JPH01172351A - Homologizing method - Google Patents

Abstract

PURPOSE: To homologize alkanole and synthetic gas at a high selectivity and velocity under mild conditions by bringing them into contact with rhodium catalyst containing bi(diorganophosphine) alkane ligand.

CONSTITUTION: In the presence of catalyst containing Rh atom, Ru atom, I atom, and bis (diorganophosphine) alkane ligand of formula I (X is alkyl, alkenyl or cyclic bivalent bridge connecting two Ps; R is H, 1-20C alkyl, aryl, aralkyl, or alkallyl in which aryl has 6-20C and alkyl has 1-10C) at the molar ratio Rh:Ru=1:10-10:1, Rh:I=1:500-500:1, Rh : ligand = 1:100-100:1, alkanole of formula II (R' is 1-20C alkyl, 2-20C alkenyl or aralkyl) is catalytic allowed to react with synthetic gas (H₂:CO molar ratio is 1:10-10:1) at 50-250°C and 7-700 kg/cm²G.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION When reacting synthesis gas alone or in admixture with other organic compounds, there are several criteria required for the catalyst system. The system should be as stable as possible under the reaction conditions to sustain the reaction, should have high selectivity for the desired product, and should have a high production rate of the desired product.

Catalyst stability relates to how long a catalyst system remains active or functional before it either breaks down or loses its catalytic effectiveness. The most desirable catalysts are those that do not lose their catalytic activity and can be cycled repeatedly.

Selectivity relates to the ability of a catalyst to produce a desired product in higher or greater amounts in preference to other products. Selectivity is determined by gas chromatography analysis of the recovered reaction product, and is expressed as area/cent or mole percent of the viable alkanol produced during this application, based on the total amount of the viable alkanol produced. do.

The production rate or rate is the rate at which the alkanol is converted into realizable alkanol per unit time.
It is expressed in mo/I//liter/hour.

Feasible alkanol is the amount of the next higher alkanol congener plus the amount of by-products that produce that higher alkanol congener when recycled. That is, for example, when methanol charged to a reactor is homogenized,
It is common to recover a reaction product mixture containing ethanol, acetaldehyde, ethyl acetate, dimethyl acetal, diethyl ether, methyl acetate, vinegar Wl, Q methyl ether, methyl ethyl ether, unreacted methanol, and methyl ester. . Feasible ethanol is ethanol, acetaldehyde present, ethyl acetate, dimethyl acetal, diethyl ether,
Based on the amount of ethanol equivalent that can be obtained from methyl ethyl ether.

The conversion rate is the amount by which the initially charged alkanol is homologated during the reaction to form a viable alkanol.

The desired goal is high values for all of the above, and efforts continue to be made to find new processes and systems to reach this goal without significantly adversely affecting the overall system. It is. The prior art has evolved with this in mind, and while there are many effective processes and systems, improvements are always desirable.

The present invention is based on the unexpected and unexpected discovery of a process using a rhodium-based homologation catalyst to selectively produce ethanol. The process uses a catalyst system containing rhodium atoms, ruthenium atoms, iodine atoms and a bis(diorganophosphino)alkane ligand of the following general formula: %Formula %. This catalyst system converts the methanol homologation reaction to z o o o pstg (70119/z”
c) J: pressures between 4000 and 3000 using an ethanol rate and a cobalt catalyst that allows it to be carried out at operating pressures that can be as low as
The possibility of using lower reaction pressures in the process of the present invention makes it possible to achieve selectivities close to the best reported in the literature in the prior art. , a significant and major breakthrough in methanol homologation technology. Catalyst systems are typically soluble and homogeneous, but if desired, the catalyst can be deposited on an inert support to make it a heterogeneous system. Both of these techniques are known to those skilled in the art.

This unexpected homologation reaction method requires the use of defined ligands. Without the presence of the ligand, the achievable ethanol rates and selectivities are negligible. As shown by Comparative Experiment A, one reaction could not be continued for any significant period of time and the selectivity to ethanol that could be achieved was not an issue.

