Alcohol conversion process

Abstract

This invention relates to an alcohol conversion process using a homogeneous transition metal catalyst. In this process, the hydrogen partial pressure is maintained within a pressure range, can be increased, or hydrogen can be removed from the system. Hydrogen can also be used as an external additive.

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] 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 1At least one complex compound is used that is selected from linear or branched C2-C3 alkyl groups in a homogeneous phase, and contains Ru(II), wherein Ru(II) is at least bidentate, and is at least one ligand L 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]

[0009] [Patent Document 1] International Publication No. 2012 / 119928 [Patent Document 2] International Publication No. 2013 / 156399 [Non-patent literature]

[0010] [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 [Overview of the project] [Problems that the invention aims to solve]

[0011] 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, with increased productivity.

[0012] Therefore, the present invention relates to an alcohol conversion process based on the Guerbet reaction, in which a homogeneous transition metal catalyst is used. This process can be economically realized by maintaining the hydrogen partial pressure within a pressure range, and the partial pressure affects the reactivity. Increasing the hydrogen partial pressure may slow down the reactivity, but at the same time may increase the alcohol selectivity of the product. Similarly, when hydrogen is removed from the system, for example, through the gas phase, an increase in rate is observed. Furthermore, hydrogen can be used as an external additive to reduce the formation of unwanted by-products in the Guerbet process, such as alcohols with higher boiling points. This results in an increase in productivity.

Means for Solving the Problems

[0013] The present invention is particularly an alcohol conversion process comprising: (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, a base, and at least one of the catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor provided according to (i), <00000@5>where R is selected from the group consisting of H and C1-C4-alkyl; (iii) subjecting the liquid mixture M prepared according to (ii) E to alcohol conversion conditions in a reaction space S R to obtain a reaction mixture M comprising at least one alcohol R-CH2-CH2-(CHR-CH2) x -OH, where x is an integer in the range from 1 to 4, the reaction space comprising the reaction mixture M G and a gas phase, and the alcohol conversion conditions comprising a temperature of the reaction mixture M in the range from 100 to 250 °C G and a pressure of the reaction space S in the range from 1×10 G to 4×10 5 Pa. 6 RThe internal pressure is included, 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 1.1x10 6 The steps further include maintaining within the range of Pa; (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) 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 20A mixture comprising at least one component selected from the group consisting of -aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydride, pyridine, halide, hydroxide, and thiophene, and a compound of formula (H) [Chemical formula] (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, S(=O)R<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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) This relates to the alcohol conversion process, including the process itself. [Brief explanation of the drawing]

[0014] [Figure 1] This figure shows that a higher conversion rate was obtained in the experiment under an overpressure of 10 bar compared to the experiment under intrinsic pressure (Example 5 vs. Example 6 vs. Comparative Example 1). [Figure 2]This is a time-time graph showing the conversion rate at different pressures. [Figure 3] These are overpressure versus time diagrams for Example 5, Example 6, and Comparative Example 1. [Modes for carrying out the invention]

[0015] 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.

[0016] 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. In further embodiments, the alcohol conversion conditions according to (iii) are in the range of 100 to 200°C, preferably 120 to 180°C, more preferably 130 to 170°C for the reaction mixture M G It is preferable to include the temperature.

[0017] 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 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 contained within. Furthermore, the alcohol conversion conditions according to (iii) are preferably for reaction mixture M GBased 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 This includes the amount of catalyst inside.

[0018] According to (ii), the reaction space S R The partial pressure of H2 in the gas phase inside is 2 x 10⁻⁶ 4 From 1.0x10 6 Preferably, it is maintained within the range of Pa, and 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 It will be maintained within the Pa range.

[0019] The partial pressure of H2 in the gas phase is preferably maintained by introducing H2 into the gas phase. Alternatively, the partial pressure of H2 in the gas phase is preferably maintained by the relaxation of the gas phase.

[0020] "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.

