Alcohol conversion process

Abstract

Invention details;

Description

[0001] An alcohol conversion process

[0002] The present invention relates to an alcohol conversion process.

[0003] A commonly used industrial production of alcohols is mainly based on an oxo process. Said process comprises the reaction of an alkene with oxo gas, which is a mixture of hydrogen and carbon monoxide in a 1 :1 molar ratio. The reaction is followed by hydrogenation of the aldehyde into the desired alcohol.

[0004] An alternative process for the synthesis of alcohols is based on the Guerbet reaction which is known for many decades (M. Guerbet, C. R. Hebd. Seances Acad. Sci. 1899, 128, p. 511-513). It is generally accepted that the mechanism leading to Guerbet alcohols comprises the following three steps: (i) dehydrogenation of a primary alcohol to the respective aldehyde; (ii) aldol condensation of two aldehyde molecules to an a,p-unsaturated aldehyde with elimination of water; and (iii) hydrogenation of the unsaturated aldehyde to the dimer alcohol. An alkaline catalyst, e.g. sodium or potassium hydroxide or sodium or potassium alkoxides, is required for the Guerbet reaction. Often homogeneous or hetereogeneous metal catalysts are added to accelerate the dehydrogenation and hydrogenation steps. However, the Guerbet reaction generally suffers from harsh conditions, poor selectivity, separation issues and low yield.

[0005] In the chemical industry, butanol is an important intermediate product and solvent for a broad variety of products, including paints and various plastics. Up to now, butanol is produced from a petro-based feedstock, leading to a significant product carbon footprint for butanol and the resulting products. Therefore, it is important for the chemical industry to find and open an economical and sustainable process route to butanol with a lower product carbon footprint.

[0006] Ethanol may be a sustainable feedstock to produce chemicals. Using ethanol in the Guerbet reaction may be a profitable and sustainable approach to produce butanol. Whereas the Guerbet reaction is used up to date to produce higher alcohols from higher boiling alcohol feedstocks than ethanol, there is so far no industrial usage for the Guerbet reaction for ethanol as the feedstock to produce butanol. While the Guerbet reaction itself may seem a simple chemical reaction, employing ethanol as the feedstock causes inherent problems particularly concerning selectivity. Because the product, n-butanol, can itself also undergo dehydrogenation, higher alcohols often result as side products in the process, making the reaction so far not profitable on an industrial scale.

[0007] 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, pages 9077 to 9080, relates to a ruthenium pincer-catalyzed Guerbet-type process for the production of biofuel from ethanol.

[0008] WO 2012 / 119928 A1 relates to a method for producing alkanol amines which comprise a primary amino group and a hydroxyl group by alcohol amination of diols comprising two hydroxyl groups, using ammonia, and elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst, which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.

[0009] 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, pages 8661 to 8664, relates to the selective synthesis of primary amines directly from alcohols and ammonia under mild conditions, precluding the need for stoichiometric amounts of toxic reagents, high pressure, and harsh experimental conditions.

[0010] WO 2013 / 156399 A1 relates to a method for producing branched alcohols using at least one alcohol of formula R1-CH2-CH2-OH, the groups R1being different or the same and being selected from C2-C3 alkyl, linear or branched, in a homogeneous phase in the presence of at least one base, characterized in that at least one complex compound containing Ru(ll) is used, in which the Ru(ll) has at least one ligand L1, which is at least bidentate, at least one coordination site of L1being a nitrogen atom.

[0011] Therefore, it was an object of the present invention to provide an alcohol conversion process allowing a profitable and sustainable approach to produce alcohols such as butanol, leading to increased productivities.

[0012] The present invention thus relates to an alcohol conversion process based on the Guerbet reaction, wherein a homogenous transition metal catalyst is used. The process is economically feasible due to matching several factors, including the productivity, i.e. the space-time yield. The catalyst, e.g. a combination of metal and ligand, is a factor influencing these parameters.

[0013] Typically, in homogenously catalyzed Guerbet reactions, metal and (pincer) ligand are used in a 1 :1 molar ratio. With the process in accordance with the present invention however, the productivity can advantageously be drastically increased due to employing the ligand in molar excess relative to the metal center employed. The excess of ligand stabilizes the active catalyst species, thus leading to increased productivities.

[0014] The present invention in particular relates to an alcohol conversion process comprising

[0015] (i) providing at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor;

[0016] (ii) preparing a liquid mixture ME comprising at least one alcohol R-CH2-CH2-OH with R being selected from the group consisting of H and Ci-C4-alkyl, the liquid mixture ME further comprising a base, the at least one of a catalyst, precursor thereof, reduced form of the catalyst or reduced form of the precursor provided according to (i), and a compound of formula (L) (iii) subjecting the liquid mixture ME prepared according to (ii) to alcohol conversion conditions in a reaction space SR and obtaining in said reaction space a reaction mixture MG comprising at least one alcohol R-CH2-CH2-(CHR-CH2)x-OH, x being an integer in the range of from 1 to 4, wherein the reaction space comprises the reaction mixture MG and a gas phase, wherein the alcohol conversion conditions comprise a temperature of the reaction mixture ME in the range of from 100 to

[0017] 250 C and a pressure in the reaction space SR in the range of from 1 x 105Pa to 4 x 106Pa;

[0018] (iv) separating the at least one alcohol R-CH2-CH2-(CHR-CH2)x-OH from the reaction mixture MG obtained according to (iii), obtaining the at least one alcohol R-CH2-CH2- (CHR-CH2)X-OH and a mixture Me comprising the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor; wherein the base is selected from the group consisting of ammonium hydroxide, alkali hydroxides, alkaline earth hydroxides, ammonium carbonate, ammonium hydrogen carbonate, alkali carbonates, alkali hydrogen carbonates, alkaline earth carbonates, alkaline hydrogen carbonates, alkali alkoxides, alkaline earth alkoxides, alkali metal amides, alkaline earth metal amides, secondary amino acids, and a mixture of two or more thereof; the catalyst comprises a compound of formula (A) wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0019] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0020] L3is selected from the RdCN, RdNC, N2, PF3, pyridine, and thiophene;

[0021] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (A) a quinolinyl unit; n is 0 or 1 ; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, OH, OR, NRd2, NH3, NRd3, and Rd2NSO2Rd;

[0022] Ra, Rb, Rc, Rd, R5, R6and R7are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cio-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-C -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C - alkyl; and

[0023] X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; wherein for the compound of formula (L), R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (L) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (L) a quinolinyl unit; n is 0 or 1 ;

[0024] X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl;

[0025] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0026] Ra, Rb, Rc, Rd, R5, R6and R7are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-C -alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Ci-C -cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Cs-Cw-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-Cw-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10- alkyl; wherein for the compound of formula (L), R1, R2, R3and R4, X, L1, L2, and n are preferably identical to R1, R2, R3and R4, L1, L2and n of the catalyst of formula (A); the precursor of the catalyst comprising a compound of formula (A) comprises a mixture comprising a compound comprising a metal M and at least one component selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, organic carbonyl compounds, Ci-Cw-alkyl, Ci-Ci2-cycloalkyl, C2-Ci2-alkenyl, Cs-Cw-cycloalkenyl, C5-C20- aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridines, halogenides, hydroxides, and thiophenes; and a compound of formula (H) wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0027] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0028] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (A) a quinolinyl unit; n is 0 or 1 ;

[0029] Ra, Rb, Rc, Rd, R5, R6and R7are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cw-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Ci-C -cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Cs-Cw-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-Cw-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10- alkyl;

[0030] X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C -alkyL

[0031] Figure 1 illustrates significantly faster reactions and better conversions by comparison of an isolated catalyst (Comparative Example 1 vs. Example 1 ) and by comparison of an in situ- formed catalyst (Comparative Example 1 vs. Example 21 Example 3).