To the best of the applicant's knowledge, the combination of the ligand and the metal atoms described above is the first reported rhodium-based homologation catalyst. Applicants have shown that this catalyst readily produces ethanol from methanol and syngas with high selectivity, conversion and rate. The use of rhodium-based catalysts to homologize methanol to ethanol is not suggested by the published prior art and the expected acids cannot be predicted. The prior art teaches that the reaction of methanol with synthesis gas over a rhodium-based catalyst results in a carbonylation reaction resulting in the selective production of esters and acids rather than alkanols as the main products.

The method of the invention provides temperatures below about 150°C and 2,
500 pmlg (18019/cy++”G)
Lower pressure, e.g. $0 (lopsif (7ah9
/cm” G) to achieve the values achieved when homogenizing methanol to ethanol/cm, the operating conditions are 180°C to 200°C.
°C and pressure a, ooo~4000pmig (280~
Known standard Co-R requiring 420 to 9/m”G)
Close to the best value reported for the u-I catalyst. The temperature and pressure reductions made possible by the rhodium-based catalyzed process of the present invention are perhaps the first major improvement in homologation technology since the introduction of the iodine promoter about 30 years ago.

In the process of the invention, alkanol R'OH is reacted with synthesis gas using a catalyst system containing rhodium atoms, ruthenium atoms, iodine atoms and the ligand R2PXPR2.

The process produces, under mild operating conditions, the next higher alkanol congener with a higher feasible ethanol selectivity and higher rate than obtained by other catalysts.

In the alkanol formula, R' is a monovalent hydrocarbyl group, preferably an alkyl group. R1 is 1 to carbon atom
about 20, preferably 1 to about 10, most preferably 1 to 4
an alkyl group having from 2 to about 20, preferably 2 to about 10, most preferably 2 to 4 carbon atoms; or an aralkyl group containing from 1 to 4 carbon atoms.

The R/ group can be linear or branched and can be unsubstituted or substituted with groups that do not adversely affect the homologation reaction; You can have more than one.

Among the preferred alcohols are methanol, ethanol, propatool, butanol, and most preferred are methanol and ethanol.

As a rhodium atom component, a single rhodium compound or two
or mixtures of more rhodium compounds can be used. The rhodium component of the catalyst system can be supplied from any number of sources, many of which are known to those skilled in the art. From this, any of the known rhodium compounds can be used, so that for their understanding it is not necessary to specifically mention every suitable type and every particular compound.

The rhodium component of the catalyst system of the present invention may be provided by introducing a compound of rhodium into the reaction zone or by introducing rhodium into the reaction zone. Among the materials that can be charged to the reaction zone to form the rhodium component of the catalyst system of the present invention is cI
Rhodium genus, rhodium salts and oxides, organorhodium compounds, rhodium coordination compounds, etc. Specific examples of materials that can serve as the rhodium component of the catalyst system of the present invention may be taken from the list of suitable materials below, but the examples below are only a partial and non-limiting example.

RhCl.

hBri RhIs-5H20 RhC1s・3H! 0 RhBr3・5H20 Rhz(CO)4c12 Rh2(Co)4Br2 Rhz(Co)4It Rh 2 (CO) @ Rh((CsHs)sr h(Co)IRh((Cs
Hs)sP)z (Co) CIRh Gold/Rh (Not)x Rh(Co)2 aesc Rh(SnC1s)((CeHs)sP)zRhCI
(Co) (C4Hs)sAs: 17, Rh I (Co
) ((C4H6)3Sb:l.