[0021] The pressure during the reaction can be monitored, for example, by determining the overall pressure and comparing it to the starting pressure. Because hydrogen tends to accumulate during the reaction, the H2 partial pressure changes, for example, increases, and the pressure rises over time. For example, by actively measuring and controlling the total pressure during the reaction, it can be ensured that the H2 partial pressure is within the requested range. If the accumulation of total pressure is too high, this tends to be a result of an increase in the H2 partial pressure, at least partially. By relaxing the gas phase, hydrogen can be removed from the gas phase and the H2 partial pressure can be maintained within the desired range. Therefore, in one preferred embodiment, it is preferable to maintain the H2 partial pressure of the gas phase within the respective ranges, preferably by monitoring the total pressure of the reaction and adjusting the total pressure as needed, preferably by relaxing the gas phase, in which case the H2 partial pressure may be decreased, or by introducing H2 into the gas phase, in which case the H2 partial pressure may be increased.

[0022] Alternatively, the hydrogen partial pressure can be determined by other means, for example, by taking a gas phase sample during the reaction and analyzing it. Another alternative is that the pressure may be monitored via online measurement and adjusted accordingly as outlined above.

[0023] This process 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).

[0024] Also, liquid mixture M prepared according to (ii) E The mixture 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.

[0025] The solvent 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. The partition coefficient of the catalyst in the solvent and water system is also preferably 0 to 0.01, more preferably 0 to 0.005, and more preferably 0 to 0.005, based on 1 kg of catalyst.

[0026] Preferably, the solvent is a mixture of at least two aromatic hydrocarbons having a boiling point of 180°C or higher. 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.

[0027] In preferred embodiments, the solvent does not contain any of benzene, toluene, xylene, or mesitylene.

[0028] 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.

[0029] Furthermore, the solvent is a mixture of biphenyl and diphenyl ether, preferably 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, more preferably in the range of 1:2.5 to 1:4.

[0030] 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 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 This includes the amount of solvent inside.

[0031] In a more preferred embodiment, 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, its precursor, or at least one reduced form of the catalyst or precursor.

[0032] Preferably, the mixture M obtained according to (iv) C The process 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. The process more preferably involves a mixture M obtained according to (iv). C This includes recirculating at least a portion of the solvent contained in (ii) or (iii) to (ii).

[0033] (iii) Liquid reaction mixture M obtained according to (iii) G The process further comprises at least one unreacted alcohol R-CH2-CH2-OH, and the liquid reaction mixture M G This includes separating at least a portion of the unreacted alcohol R-CH2-CH2-OH from the M GSeparation of at least a portion of the unreacted alcohol R-CH2-CH2-OH from is preferably carried out by distillation, extraction, flushing, or by using a membrane. Preferably, M G At least a portion of the at least one unreacted alcohol R-CH2-CH2-OH separated from is recycled to (ii) or (iii).

[0034] Step (ii) Liquid mixture M E The preparation preferably comprises at least one alcohol R-CH2-CH2-OH, a base, a solvent, and at least one catalyst or precursor provided according to (i).

[0035] In equation (A), R 1 , R 2 , R 3 and R 4 If n is hydrogen, then n is preferably 0.

[0036] Preferably, 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 , 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 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. Includes.

[0037] The catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced form 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 Rb , 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. It is also preferable to include it.

[0038] The 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 (D). [ka] (In the formula, M is selected from the group consisting of Ir, Ru, and Mn; L1 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. It is even more preferable to include it.

[0039] M is preferably selected from the group consisting of Ir and Ru, and more preferably M is Ru.

[0040] M is preferably 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 M G This includes the temperature.

[0041] L 3 It is preferably CO.

[0042] Preferably, L 1 and L 2 These are (PR a R b ) and R a and R b C1-C 10 -It is alkyl, preferably R a and R b These are isopropyl or tert-butyl, respectively. Or, L 1 and L 2 These are preferably (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 These are preferably (PR a R b ) and R a and R b C5-C 10 - It is Ariel.