[0032] The process in accordance with the present invention is preferably a continuous process. Alternatively, the process is preferably a semi-batch process or a batch process.

[0033] Preferably, the alcohol conversion conditions according to (iii) comprise the presence of at least one inert gas in the reaction space SR, wherein the at least one inert gas is preferably selected from the group consisting of nitrogen, argon, and a mixture thereof. Also preferred is that the alcohol conversion conditions according to (iii) comprise a pressure in the reaction space SR in the range of from 1 x 105to 3.5 x 106Pa, preferably in the range of from 1 x 105to 3.1 x 106Pa, more preferably in the range in the range of from 1 x 105to 2 x 106Pa, more preferably in the range in the range from 1 x 105to 1 .5 x 106Pa.

[0034] Preferably, the alcohol conversion conditions according to (iii) comprise a temperature of the reaction mixture MG in the range of from 100 to 200 °C, preferably in the range of from 120 to 180 °C, more preferably in the range of from 120 to 160 °C, more preferably in the range of from 130 to 160 °C.

[0035] The alcohol conversion conditions according to (iii) preferably comprise an amount of the base in the reaction mixture MG in the range of from 0.1 to 10 weight-%, preferably in the range of from 0.5 to 8 weight-%, more preferably in the range of from 1 to 5 weight-%, based on the total weight of the reaction mixture MG. It is also preferred that the alcohol conversion conditions according to (iii) comprise an amount of the catalyst in the reaction mixture MG in the range of from 0.001 to 2 weight-%, preferably in the range of from 0.001 to 1 weight-%, more preferably in the range of from 0.001 to 0.5 weight-%, based on the total weight of the reaction mixture MG. In a further preferred embodiment, according to (iii), the reaction space comprises the reaction mixture MG and a gas phase, wherein said gas phase comprises H2 and the alcohol conversion conditions further comprise maintaining the H2 partial pressure of the gas phase in the range of from 2 x 104to 3.1 x 106Pa, preferably in the range of from 2 x 104to 1.1 x 106Pa, more preferably in the range of from 2 x 104to 6 x 105Pa, even more preferably in the range of from 5 x 104to 6 x 105Pa, even more preferably in the range of from 7 x 104to 6 x 105Pa. Preferably, the H2 partial pressure of the gas phase is maintained by introducing H2 into the gas phase. Alternatively, the H2 partial pressure of the gas phase is preferably maintained by relaxation of the gas phase.

[0036] “Maintaining” the H2 partial pressure of the gas phase in the sense of the present invention includes ensuring that the H2 partial pressure is within the desired range during the reaction. In case the H2 partial pressure is within the desired range, no active steps have to be carried out mandatorily, but the pressure may still be adjusted to a different part of the range if desired. 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 must be adjusted in case of ensuring that the H2 partial pressure is maintained within the desired range, for example by relaxation of the gas phase, in which case the H2 partial pressure may be reduced, or, alternatively, by introducing H2 into the gas phase, in which case the H2 partial pressure may be increased. Depending upon the H2 partial pressure during the reaction, one or even both of said alternatives may be carried out if desired to adjust the H2 partial pressure and to maintain the H2 partial pressure within the desired pressure range at all times during the reaction.

[0037] Preferably, in the liquid mixture ME prepared according to (ii) and subjected to alcohol version conditions according to (iii), the molar ratio of the compound of formula (L) relative to the compound of formula (A) is in a range of from 0.01 :1 to 10:1 , preferably in the range of from 0.05:1 to 10:1 , more preferably in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.3:1 to 10:1 , more preferably in the range of from 0.5:1 to 10:1 , more preferably in the range of from 0.7:1 to 10:1 , more preferably in the range of from 0.8:1 to 10:1 , more preferably in the range of from 1 :1 to 10:1 more preferably in the range of from 1.01 :1 to 10:1 , more preferably in the range of from 1.02:1 to 8:1 , more preferably in the range from 1 .03:1 to 7:1 , more preferably in the range from 1 .04:1 to 6:1 , and more preferably in the range from 1 .05:1 to 5:1 .

[0038] Moreover, 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, more preferably wherein the additional compound is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridin-4- yl]methyl]phosphane or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridin-4- yl]methyl]phosphane.

[0039] Preparing a liquid mixture ME in step (ii) preferably comprises at least one alcohol R-CH2-CH2- OH, a base, a solvent, and the at least one of a catalyst, or precursor thereof provided according to (i).

[0040] In formula (A), preferably n is 0 if R1, R2, R3and R4are hydrogen. The at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor preferably comprises a compound of formula (B) wherein

[0041] M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0042] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra;

[0043] L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0044] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit; n is 0 or 1 , and if R1, R2, R3and R4are hydrogen, n is 0;

[0045] Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cio-alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; Cs-C -aryl; and C5-C10- heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0046] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4’ L1, L2and n are preferably identical to R1, R2, R3and R4, L1, L2and n of the catalyst of formula (B).

[0047] Alternatively, the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor preferably comprises a compound of formula (C) wherein

[0048] M is selected from the group consisting of Ir, Ru, and Mn;

[0049] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra; L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0050] Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted C1-C10 alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10 alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10 alkyl; C3-C10 heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; C5-C10 aryl; and C5-C10 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0051] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4, L1, L2, and n are preferably identical to R1, R2, R3and R4’ L1, L2, and n of the catalyst of formula (C).

[0052] In another embodiment, the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor preferably comprises a compound of formula (D) wherein

[0053] M is selected from the group consisting of Ir, Ru, and Mn;

[0054] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra;

[0055] L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0056] Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-C -alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C C -alkyl; unsubstituted or substituted Ci-C -cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C -alkyl; Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; C5-C10 aryl; and C5-C10- heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0057] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4, L1, L2and n are preferably identical to R1, R2, R3and R4’ L1, L2and n of the catalyst of formula (D).

[0058] M is preferably selected from the group consisting of Ir and Ru, preferably M is Ru. Preferably, M is Ru, and the alcohol conversion conditions according to (iii) comprise a temperature of the reaction mixture MG in the range of from 100 to 170 °C, preferably in the range of from 120 to 170 °C, more preferably in the range of from 120 to 160 °C, more preferably in the range of from 130 to 150 °C.

[0059] Preferably, L3is CO.

[0060] L1and L2are preferably each (PRaRb), and wherein Raand Rbare Ci-C -alkyl, more preferably Raand Rbare each isopropyl or tert-butyl. Alternatively, L1and L2are preferably each (PRaRb), and wherein Raand Rbare Ci-Cio-cycloalkyl, preferably wherein Raand Rbare each cyclohexyl. Alternatively, wherein L1and L2are preferably each (PRaRb), and wherein Raand Rbare C5-C10- aryl.

[0061] Y is preferably selected from the group consisting of F, Cl, Br and I, preferably wherein Y is selected from the group consisting of Cl or Br, more preferably wherein Y is Cl. Also preferred is

[0062] Y being CO.