((n-CsHs)aN)I:Rh(Co)zXt),
Here, X=Ct-1Br-1I- ((n-CaHe)i As)(Rh(Co)鵞Xn)
, where X=Cl-1I- ((n-CiHs)4P)(Rh(CO)I4)Rh(
(C@Hs)sP)g(Co)BrRh((n-C4H
+)sP)z(Co)BrRh((n-CaHe)sP
)z(Co)rRhBr((C@Hs)sP:l5 Rh I C(C@Hs)mP)s RhC1((C@Hs)sP)RhCI((C@Hs)sP'':1sHzC(CsHs
)sP)sRh (Co)HRh mushroom 03 (Rh (CsH4)*C1”h K4RhzC11(SnC12)4 to 4Rh2BFg(SnBr3)4 to 4 (RhzIz)4 Rh(RtPXPRz)1112 (where z is any suitable Among the preferred rhodium compounds are those that react with bis(diorganophosphino)alkane ligands to form rhodium-phosphine complexes.
The components can be formed when initially charged to the reactor, or they can be pre-formed and charged to the reactor.

In addition, complexes containing rhodium, ruthenium, and bis(diorganophosphino)alkanes may be formed as the components are charged to the reactor, or these complexes may be preformed and then added to the reactor. can be loaded. Additionally, any of the above complexes may be formed during the course of the reaction. Furthermore, any one of the known rhodium complexes or rhodium-ruthenium compounds or complexes can be used.

As the ruthenium atom component, a single ruthenium compound or a mixture of two or more ruthenium compounds can be used. Ruthenium compounds are well known to those skilled in the art. Examples of such ruthenium compounds include ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, ruthenium acetate, ruthenium acetylacetonate,
Ruthenium fluoropionate, ruthenium octanoate, ruthenium dioxide, ruthenium tetroxide, ruthenium carbonyl, triruthenium dobucarboel, and the like can be mentioned. Convenient sources of ruthenium are ruthenium trichloride and triruthenium dodecacarbonyl.

Also useful are those compounds containing both rhodium and ruthenium atoms in the same molecule. They can be used alone or in combination with the rhodium and ruthenium compounds mentioned above.

The halide component of the catalyst can be iodine, bromine or chlorine, or a halogen compound containing two or more of these, or the halogen element itself, or any mixture of compounds and/or elements. can. Their nature is well known to those skilled in the art. A preferred halogen compound is iodine or an inorganic or organic compound containing an iodine atom.

As mentioned above, the average number of suitable halogen compounds is well known to those skilled in the art and it is not necessary to give an exhaustive list for their understanding. As examples of suitable halogen compounds, the following may be mentioned: barium iodide,
Hydroiodic acid, cobalt iodide, potassium iodide, lithium iodide, sodium iodide, calcium iodide, ammonium iodide, methyl iodide, ethyl iodide, propyl iodide, 2-ethylhexyl iodide, eyelid n-decyl, acetyl iodide, propionyl iodide; R#/4
Organic ammonium iosito of the formula N I and B ///
4p Organic phosphonium iositoide of the formula 1 (wherein R″′
is saturated or unsaturated, substituted or unsubstituted alkyl having 1 to about 10 ring carbon atoms or unsubstituted or substituted aryl having 6 to 10 ring carbon atoms), such as trimethylammonium Iosite, tetraethylammonium iodide, tetra-2-ethylhexyl ammonium iosite, tetraphenylammonium iosite, tetramethylphosphonium iosite, tetramethylphosphonium iosite, tetra-2-ethylhexylphosphonium iosite, tetraprobyl phosphor Yum Iodide 1
Tetra-2-ethylhexylphosphonium iosito, methyltriphenylphosphonium iosito, etc.; methylammonium iosito, ) lyl-tolyl-ammonium carbonate, decylammonium iosito, ethylphosphonium iosito, triphenylphosphonium iosito ,
tricyclohexylphosphonium iosito, tri-p-
) lylphosphoniumzidide, etc.; also useful are bromine and its corresponding compounds, chlorine and its corresponding compounds. Any source of halogen atoms can be used as long as it does not adversely affect the reaction. A preferred iodine source is methyl iodide.