[0043] Y is preferably selected from the group consisting of F, Cl, Br, and I, more preferably selected from the group consisting of Cl or Br, and more preferably Y is Cl. It is also preferable that Y is CO.

[0044] Preferably, 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 (E). [Chemical formula] (where Cy is cyclohexyl) contains

[0045] The reduced form of the catalyst is a compound of formula (E’) [Chemical formula] (where Cy is cyclohexyl) also preferably contains

[0046] 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) [Chemical formula] (where iPr is isopropyl) more preferably contains

[0047] The reduced form of the catalyst is a compound of formula (F’) [Chemical formula] (where iPr is isopropyl) also preferably contains

[0048] 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 (G) [Chemical formula] (where tBu is tert-butyl) more preferably contains

[0049] Preferably, the reduced form of the catalyst is a compound of formula (G’) [Chemical formula] (where tbu is tert-butyl) contains

[0050] The catalyst, its precursor, the reduced form of the catalyst, or at least one of the reduced forms of the precursor is preferably 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. Alternatively, 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) 12A 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.

[0051] Preferably, the reduced form of the precursor is a compound of formula (P-I) or (P-II):

Chemical formula

[0053] 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.

[0054] Preferably, the integer x is 1 or 2, and more preferably x is 1.

[0055] Preferably, 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.

[0056] In a preferred embodiment, liquid mixture M prepared according to (ii) E Preferably, the compound of formula (H'): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are R of the catalyst in formula (A). 1 , R 2 , R 3 and R 4, L 1 , L 2 (and is identical to n) It also includes.

[0057] 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 (H) 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 1.04:1 to 6:1, and more preferably in the range of 1.05:1 to 5:1.

[0058] Preferably, the compound of formula (H) 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 compound of formula (H) is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane.

[0059] Preferably, the base is selected from the group consisting of alkali hydroxides, alkali alkoxides, and mixtures thereof. The alkali hydroxide is preferably selected from the group consisting of NaOH, KOH, and mixtures thereof, and preferably the alkali hydroxide is KOH. The alkali alkoxide is preferably selected from the group consisting of sodium alkoxides, potassium alkoxides, and mixtures thereof, and preferably selected from the group consisting of sodium ethoxides, potassium ethoxides, and mixtures thereof.

[0060] 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.

[0061] In the process according to the present invention, reaction space S R The reaction vessel is contained within a reaction vessel, which is preferably a fully mixed reaction vessel.

[0062] 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.

[0063] 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 comprising at least one alcohol R-CH2-CH2-OH, a base, and at least one catalyst, its precursor, a reduced form of the catalyst, or a reduced form of the precursor. E A step of preparing a product, wherein R is selected from the group consisting of H and C1-C4-alkyl groups; (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 and a gas phase, wherein the alcohol conversion conditions are in the range of 100 to 250°C. G Temperature and 1x10 5 From 4x10 6 Reaction space S in the range of Pa R The internal pressure is included, 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 1.1x10 6 The steps further include maintaining within the range of Pa; (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 dSelected 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) 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] (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 , SRa 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.

[0064] 2. The process according to Embodiment 1, wherein the process is a continuous process.

[0065] 3. The process according to Embodiment 1, wherein the process is a semi-batch process or a batch process.

[0066] 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.

[0067] 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 2x106 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.

[0068] 6.(iii) The alcohol conversion conditions are in the range of 100 to 200°C, preferably 120 to 180°C, more preferably 130 to 160°C for the reaction mixture M G The process according to any one of embodiments 1 to 5, including the temperature.

[0069] 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.

[0070] 8.(iii) The alcohol conversion conditions 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.

[0071] According to 9.(ii), the reaction space S R The partial pressure of H2 in the gas phase inside is 2 x 10 4 From 3.1x10 6 Range of Pa, preferably 2x10 4 from 1.1x10 6 Pa range, more preferably 2x10 4 From 6x10 5 A process according to any one of embodiments 1 to 8, maintained in the range of Pa.