[0063] The at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor preferably comprises a compound of formula (E) wherein Cy is cyclohexyl, and wherein the compound of formula (L) is preferably:

[0064] Also preferred is that the reduced form of the catalyst comprises a compound of formula (E’) wherein Cy is cyclohexyl, and wherein the compound of formula (L) is preferably:

[0065] Moreover, it is preferred that the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (F) wherein iPr is isopropyl, and wherein the compound of formula (L) is preferably: Preferably, the reduced form of the catalyst comprises a compound of formula (F’) wherein iPr is isopropyl, and wherein the compound of formula (L) is preferably: It is further preferred that the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (G) wherein tBu is tert-butyl, and wherein the compound of formula (L) is preferably:

[0066] Moreover, it is preferred that the reduced form of the catalyst comprises a compound of formula

[0067] (G’) wherein tBu is tert-butyl, and wherein the compound of formula (L) is preferably:

[0068] Preferably, the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound comprising a metal M selected from the group consisting of lrCI3x H2O, [lr(COD)CI]2, [lr(COE)2CI]2, [lr(C2H4)2CI]2, [lr(COD)OH]2, [lr(COD)MeO]2, [lrCp*CI2], [IrCp Cl2], lr4(CO)i2, [lr(PPh3)2(CO)CI], [lr(acetylacetonate)3], and [lr(acetylacetonate)(COD)], wherein Cp is cylclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1 ,5-cyclooctadienyl, COE is cyclooctenyl, and methylallyl is 2-methylallyL Also preferred is that the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound comprising a metal M selected from the group consisting of [Ru(p-cymene)CI2]2, [Ru(benzene)Cl2]y, [Ru(CO)2Cl2]y, where y is in each case in the range from 1 to 1000, [RU(CO)3CI2]2, [Ru(COD)(allyl)], R11CI3 X H2O, [Ru(acetylacetonate)3], [Ru(DMSO)4Cl2], [Ru(cyclopentadienyl)(CO)2CI], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2CI], [Ru(Cp*)(CO)2H], [Ru(Cp*)(CO)2]2, [Ru(indenyl)(CO)2CI], [Ru(indenyl)(CO)2H], [Ru(indenyl)(CO)2]2, ruthenocene, [Ru(COD)CI2]2, [Ru(Cp*)(COD)CI], [RU3(CO)I2], [Ru(PPh3)4(H)2], [Ru(PPh3)3(CI)2], [Ru(PPh3)3(CO)(CI)2], [Ru(PPh3)3(CO)(CI)(H)], [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], wherein Cp is cylclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1 ,5-cyclooctadienyl, and methylallyl is 2- methylallyl.

[0069] Preferably, the reduced form of the precursor comprises a compound of formula (P-l) or (P-ll): wherein R1, R2, R3and R4either are hydrogen, or form together with the N-containing ring a tetrahydroquinoline unit, a decahydroquinoline unit, a tetrahydroacridine unit, or a tetradecahydroacridine unit; and wherein L1and L2are, independently of each other, as defined above; wherein R1, R2, R3and R4are hydrogen; and wherein L1and L2are, independently of each other, as defined above.

[0070] More preferred is that the reduced form of the precursor comprises a compound of formula (P-l): wherein R1, R2, R3and R4either are hydrogen, or form together with the N-containing ring a tetrahydroacridine unit, or a tetradecahydroacridine unit.

[0071] In another more preferred embodiment, the reduced form of the precursor comprises a compound of formula (P-ll): wherein R1, R2, R3and R4are hydrogen; and wherein L1and L2are, independently of each other, as defined above.

[0072] Preferably, integer x is 1 or 2, more preferably integer x is 1 .

[0073] R is preferably selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl, more preferably from the group consisting of H, methyl, ethyl, propyl, and isopropyl, more preferably from the group consisting of H, ethyl, and propyl, wherein more preferably R is H.

[0074] The base is preferably selected from the group consisting of alkali hydroxides, alkali alkoxides, and a mixture thereof. Preferably, the alkali hydroxide is selected from the group consisting of NaOH, KOH, and a mixture thereof, preferably wherein the alkali hydroxide is KOH. Also preferred is the alkali alkoxide being selected from the group consisting of sodium alkoxide, potassium alkoxide, and a mixture thereof, preferably from the group consisting of sodium ethoxide, potassium ethoxide, and a mixture thereof.

[0075] The at least one alcohol R-CH2-CH2-OH is preferably a bio-based alcohol, preferably obtainable or obtained from sugar-containing crops, preferably from one or more of sugar cane and corn.

[0076] The process in accordance with the present invention preferably further comprises recycling at least a part of the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprised in the mixture Me obtained according to (iv) to (ii) or (iii).

[0077] Preferably, the liquid mixture ME prepared according to (ii) further comprises a solvent. The solvent preferably has a boiling point of 110 °C or more, more preferably a boiling point of 140 °C or more, more preferably a boiling point of 160 °C or more, more preferably a boiling point of 180 °C or more, more preferably a boiling point of 190 °C or more. Also preferred is that the solvent has a solubility in water at 25 °C of from 0 to 0.5 weight-%, preferably a solubility in water at 25 °C of from 0 to 0.1 weight-%, more preferably a solubility in water at 25 °C of from 0 to 0.05 weight-%, more preferably a solubility in water at 25 °C of from 0 to 0.01 weight-%, based on 100 weight-% water. It is moreover preferred that the distribution coefficient of the catalyst in a system of the solvent and water is from 0 to 0.01 , preferably from 0 to 0.005, more preferably from 0 to 0.005, based on 1 kg catalyst. Preferably, the solvent is a mixture of at least two aromatic hydrocarbons with a boiling point of 180 °C or more.

[0078] In a preferred embodiment, the solvent does not include any one of benzene, toluene, xylene or mesitylene. Preferably, the solvent does not form an azeotrope with water. An azeotrope or a constant heating point mixture is a mixture of two or more components in fluidic states whose proportions cannot be altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Each azeotrope has a characteristic boiling point. It is not possible to separate the components by fractional distillation.

[0079] The solvent is preferably selected from the group consisting of biphenyl, diphenyl ether, 1-tert- butyl-3,5-dimethyl-benzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decaline, n-butylbutyrate, n-hexylhexyrate, n-octyloctyrate, texanole, di-n- butylether, di-iso-butylether, di-sec-butylether, and a mixture of two or more thereof, preferably from the group consisting of biphenyl, diphenyl ether, and a mixture thereof, wherein more preferably, the solvent is a mixture of biphenyl and diphenyl ether. Also preferred is the solvent being a mixture of biphenyl and diphenyl ether, preferably wherein the solvent is a mixture of biphenyl and diphenyl ether at a molar ratio of biphenyl relative to diphenyl ether in the range of from 1 :2 to 1 :6, preferably in the range of from 1 :2.5 to 1 :4.

[0080] Preferably, the alcohol conversion conditions according to (iii) comprise an amount of the solvent in the reaction mixture MG in the range of from 5 to 50 weight-%, more preferably in the range of from 5 to 30 weight-%, more preferably in the range of from 5 to 10 weight-%, based on the total weight of the reaction mixture MG.

[0081] Preferably, from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the liquid mixture ME prepared according to (ii) consist of the at least one alcohol R-CH2-CH2-OH, the base, the solvent and the catalyst.

[0082] The mixture Me obtained according to (iv) preferably comprises the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor and further comprises the solvent.

[0083] The process preferably further comprises recycling at least a part of the solvent comprised in the mixture Me obtained according to (iv) to (ii) or (iii).

