any one of claims 1 to 9, wherein the integer x is 1; and / or R is selected from the group consisting of H, ethyl, and propyl.

11. The reduced form of the aforementioned precursor is a compound of formula (P-I) or (P-II): 【Chemistry 16】 (In the formula, R １ , R ２ , R ３ and R ４ is either hydrogen or, together with an N-containing ring, forms a tetrahydroquinoline unit, a decahydroquinoline unit, a tetrahydroacridine unit, or a tetradecahydroacridine unit; L １ and L ２ (These are independent of each other, as defined above); 【Chemistry 17】 (In the formula, R １ , R ２ , R ３ and R ４ is hydrogen; L １ and L ２ (These are independent of each other, as defined above.) The process according to any one of claims 1 to 10, including the process described in any one of claims 1 to 10.

12. The mixture M obtained according to (iv) Ｃ The process according to any one of claims 1 to 11, further comprising recycling at least one portion of the catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor into (ii) or (iii).

13. The liquid mixture M prepared according to (ii) Ｅ The process according to any one of claims 1 to 12, further comprising a solvent having a boiling point of 110°C or higher.

14. The mixture M obtained according to (iv) Ｃ The mixture M obtained according to (iv) comprises at least one of a catalyst, its precursor, a reduced form of the catalyst, or a reduced form of the precursor, and further comprises the solvent. Ｃ The process according to any one of claims 1 to 13, further comprising recirculating at least a portion of the solvent contained in to (ii) or (iii).

15. The liquid reaction mixture M obtained according to (iii) Ｇ However, at least one unreacted alcohol R-CH ２ -CH ２ -OH further comprises the process, and the unreacted alcohol R-CH ２ -CH ２ - At least a portion of the OH is in the liquid reaction mixture M Ｇ Further including separation from M Ｇ The at least one unreacted alcohol R-CH4 separated from ２ -CH ２ The process according to any one of claims 1 to 14, wherein at least a portion of the -OH is recycled to (ii) or (iii).

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