[0072] 10. The process according to any one of Embodiments 1 to 9, wherein the partial pressure of H2 in the gas phase is maintained by introducing H2 into the gas phase.

[0073] 11. The process according to any one of embodiments 1 to 9, wherein the partial pressure of H2 in the gas phase is maintained by relaxation of the gas phase.

[0074] 12. The process according to any one of claims 1 to 11, wherein the partial pressure of H2 in the gas phase is maintained by monitoring the total pressure during the reaction, preferably by monitoring the total pressure of the gas phase and adjusting the total pressure of the gas phase as necessary, more preferably by adjusting the total pressure of the gas phase by gas phase relaxation, and / or by introducing H2 into the gas phase.

[0075] 13. The process according to any one of claims 1 to 11, wherein the partial pressure of H2 in the gas phase is maintained by taking a sample of the gas phase during the reaction and analyzing it, and, if necessary, by adjusting the total pressure of the gas phase, preferably by adjusting the total pressure of the gas phase, more preferably by relaxing the gas phase, and / or by introducing H2 into the gas phase.

[0076] Mixture M obtained according to 14.(iv) C The process according to any one of Embodiments 1 to 13, 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).

[0077] Liquid mixture M prepared according to 15.(ii) E The process according to any one of Embodiments 1 to 14, further comprising a solvent.

[0078] 16. The process according to Embodiment 15, 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.

[0079] 17. The process according to Embodiment 15 or 16, 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, and more preferably 0 to 0.01% by weight, based on 100% by weight of water.

[0080] 18. The process according to any one of Embodiments 15 to 17, 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.

[0081] 19. The process according to any one of embodiments 15 to 18, wherein the solvent is a mixture of at least two aromatic hydrocarbons having a boiling point of 180°C or higher.

[0082] 20. The process according to Embodiments 15 to 19, wherein 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 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.

[0083] 21. The process according to any one of Embodiments 15 to 20, 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.

[0084] 22. The process according to any one of embodiments 15 to 21, wherein the solvent does not form an azeotrope with water.

[0085] 23. The process according to any one of Embodiments 15 to 22, wherein the solvent does not contain any one of benzene, toluene, xylene, or mesitylene.

[0086] The alcohol conversion conditions according to 24.(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 15 to 23, including the amount of solvent in the solvent.

[0087] Liquid mixture M prepared according to 25.(ii) E The process according to any one of Embodiments 15 to 24, 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 process comprises at least one alcohol R-CH2-CH2-OH, a base, a solvent, and a catalyst, its precursor, or at least one reduced form of the catalyst or precursor.

[0088] Mixture M obtained according to 26.(iv) C The process according to any one of Embodiments 15 to 25, 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.

[0089] Mixture M obtained according to 27.(iv) C The process according to Embodiment 26, further comprising recirculating at least a portion of the solvent contained in to (ii) or (iii).

[0090] Liquid reaction mixture M obtained according to 28.(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 27, further comprising separating at least a portion of the unreacted alcohol R-CH2-CH2-OH from the alcohol.

[0091] 29.M G The process according to Embodiment 28, wherein at least a portion of the unreacted alcohol R-CH2-CH2-OH is separated from the mixture by distillation, extraction, flushing, or by using a membrane.

[0092] 30.M G The process according to embodiment 28 or 29, wherein at least a portion of the at least one unreacted alcohol R-CH2-CH2-OH separated from is recycled to (ii) or (iii).

[0093] 31. In step (ii), liquid mixture M E The process according to any one of Embodiments 1 to 30 comprises at least one alcohol R-CH2-CH2-OH, a base, a solvent, and at least one catalyst or precursor provided according to (i).

[0094] 32. In equation (A), R 1 , R 2 , R 3 and R 4 The process according to any one of Embodiments 1 to 31, wherein n is 0 when is hydrogen.

[0095] 33. 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 (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 , 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 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. A process according to any one of embodiments 1 to 31, including the process described above.