[0084] Preferably, the liquid reaction mixture MG obtained according to (iii) further comprises at least one unreacted alcohol R-CH2-CH2-OH, the process further comprising separating at least a part of said unreacted alcohol R-CH2-CH2-OH from the liquid reaction mixture MG. More preferred is that separating at least a part of the unreacted alcohol R-CH2-CH2-OH from MG is carried out by distillation, extraction, flashing, or by employing a membrane. Also preferred is that at least a part of the at least one unreacted alcohol R-CH2-CH2-OH separated from MG is recycled to (ii) or (iii). The reaction space SR is preferably comprised in a reactor vessel, wherein the reactor vessel is preferably a complete-mixing reactor vessel.

[0085] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2, 3 and 4". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0086] 1 . An alcohol conversion process, comprising

[0087] (i) providing at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor;

[0088] (ii) preparing a liquid mixture ME comprising at least one alcohol R-CH2-CH2-OH with R being selected from the group consisting of H and Ci-C4-alkyl, the liquid mixture ME further comprising a base, the at least one of a catalyst, precursor thereof, reduced form of the catalyst or reduced form of the precursor provided according to (i), and a compound of formula (L)

[0089] (iii) subjecting the liquid mixture ME prepared according to (ii) to alcohol conversion conditions in a reaction space SR and obtaining in said reaction space a reaction mixture MG comprising at least one alcohol R-CH2-CH2-(CHR-CH2)x-OH, x being an integer in the range of from 1 to 4, wherein the reaction space comprises the reaction mixture MG and a gas phase, wherein the alcohol conversion conditions comprise a temperature of the reaction mixture ME in the range of from 100 to

[0090] 250 °C and a pressure in the reaction space SR in the range of from 1 x 105Pa to 4 x 106Pa;

[0091] (iv) separating the at least one alcohol R-CH2-CH2-(CHR-CH2)x-OH from the reaction mixture MG obtained according to (iii), obtaining the at least one alcohol R-CH2-CH2- (CHR-CH2)X-OH and a mixture Me comprising the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor; wherein the base is selected from the group consisting of ammonium hydroxide, alkali hydroxides, alkaline earth hydroxides, ammonium carbonate, ammonium hydrogen carbonate, alkali carbonates, alkali hydrogen carbonates, alkaline earth carbonates, alkaline hydrogen carbonates, alkali alkoxides, alkaline earth alkoxides, alkali metal amides, alkaline earth metal amides, secondary amino acids, and a mixture of two or more thereof; the catalyst comprises a compound of formula (A) wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0092] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0093] L3is selected from the RdCN, RdNC, N2, PF3, pyridine, and thiophene;

[0094] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (A) a quinolinyl unit; n is 0 or 1 ;

[0095] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, OH, OR, NRd2, NH3, NRd3, and Rd2NSO2Rd;

[0096] Ra, Rb, Rc, Rd, R5, R6and R7are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cio-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-C -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10- alkyl; and X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C -alkyl; wherein for the compound of formula (L), R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (L) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (L) a quinolinyl unit; n is 0 or 1 ;

[0097] X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl;

[0098] L1and L2, are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0099] Ra, Rb, Rc, Rd, R5, R6and R7, are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cw-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Ci-C -cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted Cs-Cw-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cw-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-Cw-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C - alkyl; wherein for the compound of formula (L), R1, R2, R3and R4, X, L1, L2, and n are preferably identical to R1, R2, R3and R4’ L1, L2, and n of the catalyst of formula (A); the precursor of the catalyst comprising a compound of formula (A) comprises a mixture comprising a compound comprising a metal M and at least one component selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, organic carbonyl compounds, Ci-Cw-alkyl, Ci-Cw-cycloalkyl, C2-Ci2-alkenyl, Cs-Cw-cycloalkenyl, C5-C20- aryl, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydrides, pyridines, halogenides, hydroxides, and thiophenes; and a compound of formula (H) wherein M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0100] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryl containing at least one heteroatom selected from nitrogen and sulfur, AsRaRb, SbRaRb, and a N-heterocyclic carbene represented by the structures:

[0101] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit, or R1and R2or R3and R4form together with the pyridyl unit of the catalyst of formula (A) a quinolinyl unit; n is 0 or 1 ;

[0102] Ra, Rb, Rc, Rd, R5, R6and R7are, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-Cio-alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; unsubstituted or substituted C5-C10- aryl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; and unsubstituted or substituted Cs-C -heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10- alkyl;

[0103] X is selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at the carbon atom on the pyridyl unit, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C -alkyl.

[0104] 2. The process of embodiment 1 , wherein the process is a continuous process.

[0105] 3. The process of embodiment 1 , wherein the process is a semi-batch process or a batch process.

[0106] 4. The process of any one of embodiments 1 to 3, wherein the alcohol conversion conditions according to (iii) comprise the presence of at least one inert gas in the reaction space SR, wherein the at least one inert gas is preferably selected from the group consisting of nitrogen, argon, and a mixture thereof.

[0107] 5. The process of any one of embodiments 1 to 4, wherein the alcohol conversion conditions according to (iii) comprise a pressure in the reaction space SR in the range of from 1 x 105to 3.5 x 106Pa, preferably in the range of from 1 x 105to 3.1 x 106Pa, more preferably in the range in the range of from 1 x 105to 2 x 106Pa, more preferably in the range in the range from 1 x 105to 1 .5 x 106Pa.

[0108] 6. The process of any one of embodiments 1 to 5, wherein the alcohol conversion conditions according to (iii) comprise a temperature of the reaction mixture MG in the range of from 100 to 200 °C, preferably in the range of from 120 to 180 °C, more preferably in the range of from 120 to 160 °C, more preferably in the range of from 130 to 160 °C.

[0109] 7. The process of any one of embodiments 1 to 6, wherein the alcohol conversion conditions according to (iii) comprise an amount of the base in the reaction mixture MG in the range of from 0.1 to 10 weight-%, preferably in the range of from 0.5 to 8 weight-%, more preferably in the range of from 1 to 5 weight-%, based on the total weight of the reaction mixture MG.

[0110] 8. The process of any one of embodiments 1 to 7, wherein the alcohol conversion conditions according to (iii) comprise an amount of the catalyst in the reaction mixture MG in the range of from 0.001 to 2 weight-%, preferably in the range of from 0.001 to 1 weight-%, more preferably in the range of from 0.001 to 0.5 weight-%, based on the total weight of the reaction mixture MG.

[0111] 9. The process of any one of embodiments 1 to 8, wherein according to (iii), the reaction space comprises the reaction mixture MG and a gas phase, wherein said gas phase comprises H2 and the alcohol conversion conditions further comprise maintaining the H2 partial pressure of the gas phase in the range of from 2 x 104to 3.1 x 106Pa, preferably in the range of from 2 x 104to 1 .1 x 106Pa, more preferably in the range of from 2 x 104to 6 x 105Pa, even more preferably in the range of from 5 x 104to 6 x 105Pa, even more preferably in the range of from 7 x 104to 6 x 105Pa.

[0112] 10. The process of embodiment 9, wherein the H2 partial pressure of the gas phase is maintained by introducing H2 into the gas phase.

[0113] 11 . The process of embodiment 9, wherein the H2 partial pressure of the gas phase is maintained by relaxation of the gas phase.

[0114] 12. The process of any one of embodiments 1 to 11 , wherein in the liquid mixture ME prepared according to (ii) and subjected to alcohol version conditions according to (iii), the molar ratio of the compound of formula (L) relative to the compound of formula (A) is in a range of from 0.01 :1 to 10:1 , preferably in the range of from 0.05:1 to 10:1 , more preferably in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.1 :1 to 10:1 , more preferably in the range of from 0.3:1 to 10:1 , more preferably in the range of from 0.5:1 to 10:1 , more preferably in the range of from 0.7:1 to 10:1 , more preferably in the range of from 0.8:1 to 10:1 , more preferably in the range of from 1 :1 to 10:1 more preferably in the range of from 1 .01 :1 to 10:1 , more preferably in the range of from 1 .02:1 to 8:1 , more preferably in the range from 1 .03:1 to 7:1 , more preferably in the range from 1.04:1 to 6:1 , and more preferably in the range from 1.05:1 to 5:1. The process of any one of embodiments 1 to 12, wherein 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, preferably wherein the additional compound is cyclohexyl-[[5- (dicyclohexylphosphanylmethyl)acridin-4-yl]methyl]phosphane or diisopropyl-[[5- (diisopropylphosphanylmethyl)acridin-4-yl]methyl]phosphane. The process of any one of embodiments 1 to 13, wherein preparing a liquid mixture ME in step (ii) comprises at least one alcohol R-CH2-CH2-OH, a base, a solvent, and the at least one of a catalyst, or precursor thereof provided according to (i). The process of any one of embodiments 1 to 14, wherein in formula (A) n is 0 if R1, R2, R3and R4are hydrogen. The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (B) wherein

[0115] M is selected from the group consisting of Ir, Mn, Os, Pd, Pt, Rh, and Ru;

[0116] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra;

[0117] L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0118] R1, R2, R3and R4either are hydrogen, or form together with the pyridyl unit of the catalyst of formula (A) an acridinyl unit; n is 0 or 1 , and if R1, R2, R3and R4are hydrogen, n is 0; Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-C -alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C C -alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-Cio-alkyl; Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; Cs-C -aryl; and C5-C10- heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0119] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4’ L1, L2and n are preferably identical to R1, R2, R3and R4, L1, L2and n of the catalyst of formula (B).

[0120] 17. The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (C) wherein

[0121] M is selected from the group consisting of Ir, Ru, and Mn;

[0122] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra;

[0123] L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0124] Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted C1-C10 alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10 alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10 alkyl; C3-C10 heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; C5-C10 aryl; and C5-C10 heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0125] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4, L1, L2, and n are preferably identical to R1, R2, R3and R4’ L1, L2, and n of the catalyst of formula (C).

[0126] 18. The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (D) wherein

[0127] M is selected from the group consisting of Ir, Ru, and Mn;

[0128] L1and L2are, independently of each other, PRaRb, NRaRb, SRa, SH, and S(=O)Ra;

[0129] L3is selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, pyridine, and thiophene;

[0130] Ra, Rb, Rcand Rdare, independently of each other, selected from the group consisting of H, unsubstituted or substituted Ci-C -alkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C C -alkyl; unsubstituted or substituted Ci-Cio-cycloalkyl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and Ci-C -alkyl; Cs-C -heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S; C5-C10 aryl; and C5-C10- heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S;

[0131] Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O)CF3, OSO2CF3, CN, CO, and OH; and wherein for the compound of formula (L), R1, R2, R3and R4, L1, L2and n are preferably identical to R1, R2, R3and R4’ L1, L2and n of the catalyst of formula (D).

[0132] 19. The process of any one of embodiments 1 to 18, wherein M is selected from the group consisting of Ir and Ru, preferably wherein M is Ru.

[0133] 20. The process of any one of embodiments 1 to 19, wherein M is Ru, and wherein the alcohol conversion conditions according to (iii) comprise a temperature of the reaction mixture MG in the range of from 100 to 170 °C, preferably in the range of from 120 to 1700C, more preferably in the range of from 120 to 160 °C, more preferably in the range of from 130 to 150 °C.

[0134] 21 . The process of any one of embodiments 1 to 20, wherein L3is CO.

[0135] 22. The process of any one of embodiments 1 to 21 , wherein L1and L2are each (PRaRb), and wherein Raand Rbare Ci-Cio-alkyl, preferably wherein Raand Rbare each isopropyl or tert-butyl.

[0136] 23. The process of any one of embodiments 1 to 21 , wherein L1and L2are each (PRaRb), and wherein Raand Rbare Ci-Cio-cycloalkyl, preferably wherein Raand Rbare each cyclohexyl. 24. The process of any one of embodiments 1 to 21 , wherein L1and L2are each (PRaRb), and wherein Raand Rbare Cs-C -aryl.

[0137] 25. The process of any one of embodiments 1 to 24, wherein Y is selected from the group consisting of F, Cl, Br and I, preferably wherein Y is selected from the group consisting of Cl or Br, more preferably wherein Y is Cl.

[0138] 26. The process of any one of embodiments 1 to 24, wherein Y is CO.

[0139] 27. The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (E) wherein Cy is cyclohexyl, and wherein the compound of formula (L) is preferably:

[0140] 28. The process of any one of embodiments 1 to 14, wherein the reduced form of the catalyst comprises a compound of formula (E’) wherein Cy is cyclohexyl, and wherein the compound of formula (L) is preferably: 29. The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (F) wherein iPr is isopropyl, and wherein the compound of formula (L) is preferably: 30. The process of any one of embodiments 1 to 14, wherein the reduced form of the catalyst comprises a compound of formula (F’) wherein iPr is isopropyl, and wherein the compound of formula (L) is preferably:

[0141] 31 . The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound of formula (G) wherein tBu is tert-butyl, and wherein the compound of formula (L) is preferably:

[0142] The process of any one of embodiments 1 to 14, wherein the reduced form of the catalyst comprises a compound of formula (G’) wherein tBu is tert-butyl, and wherein the compound of formula (L) is preferably:

[0143] The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound comprising a metal M selected from the group consisting of I rCh x H2O, [lr(COD)CI]2, [lr(COE)2CI]2, [lr(C2H4)2CI]2, [lr(COD)OH]2, [lr(COD)MeO]2, [lrCp*CI2], [IrCp Cl2], lr4(CO)i2, [lr(PPh3)2(CO)CI], [lr(acetylacetonate)3], and [lr(acetylacetonate)(COD)], wherein Cp is cylclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1 ,5-cyclooctadienyl, COE is cyclooctenyl, and methylallyl is 2-methylallyl.

[0144] The process of any one of embodiments 1 to 14, wherein the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprises a compound comprising a metal M selected from the group consisting of, [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2]y, [Ru(CO)2Cl2]y, where y is in each case in the range from 1 to 1000, [Ru(CO)3CI2]2, [Ru(COD)(allyl)J, RuCI3x H2O, [Ru(acetylacetonate)3], [Ru(DMSO)4Ch], [Ru(cyclopentadienyl)(CO)2CI], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(Cp)(CO)2CI], [Ru(Cp*)(CO)2H], [Ru(Cp*)(CO)2]2, [Ru(indenyl)(CO)2CI], [Ru(indenyl)(CO)2H], [Ru(indenyl)(CO)2]2, ruthenocene, [Ru(COD)CI2]2, [Ru(Cp*)(COD)CI], [RU3(CO)I2], [Ru(PPh3)4(H)2], [Ru(PPh3)3(CI)2], [Ru(PPh3)3(CO)(CI)2], [Ru(PPh3)3(CO)(CI)(H)J, [Ru(PPh3)3(CO)(H)2], and [Ru(cyclooctadienyl)(methylallyl)2], wherein Cp is cylclopentadienyl, Cp* is pentamethylcyclopentadienyl, COD is 1 ,5-cyclooctadienyl, and methylallyl is 2-methylallyl.