[0096] 33. 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. A process according to any one of embodiments 1 to 31, including the process described above.

[0097] 35. 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 (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, 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. A process according to any one of embodiments 1 to 31, including the process described above.

[0098] 36. The process according to any one of Embodiments 1 to 35, wherein M is selected from the group consisting of Ir and Ru, and preferably M is Ru.

[0099] 37. 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 36, including the temperature.

[0100] 38.L 3 The process according to any one of embodiments 1 to 37, wherein CO is

[0101] 39.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 38, wherein the respective isopropyl or tert-butyl.

[0102] 40L 1 and L 2 Each of them (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 38, wherein each of the elements is cyclohexyl.

[0103] 41.L 1 and L 2 Each of them (PR a R b ) and R a and R b C5-C 10 - The process according to any one of embodiments 1 to 38, which is an aryl.

[0104] 42. The process according to any one of Embodiments 1 to 41, 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.

[0105] 43. The process according to any one of Embodiments 1 to 41, wherein Y is CO.

[0106] 44. 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.) A process according to any one of embodiments 1 to 31, including the process described above.

[0107] 45. The reduced form of the catalyst is a compound of formula (E'). [ka] (In the formula, Cy is cyclohexyl.) A process according to any one of embodiments 1 to 31, including the process described above.

[0108] 46. ​​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) A process according to any one of embodiments 1 to 31, including the process described above.

[0109] 47. The reduced form of the catalyst is a compound of formula (F'). [ka] (In the formula, iPr is isopropyl) A process according to any one of embodiments 1 to 31, including the process described above.

[0110] 48. 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). [ka] (In the formula, tbu is tert-butyl.) A process according to any one of embodiments 1 to 31, including the process described above.

[0111] 49. The reduced form of the catalyst is a compound of formula (G'). [ka] (In the formula, tbu is tert-butyl.) A process according to any one of embodiments 1 to 31, including the process described above.

[0112] 50. 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) 12The process according to any one of Embodiments 1 to 31, 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.

[0113] 51. 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 The process according to any one of Embodiments 1 to 31, 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.

[0114] 52. 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 51, including the process described above.

[0115] 53. 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 (This is either hydrogen or, together with an N-containing ring, forms a tetrahydroacridine unit or a tetradecahydroacridine unit.) A process according to any one of embodiments 1 to 52, including the process described above.

[0116] 54. 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 53, including the process described above.

[0117] 55. The process according to any one of Embodiments 1 to 54, wherein the integer x is 1 or 2, preferably the integer x is 1.

[0118] 56. The process according to any one of Embodiments 1 to 55, 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.

[0119] Liquid mixture M prepared according to 57.(ii) E However, the compound of formula (H'): [ka] (In the formula, R 1 , R 2 , R 3 and R 4 , L 1 , L 2 and n are R of the catalyst in formula (A). 1 , R 2 , R 3 and R 4 , L 1 , L 2 (and is identical to n) The process according to any one of embodiments 1 to 56, further including the process described above.

[0120] Liquid mixture M prepared according to 58.(ii) and subjected to alcohol conversion conditions according to (iii) EThe process according to Embodiment 57, wherein the molar ratio of the compound of formula (H) 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 1.04:1 to 6:1, and more preferably in the range of 1.05:1 to 5:1.

[0121] 59. The process according to Embodiment 57 or 58, wherein the compound of formula (H) 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-(diisopropylphosphanylmethyl)pyridine-4-yl]methyl]phosphane, and preferably the compound of formula (H) is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridine-4-yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridine-4-yl]methyl]phosphane.

[0122] 60. The process according to any one of Embodiments 1 to 59, wherein the base is selected from the group consisting of alkali hydroxides, alkali alkoxides, and mixtures thereof.

[0123] 61. The process according to Embodiment 60, wherein the alkali hydroxide is selected from the group consisting of NaOH, KOH, and mixtures thereof, and preferably the alkali hydroxide is KOH.