[0145] The process of any one of embodiments 1 to 34, wherein the reduced form of the precursor comprises a compound of formula (P-l) or (P-l I): wherein R1, R2, R3and R4either are hydrogen, or form together with the N-containing ring a tetrahydroquinoline unit, a decahydroquinoline unit, a tetrahydroacridine unit, or a tetradecahydroacridine unit; and wherein L1and L2are, independently of each other, as defined above; wherein R1, R2, R3and R4are hydrogen; and wherein L1and L2are, independently of each other, as defined above.

[0146] The process of any one of embodiments 1 to 34, wherein the reduced form of the precursor comprises a compound of formula (P-l): wherein R1, R2, R3and R4either are hydrogen, or form together with the N-containing ring a tetrahydroacridine unit, or a tetradecahydroacridine unit. The process of any one of embodiments 1 to 34, wherein the reduced form of the precursor comprises a compound of formula (P-ll): wherein R1, R2, R3and R4are hydrogen; and wherein L1and L2are, independently of each other, as defined above. The process of any one of embodiments 1 to 37, wherein integer x is 1 or 2, preferably wherein integer x is 1. The process of 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, wherein more preferably R is H. The process of any one of embodiments 1 to 39, wherein the base is selected from the group consisting of alkali hydroxides, alkali alkoxides, and a mixture thereof. The process of embodiment 40, wherein the alkali hydroxide is selected from the group consisting of NaOH, KOH, and a mixture thereof, preferably wherein the alkali hydroxide is KOH. The process of embodiment 40, wherein the alkali alkoxide is selected from the group consisting of sodium alkoxide, potassium alkoxide, and a mixture thereof, preferably from the group consisting of sodium ethoxide, potassium ethoxide, and a mixture thereof. The process of any one of embodiments 1 to 42, wherein the at least one alcohol R-CH2- CH2-OH is a bio-based alcohol, preferably obtainable or obtained from sugar-containing crops, preferably from one or more of sugar cane and corn. The process of any one of embodiments 1 to 43, further comprising recycling at least a part of the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor comprised in the mixture Me obtained according to (iv) to (ii) or (iii). The process of any one of embodiments 1 to 44, wherein the liquid mixture ME prepared according to (ii) further comprises a solvent. The process of embodiment 45, wherein the solvent has a boiling point of 110 °C or more, preferably a boiling point of 140 °C or more, more preferably a boiling point of 160 °C or more, more preferably a boiling point of 180 °C or more, more preferably a boiling point of 190 °C or more.

[0147] 47. The process of embodiment 45 or 46, wherein the solvent has a solubility in water at 25 °C of from 0 to 0.5 weight-%, preferably a solubility in water at 25 °C of from 0 to 0.1 weight-%, more preferably a solubility in water at 25 °C of from 0 to 0.05 weight-%, more preferably a solubility in water at 25 °C of from 0 to 0.01 weight-%, based on 100 weight- % water.

[0148] 48. The process of any one of embodiments 45 to 47, wherein the distribution coefficient of the catalyst in a system of the solvent and water is from 0 to 0.01 , preferably from 0 to 0.005, more preferably from 0 to 0.005, based on 1 kg catalyst.

[0149] 49. The process of any one of embodiments 45 to 48, wherein the solvent is a mixture of at least two aromatic hydrocarbons with a boiling point of 180 °C or more.

[0150] 50. The process of 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-dimethyl-benzene, ethylbenzene, cyclododecane, cyclononane, cyclooctane, cycloheptane, decaline, n- butylbutyrate, n-hexylhexyrate, n-octyloctyrate, texanole, di-n-butylether, di-iso-butylether, di-sec-butylether, and a mixture of two or more thereof, preferably from the group consisting of biphenyl, diphenyl ether, and a mixture thereof, wherein more preferably, the solvent is a mixture of biphenyl and diphenyl ether.

[0151] 51 . The process of any one of embodiments 45 to 50, wherein the solvent is a mixture of biphenyl and diphenyl ether, preferably wherein the solvent is a mixture of biphenyl and diphenyl ether at a molar ratio of biphenyl relative to diphenyl ether in the range of from 1 :2 to 1 :6, preferably in the range of from 1 :2.5 to 1 :4.

[0152] 52. The process of any one of embodiments 45 to 51 , wherein the solvent does not form an azeotrope with water.

[0153] 53. The process of any one of embodiments 45 to 52, wherein the solvent does not include any one of benzene, toluene, xylene or mesitylene.

[0154] 54. The process of any one of embodiments 45 to 53, wherein the alcohol conversion conditions according to (iii) comprise an amount of the solvent in the reaction mixture MG in the range of from 5 to 50 weight-%, preferably in the range of from 5 to 30 weight-%, more preferably in the range of from 5 to 10 weight-%, based on the total weight of the reaction mixture MG.

[0155] 55. The process of any one of embodiments 45 to 54, wherein from 90 to 100 weight-%, preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, more preferably from 99 to 100 weight-% of the liquid mixture ME prepared according to (ii) consist of the at least one alcohol R-CH2-CH2-OH, the base, the solvent and the catalyst.

[0156] 56. The process of any one of embodiments 45 to 55, wherein the mixture Me obtained according to (iv) comprises the at least one of a catalyst, a precursor thereof, a reduced form of the catalyst, or a reduced form of the precursor and further comprises the solvent.

[0157] 57. The process of embodiment 56, further comprising recycling at least a part of the solvent comprised in the mixture Me obtained according to (iv) to (ii) or (iii).

[0158] 58. The process of any one of embodiments 1 to 57, wherein the liquid reaction mixture MG obtained according to (iii) further comprises at least one unreacted alcohol R-CH2-CH2- OH, the process further comprising separating at least a part of said unreacted alcohol R- CH2-CH2-OH from the liquid reaction mixture MG.

[0159] 59. The process of embodiment 58, wherein separating at least a part of the unreacted alcohol R-CH2-CH2-OH from MG is carried out by distillation, extraction, flashing, or by employing a membrane.

[0160] 60. The process of embodiment 58 or 59, wherein at least a part of the at least one unreacted alcohol R-CH2-CH2-OH separated from MG is recycled to (ii) or (iii).

[0161] 61 . The process of any one of embodiments 1 to 60, wherein the reaction space SR is comprised in a reactor vessel, wherein the reactor vessel is preferably a complete-mixing reactor vessel.

[0162] The present invention is further illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.

[0163] Examples

[0164] The determination of the distribution coefficient of the solvent in water comprises the following steps:

[0165] 1 . combining the two components, e.g. feed and solvent, in a predefined solvent ratio;

[0166] 2. turbulent mixing of the combined components over a longer period of time (> 10 min) at a defined extraction temperature;

[0167] 3. allowing for phase separation;

[0168] 4. taking samples of each phase at the extraction temperature;

[0169] 5. centrifuging the samples and withdrawing clear samples at the extraction temperature;

[0170] 6. analyzing the samples; and

[0171] 7. comparing the results of extract- and raffinate - calculation of the partition equilibrium / partition coefficient at the selected temperature. Comparative Example 1

[0172] 70.09 g Ethanol, 3.80 g (3 mol%) potassium ethoxide and 172.6 mg (Cy-Acr-PNP)RuHCI(CO) (0.015 mol%) were weighed into a screw thread bottle and stirred overnight at room temperature. The reactant suspension was poured into an autoclave using a syringe in a countercurrent flow of the starting material, and the screw-threaded bottle was rinsed with ethanol. Then, 7.71 g diphenyl and diphenyl ether were added as solvent in a molar ratio of 1 :3.