[0124] 62. The process according to Embodiment 61, 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.

[0125] 63. The process according to any one of Embodiments 1 to 62, wherein at least one alcohol R-CH2-CH2-OH is a bio-based alcohol and can or can be obtained from a sugar-containing crop, preferably from one or more of sugarcane and maize.

[0126] 64. Reaction space S R The process according to any one of Embodiments 1 to 63, wherein the reaction vessel is included and the reaction vessel is preferably a complete mixing reaction vessel.

[0127] 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]

[0128] 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.

[0129] Example 1 137.5 g of ethanol, 251.5 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 10.11 g of potassium ethoxide (4 mol%) were weighed in a glove box and poured into a 300 mL autoclave. The stirrer was switched to 700 rpm. The reaction mixture was then heated to 150°C and stirred at inert pressure for 6 hours. After the reaction solution was cooled to room temperature, the autoclave was reduced to pre-shift pressure. The autoclave was removed in the air. Aliquots of the orange-brown solution containing a small amount of dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC. [ka]

[0130] Example 2 69 g of ethanol, 125.8 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 5.06 g of potassium ethoxide (4 mol%) were weighed in a glove box and poured into a 300 mL autoclave. The stirrer was switched to 700 rpm. The reaction mixture was then heated to 150°C and stirred at inertia pressure for 6 hours. After the reaction solution was cooled to room temperature, the autoclave was reduced to preshift. The autoclave was removed in the air. Aliquots of the orange-brown solution containing a small amount of dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC.

[0131] Example 3 34.4 g of ethanol, 62.9 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 2.53 g of potassium ethoxide (4 mol%) were weighed in a glove box and poured into a 300 mL autoclave. The stirrer was switched to 700 rpm. The reaction mixture was then heated to 150°C and stirred at inertia pressure for 6 hours. After the reaction solution was cooled to room temperature, the autoclave was reduced to preshift. The autoclave was removed in the air. Aliquots of the orange-brown solution containing a small amount of dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC.

[0132] Example 4 17.2 g of ethanol, 31.5 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 1.27 g of potassium ethoxide (4 mol%) were weighed in a glove box and poured into a 300 mL autoclave. The stirrer was switched to 700 rpm. The reaction mixture was then heated to 150°C and stirred at inertia pressure for 6 hours. After the reaction solution was cooled to room temperature, the autoclave was reduced to pre-shift pressure. The autoclave was removed in the air. Aliquots of the orange-brown solution containing a small amount of dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC.

[0133] [Table 1]

[0134] As can be seen from Table 1, the yield of (by)products quantified by GC increases as the ratio of liquid reaction volume to autoclave volume decreases / overpressure decreases: a 62% liquid reaction volume results in a conversion rate of 16.0%, and a 30% liquid reaction volume results in a conversion rate of 25.0%.

[0135] Example 5 70.09 g of ethanol, 3.80 g of potassium ethoxide (3 mol%), 172.6 mg of (Cy-Acr-PNP)RuHCl(CO) (0.015 mol%), and 135.2 mg of Cy-Acr-PNP (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 under countercurrent of nitrogen, and the screw-top bottle was rinsed with ethanol. Finally, a mixture of 7.71 g of diphenyl and diphenyl ether in a molar ratio of 1:3 was added as the solvent. The reaction mixture was heated to 150°C for about 15 minutes with the outlet valve closed at a heating power of 85% while stirring at 750 rpm. Overpressure, e.g., pressure above atmospheric pressure, was maintained at about 10 bar during the reaction by measuring gas phase overpressure and relaxation as needed.

[0136] After the reaction temperature reached 150°C, a "zero sample" was taken. It 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.

[0137] Example 6 Example 6 was carried out according to Example 5, but the overpressure was not maintained at 10 bar throughout the reaction; instead, the reaction was carried out under intrinsic pressure.

[0138] Example 7 Example 7 was carried out according to Example 5, but the overpressure was not maintained at 10 bar throughout the reaction; instead, the overpressure was maintained at approximately 12 bar during the reaction.