[0173] The reaction mixture was heated to 150 °C for about 15 min with the outlet valve closed at 85% heating power with 750 rpm stirring. The pressure was maintained at about 10 bar during the reaction. After reaching the reaction temperature of 150 °C, a "zero sample" was taken. Filtered through a 2 pm syringe filter, the sample was spiked with the internal standard 1 ,4-dioxane and analyzed by GC. Further samples were taken after 1 , 2, 3, 6 and 24 h and processed / analyzed analogously.

[0174] Example 1

[0175] The procedure was carried out as disclosed in Comparative Example 1 , wherein 135.2 mg (0.015 mol%) dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridin-4-yl]methyl]phosphane was additionally weighed into the screw thread vial.

[0176] Example 2

[0177] The procedure was the same as in Comparative Example 1 , but instead of 172.6 mg (Cy-Acr- PNP)RuHCI(CO), 90.3 mg (0.015 mol%) Ru(acac)s (ruthenium(lll) acetylacetonate), and additionally 273.1 mg Cy-Acr-PNP (0.03 mol%) were weighed into the screw-threaded bottle.

[0178] Example 3

[0179] The procedure was the same as in Comparative Example 1 , but instead of 172.6 mg (Cy-Acr- PNP)RuHCI(CO), 6 g (0.015 mol%) Ru(acac)s (ruthenium(lll) acetylacetonate), and additionally 676 mg Cy-Acr-PNP (0.075 mol%) were weighed into the screw-threaded bottle.

[0180] In this series of experiments, it was found that an excess of ligand leads to significantly faster reactions and better conversions. This was demonstrated with an isolated catalyst (Comparative Example 1 vs. Example 1) and with an in situ-formed catalyst (Comparative Example 1 vs. Example 2 / Example 3), as illustrated by Figure 1. The excess ligand stabilizes the active catalyst species, preventing catalyst decomposition.

[0181] Cited literature:

[0182] M. Guerbet, C. R. Hebd. Seances Acad. Sci. 1899, 128, p. 511-513 - Y.Xie et aL, “Highly efficient Process for Production of Biofuel from ethanol Catalyzed by

[0183] Ruthenium Pincer Complexes”, Journal of the American Society, vol. 138, no. 29, 2016- 07-18, pages 9077 to 9080

[0184] - WO 2012 / 119928 A1

[0185] 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, pages 8661 to 8664

[0186] - WO 2013 / 156399 A1

Claims

DEPCT691. An alcohol transformation process which includes (i) the provision of at least one type of catalyst, a reactant of such substance, a reduced form of the catalyst or a reduced form of the reactant; (ii) the preparation of a liquid ME mixture which contains at least one type of R-CH2-CH2-OH alcohol with R chosen from the H-containing and alkyl C1-C4 groups, in which the liquid ME mixture is further incorporated with a base, at least one type of catalyst, a reactant of such substance,(i) the reduced form of the catalyst or the reduced form of the reactant provided according to (i) and the compound with the formula (L) (chemical formula) (L); (iii) the introduction of the liquid ME mixture prepared according to (ii) to the alcohol transformation state in the SR reaction area and the obtaining of the reaction mixture MG which contains at least one alcohol R-CH2-CH2-(CHR-CH2)x-OH in such reaction area where x is an integer in the range from 1 to 4 where the reaction area contains the reaction mixture MG. and the gas phase in which the alcohol transformation conditions consist of a temperature of the ME reaction mixture in the range of 100 to 250 °C and a pressure in the SR reaction zone in the range of 1x10⁵Pa to 4x10⁶Pa; (iv) the separation of at least one R-CH2-CH2-(CHR-CH2)x-OH alcohol from the MG reaction mixture obtained according to (iii), which yields at least one R-CH2-CH2-(CHR-CH2)x-OH alcohol and an MC mixture which contains at least one type of catalyst, a reactant of such substance,The reduced form of the catalyst or the reduced form of the substrate in which a base is chosen from a group consisting of ammonium hydroxide, alkali hydroxide, alkaline earth hydroxide, ammonium carbonate, ammonium hydrogen carbonate, alkali carbonate, alkali hydrogen carbonate, alkaline earth carbonate, alkaline hydrogen carbonate, alkali alkoxide, alkaline earth alkoxide, alkali metal amides, alkaline earth metal amides, secondary amino acids, and a mixture of two or more of such substances. Furthermore; the catalyst is composed of a compound with the formula (A)(chemical formula)(A) in which M is chosen from a group consisting of Ir, Mn, Os, Pd, Pt, Rh and Ru; L1 and L2 independently are PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryls with at least one heteroatom chosen from nitrogen and sulfur, AsRaR, SbRaRb and N-heterocyclic carbine represented by the structures:(chemical formula) or (chemical formula); L3 is chosen from a group consisting of CO, PRaRbRc, AsRaRbRc, SbRaRbRc, SRaRb, RdCN, RdNC, N2, PF3, pyridine and thiophene; R1, R2,R3 and R4 either form hydrogen or, together with the pyridyl unit of the catalyst with formula (A), produce acridinyl units; or R1 and R2 or R3 and R4, together with the pyridyl unit of the catalyst with formula (A), produce quinolinyl units; n is 0 or 1; Y is selected from the group consisting of H, F, Cl, Br, I, OC(=O), CF3, OSO2 CF3, CN, CO, OH, OR, NRd2, NH3, NRd3 and Rd2NSO2 Rd; Ra, Rb, Rc, Rd, R5, R6 and R7 are independently selected from the group consisting of H, alkyl C1-C10, either unsubstituted or substituted where the substituents are selected from the group consisting of With F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; unsubstituted or substituted cycloalkyl C1-C10 where the substituent is chosen from the group consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; unsubstituted or substituted heterocyclyl C3-C10 which includes at least one heteroatom chosen from the group consisting of N, O and S where the substituent is chosen from the group consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; unsubstituted or substituted aryl C5-C10 where the substituent is chosen from the group consisting of F, Cl, Br, OH, CN, NH2,NH2 and alkyl C1-C10 and heteroaryl C5-C10, either unsubstituted or substituted, which include at least one heteroatom selected from the group consisting of N, O, and S, where substituents selected from the group consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10 and X are selected from the group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four, and five substituents positioned at any carbon atom on the quinolinyl unit, or groups A substituent is assigned a position at the carbon atom on the pyridyl unit, where the substituent is chosen from a group consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10, where for compounds with the formula (L) R1, R2, R3 and R4 either form hydrogen or, together with the pyridyl unit of the catalyst with the formula (L), form an acridinyl unit, or R1 and R2 or R3 and R4, together with the pyridyl unit of the catalyst with the formula (L), form a quinolinyl unit; n is 0 or 1; X is chosen from a group consisting of the first, second, third, fourth, fifth substituents.Six and seven substituents are assigned to any carbon atom on the acridinyl unit, or the first, second, third, fourth, and fifth substituents are assigned to any carbon atom on the quinolinyl unit, or one substituent is assigned to a carbon atom on the pyridyl unit, where the substituents are chosen from groups consisting of F, Cl, Br, OH, CN, NH2, and alkyl C1-C10; L1 and L2 independently as PRaRb, NRaR, SRa, SH, S(=O)Ra, heteroaryls with at least one heteroatom chosen from nitrogen and sulfur, AsRaRb, SbRaRb, and N-heterocyclic carbs. The elements represented by the structure: (chemical formula) or (chemical formula) Ra, Rb, Rc, Rd, R5, R6, and R7 are independently selected from a group consisting of H, alkyl C1-C10 unsubstituted or substituted substituents chosen from a group consisting of F, Cl, Br, OH, CN, NH2, and alkyl C1-C10; cycloalkyl C1-C10 unsubstituted or substituted substituents chosen from a group consisting of F, Cl, Br, OH, CN, NH2, and alkyl C1-C10; heterocyclyl C3-C10 unsubstituted or substituted which include at least one heteroatom selected from a group consisting of N,O and S where substituents are chosen from groups consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; unsubstituted or substituted aryl C5-C10 where substituents are chosen from groups consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; and unsubstituted or substituted heteroaryl C5-C10 which include at least one heteroatom chosen from groups consisting of N, O and S where substituents are chosen from groups consisting of F, Cl, Br, OH, CN, NH2 and alkyl C1-C10, where for compounds with the formula (L) R1, R2, R3 and R4, X, L1, L 2 and n are popularly considered to be the same as R1, R2, R3 and R4, L1, L2 and n of the catalyst with formula (A); the catalytic substrate which is composed of a compound with formula (A) is composed of a mixture which is composed of a compound which is composed of metal M and at least one component selected from the group consisting of CO, PRaRbRc, SRaRb, RaCN, RaNC, N2, PF3, organic carbonyl compounds, alkyl C1-C10, cycloalkyl C1-C12, alkenyl C2-C12, cycloalkenyl C3-C15, aryl C5-C20, CN, CO, OH, OC(=O)CF3, OSO2CF3, hydride, pyridine, halogenide,Hydroxides and thiophenes and compounds with the formula (H)(chemical formula)(H) in which M is chosen from groups consisting of Ir, Mn, Os, Pd, Pt, Rh and Ru; L1 and L2 independently are PRaRb, NRaRb, SRa, SH, S(=O)Ra, heteroaryls with at least one heteroatom chosen from nitrogen and sulfur, AsRaRb, SbRaRb and N-heterocyclic carbine represented by the structure:(chemical formula) or (chemical formula); R1, R2, R3 and R4 are either hydrogen or together with the pyridyl unit of a catalyst with a The catalyst (A) gives rise to acridinyl units or R1 and R2 or R3 and R4 together with the pyridyl unit of the catalyst with formula (A) gives rise to quinolinyl units; n is 0 or 1; Ra, Rb, Rc, Rd, R5, R6 and R7 independently selected from groups containing H, alkyl C1-C10 unsubstituted or substituted where substituents are selected from groups containing F, Cl, Br, OH, CN, NH2 and alkyl C1-C10; cycloalkyl C1-C10 unsubstituted or substituted where substituents are selected from groups containing F, Cl, Br, OH, CN,NH2 and alkyl C1-C10; unsubstituted or substituted heterocyclic C3-C10 containing at least one heteroatom selected from the N, O, and S group where the substituent is chosen from the group containing F, Cl, Br, OH, CN, NH2, and alkyl C1-C10; unsubstituted or substituted aryl C5-C10 where the substituent is chosen from the group containing F, Cl, Br, OH, CN, NH2, and alkyl C1-C10; and unsubstituted or substituted heteroaryl C5-C10 containing at least one heteroatom selected from the group. A substituent group composed of N, O, and S, where a selected substituent from a group composed of F, Cl, Br, OH, CN, NH2, and alkyl C1-C10X is chosen from a group consisting of one, two, three, four, five, six, and seven substituents positioned at any carbon atom on the acridinyl unit, or one, two, three, four, and five substituents positioned at any carbon atom on the quinolinyl unit, or one substituent positioned at a carbon atom on the pyridyl unit, where a selected substituent from a group composed of F, Cl, Br, OH, CN,NH2 and alkyl C1-C102. The process according to claim 1 in which according to (iii) the reaction area consists of a mixture of the reaction MG and a gas phase in which the gas phase consists of H2 and the alcohol transformation conditions consist of the maintenance of the partial pressure of the gas phase H2 in the range of 2x10⁴ to 3.1x10⁶Pa.