[0139] Example 8 Example 8 was carried out according to Example 5, but the overpressure was not maintained at 10 bar throughout the reaction; instead, the overpressure was maintained at approximately 14 bar during the reaction.

[0140] Comparative Example 1 Comparative Example 1 was carried out according to Example 5, but H2 was compressed at 10 bar before heating, and the reaction was carried out under intrinsic pressure.

[0141] As can be seen from the results shown in Figure 1, a higher conversion rate was obtained in the experiment under a pressurization of 10 bar compared to the experiment under intrinsic pressure (Example 5 vs. Example 6). The lower hydrogen partial pressure enables a higher conversion rate in Example 5 compared to Example 6.

[0142] When the reaction is carried out under hydrogen pressure, the conversion rate decreases even further (Comparative Example 1).

[0143] Figure 2 shows the results of the reactions carried out under intrinsic pressure and different overpressures, with the pressure kept constant (overpressures of 10 bar, 12 bar, and 14 bar, respectively). When the experiment was carried out under isobaric conditions under otherwise identical conditions, an increase in conversion rates from 37% to 41% to 47% was observed after 6 hours when the overpressure was adjusted (and maintained) from 14 bar and from 12 bar to 10 bar, respectively.

[0144] Therefore, compared to reactions carried out under intrinsic pressure, a decrease in the partial pressure of hydrogen in isobaric reactions leads to an increase in conversion rate, indicating that ideally, the partial pressure of H2 should be maintained (and preferably actively controlled) within a specific pressure range for optimal conditions and results.

[0145] Figure 3 shows the overpressure versus time for Examples 5, 6, and Comparative Example 1. As can be seen from Figure 3, in Example 5, the overpressure was actively controlled, as is also slightly evident from the initial curve showing a slight rise and fall due to gas phase relaxation. Example 6 was performed under intrinsic pressure, with H2 at 10 bar initially being compressed, as in Comparative Example 1. Figure 3 also shows that, ideally, the H2 partial pressure should be maintained (and preferably actively controlled) within a specific pressure range for optimal conditions and results.

[0146] Example 9 69 g of ethanol, 125.8 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 5.06 g of potassium ethoxide (4 mol%) were weighed in a glove box and poured into a 300 mL autoclave. The stirrer was switched to 700 rpm. The reaction mixture was then heated to 150 °C and stirred at inertia pressure for 12 hours. After the reaction solution was cooled to room temperature, the autoclave was reduced to preshift. The autoclave was removed in the air. Aliquots of the orange-brown solution containing a small amount of dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC.

[0147] Example 10 An autoclave was filled in a glove box with 69 g of ethanol, 125.8 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 5.06 g of potassium ethanol (4 mol%). The stirrer was set to 700 rpm and the reaction mixture was heated to 150°C. The reaction mixture was held under autogenous pressure for 6 hours and then cooled to room temperature. The autoclave was carefully depressurized. Then, 10 bar of H2 was injected and the reaction mixture was stirred at 100°C for 1 hour. After carefully depressurizing the autoclave, the reaction mixture was again heated to 150°C and stirred under autogenous pressure for a further 6 hours. The autoclave was cooled to room temperature, carefully depressurized, and removed under air. Aliquots of the orange-brown solution containing a dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%) and then analyzed by GC.

[0148] Example 11 An autoclave was filled in a glove box with 69 g of ethanol, 125.8 mg of (Cy-Acr-PNP)RuHCl(CO) (0.01 mol%), and 5.06 g of potassium ethanol (4 mol%). The stirrer was set to 700 rpm and the reaction mixture was heated to 150°C. The reaction mixture was held under autogenous pressure for 6 hours and then cooled to room temperature. The autoclave was carefully depressurized. The reaction mixture was then heated again to 150°C and stirred under autogenous pressure for a further 6 hours. After the autoclave cooled to room temperature, it was carefully depressurized and removed under air. Aliquots of the orange-brown solution containing a dark brown solid were filtered and mixed with the internal standard 1,4-dioxane (20 wt%), and then analyzed by GC.