3. The process according to claim 2 in which the partial pressure of the gas phase H2 is maintained by the introduction of H2 into the gas phase or in which the partial pressure of the gas phase H2 is maintained by the relaxation of the gas phase.

4. The process according to claim 2 One of the three claims in which the liquid ME mixture prepared according to (ii) and brought to the alcohol transformation conditions according to (iii) has a molar ratio of the compound formulated (L) relative to the compound formulated (A) ranging from 0.01:1 to 10:1, preferably ranging from 0.05:1 to 10:1, more commonly ranging from 0.1:1 to 10:

15. One of the four claims in which the compound formulated (L) is selected from a group consisting of dicyclohexyl-[[5-(dicyclohexyl phosphanyl methyl)acridin-4-yl]methyl]phosphan,Diisopropyl-[[5-(diisopropylphosphanylmethyl)acridin-4-il]methyl]phosphan, dicyclohexyl-[[5-(dicyclohexylphosphanylmethyl)pyridin-4-il]methyl]phosphan and diisopropyl-[[5-(diisopropylphosphanylmethyl)pyridin-4-il]methyl]phosphan, where additional compounds are specified. M is cyclohexyl-[[5-(dicyclohexylphosphanylmethyl)acridin-4-il]methyl]phosphan or diisopropyl-[[5-(diisopropylphosphanylmethyl)acridin-4-il]methyl]phosphan.

6. Any of the processes under claims 1 to 5 where M is Ru and where the alcohol transformation conditions under (ii i) The reaction mixture temperature of the MG reaction ranges from 100 to 170 degrees Celsius.

7. Any one of the processes under claims 1 to 6 in which at least one type of catalyst, such reactant, reduced form of the catalyst or reduced form of the reactant is composed of a compound with the formula (E) (chemical formula) (E) in which Cy is cyclohexyl and in which the compound with the preferred formula (L) is: (chemical formula).

8. Any one of the processes under claims 1 to 6 in which at least one type of catalyst, such reactant,9. Any process under claims 1 to 6 in which at least one type of catalyst, such reactant, reduced form of catalyst or reduced form of reactant is composed of a compound with the formula (F) (chemical formula) (F) in which iPr is isopropyl and in which the compound with the formula (L) is commonly: (chemical formula) 10. Any one of the processes under claims 1 through 9 where the integer x is 1 and / or where R is chosen from a group consisting of H, ethyl, and propyl.

11. Any one of the processes under claims 1 through 10 where the reduced form of the reactant is composed of a compound with the formula (PI) or (P-II): (chemical formula) (PI) where one of R1, R2, R3, and R4 is hydrogen or, together with an N-containing ring, forms the tetrahydroquinoline unit, the decahydroquinoline unit,12. Any process under claims 1 to 11 which includes the recycling of at least part of at least one type of catalyst, a reactant of such substance, a reduced form of the catalyst or a form of 13. Any of the processes under claims 1 to 12 in which the liquid ME mixture prepared under (ii) is further incorporated with a solvent and in which the solvent has a boiling point of 110 °C or more.

14. Any of the processes under claims 1 to 13 in which the MC mixture prepared under (iv) contains at least one type of catalyst, a reactant of such catalyst,Reduced form of the catalyst or reduced form of the reactant and further incorporated with a solvent and further incorporated by recycling at least part of the solvent incorporated into the MC mixture obtained according to (iv) to (ii) or (iii);15. Any of the processes under claims 1 to 14 in which the liquid reaction mixture of MG obtained according to (iii) is further incorporated with at least one non-reactive alcohol R-CH2-CH2-OH in which the process is further incorporated by separating at least part of such non-reactive alcohol R-CH2-CH2-OH from the liquid reaction mixture of MG in which at least part of the non-reactive alcohol R-CH2-CH2-OH separated from MG is recycled to (ii) or (iii);

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