[0149] [Table 2]

[0150] In Examples 2 and 9, the reaction did not result in further conversion after 6 hours. However, when the gas phase was relaxed (Examples 10 / 11), it was observed that conversion improved even after 6 hours. This result indicates that hydrogen accumulates in the gas phase and deactivates the catalyst.

[0151] References: -M.Guerbet,CRHebd.Seances Acad.Sci.1899,128,p.511-513 - Y. - International Publication No. 2012 / 119928 - 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 A liquid mixture M comprising at least one of -OH, a base, a catalyst, its precursor, the reduced form of the catalyst, or the reduced form of the precursor. Ｅ A step of preparing a mixture in which R is H and C １ -C ４ - A step selected from the group consisting of alkyl groups; (iii) The liquid mixture M prepared according to (ii) Ｅ is subjected to alcohol conversion conditions in a reaction space S Ｒ to obtain, in the reaction space, 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, 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 Ｇ to 4×10 ５ Pa, the gas phase contains H ６ , and the alcohol conversion conditions further include maintaining the partial pressure of H in the gas phase in the range from 2×10 Ｒ to 1.1×10 ２ Pa, the step;​​​​​​ The reaction mixture M obtained according to (iv)(iii) Ｇ From at least one alcohol R-CH ２ -CH ２ - (CHR-CH ２ ) ｘ Separate the -OH group and obtain 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 1】 (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: 【Chemistry 2】 or 【Transformation 3】 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 each other, H, unsubstituted or substituted C １ -C １０ -alkyl (the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH ２ and C １ -C １０ -alkyl); unsubstituted or substituted C​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 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) Includes, 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). 【Chemistry 4】 (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 5】 or 【Transformation 6】 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; 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. (ii) In the reaction space S Ｒ The H of the gas phase inside ２ The divided pressure is 2 x 10 ４ From 6x10 ５ The process according to claim 1, maintained within the range of Pa.

3. The H of the gas phase ２ Partial pressure, H ２ The process according to claim 1 or 2, which is maintained by introducing into the gas phase.

4. The H of the gas phase ２ The process according to claim 1 or 2, wherein the partial pressure is maintained by the relaxation of the gas phase.

5. The mixture M obtained according to (iv) Ｃ The process according to any one of claims 1 to 4, 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).

6. The liquid mixture M prepared according to (ii) Ｅ The process according to any one of claims 1 to 5, further comprising a solvent having a boiling point of 110°C or higher.

7. The mixture M obtained according to (iv) Ｃ The process according to claim 6, further comprising recirculating at least a portion of the solvent contained in to (ii) or (iii).

8. 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 7, wherein at least a portion of the -OH is recycled to (ii) or (iii).

9. 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 8, including the temperature.

10. 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). 【Transformation 7】 (In the formula, Cy is cyclohexyl.) The process according to any one of claims 1 to 9, including the process described in any one of claims 1 to 9.

11. 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). 【Transformation 8】 (In the formula, iPr is isopropyl.) The process according to any one of claims 1 to 9, including the process described in any one of claims 1 to 9.

12. 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 9】 (In the formula, tBu is tert-butyl.) The process according to any one of claims 1 to 9, including the process described in any one of claims 1 to 9.

13. The process according to any one of claims 1 to 12, wherein the integer x is 1.

14. The process according to any one of claims 1 to 13, wherein R is selected from the group consisting of H, ethyl, and propyl.

15. The liquid mixture M prepared according to (ii) Ｅ However, the compound of formula (H'): 【Chemistry 10】 (In the formula, R １ , R ２ , R ３ and R ４ , L １ , L ２ and n are R of the catalyst in formula (A). １ , R ２ , R ３ and R ４ , L １ , L ２ (and is identical to n) The process according to any one of claims 1 to 14, further comprising:

Images