Bis(diorganophosphino)alkane ligands are represented by the following general formula: IhPXPR2, where X is a linear or branched alkyl or alkenyl or 1 to 1 carbon atom between two P atoms. 10, preferably 2-
A cyclic pridging divalent group having about 6, most preferably 3, unsubstituted K or any group that does not significantly reduce the catalytic activity of the reaction (e.g., phenyl, nitro, halogen,
alkyl, alkaryl, aralkyl) and R is (1) a hydrogen atom, provided that no more than one hydrogen atom is attached to the P atom, or (ii) one carbon atom. ~101, preferably 2 to about 5 alkyl groups (can be #-shaped or branched)
, or (iii) the aryl moiety (phenyl, naphthyl) K has from 6 to 1 carbon atoms and the alkyl moiety has from 1 to about 10 carbon atoms. Preferably it is an aryl, aralkyl or alkaryl group having 1 to 3).

The R radicals can be the same or different. A preferred ligand is bis(diphenylphosphino)propane.

As examples of suitable bis(:)organophosphino)alkane ligands, mention may be made of: bis(diphenylphosphino)methane, 1s-bis(diphenylphosphino)propane, 110-bis(diphenylphosphino). Tecan, 13-bis(diethylphosphino)propane, t3-bis(ethylphenylphosphino)furone, 1,4-bis(diphenylphosphino)butane, t3-
Bis(dipropylphosphino) furonone, 1-diethylphosphino-5-dipropylphosphinopropane, t3-bis(diphenylphosphino)-2-methylpropane, t3-bis(diphenylphosphino)-1-butylpropane , 1-riamylphosphino-3-diphenylphosphine/-
15-diethylpropane, i,5-bis(diphenylphosphino)-λ2-dimethylpropane, t2-bis(diphenylphosphino)propane, t2-
Bis(diphenylphosphino)benzene, etc.

If desired, minor amounts of any of the other known organic ligands can be present as second ligands. Although the presence of these other known or secondary ligands is not necessary, the presence of the bis(diorganophosphino)alkane is. As used herein, the term "secondary ligand" refers to any of the known ligands useful in homologation reactions, different from the RlPXPR, ligand defined herein. represents something.

These secondary ligands are well known in the art and any of these can be used as long as it does not adversely affect the reaction. Among those of particular utility are mono-tertiary amine, tetravalent and pentaphosphorous compounds. Those skilled in the art will be aware of these compounds, but examples of suitable compounds may be mentioned below: nitriethylphosphine,
Tributylphosphine, tri-2-ethylhexylphosphine, triphenylphosphine, tri(4-methoxyphenyl)phosphine, tri-p-)lylphosphine,
Tri(3-chlorophenyl)phosphine, diphenylhexylphosphine, dimethyl(3-methoxyphenyl)
Phosphine, dibutylstearylphosphine, tribenzylphosphine, dipropylphenylphosphine, ethyldibutylphosphine, tricyclohexylphosphine, cyclohexyldibutylphosphine, propyldiphenylphosphine, '/dipropylphenylphosphine phenyldiethylphosphine, tridecylphosphine,
triotadecylphosphine, tribenzylphosphine, methyldiethylphosphine, ethyldiphenylphosphine, tolyldiethylphosphine, cyclohexyldiethylphosphine, diethylcyclohexylphosphine,
Trimethylamine, triethylamine, tri-n-butylamine, tri-t-butylamine, tri-2-ethylhexylamine, methyldibutylamine, tridodecylamine, tristearylamine, ethyldibutylamine, tricyclohexylamine, triphenylamine, tri(4-methoxyphenyl) amine, tri(p-chloro7ethyl)amine, dibutylphenylamine, diphenylcyclopentylamine, ethyldiphenylamine, trinaphthylamine, tri-p-tolylamine, tribenzylamine, tri(3-methylcyclohexyl)amine, and the above-mentioned phosphines; Arsine, stibine and bismuthine corresponding to the amines. These and many others are known in the art. They can be used alone or, if desired, mixtures containing two or more ligands. Phosphine oxides or phosphites corresponding to the above-mentioned phosphines can also be used as ligands, and these are also well known.

In addition, a solvent that does not interfere with the reaction can be present if necessary. Many solvents are known to be useful in homologation reactions and are essentially inert and should not interfere with the reaction to a significant degree. An example of a solvent is t4
-Dioxane, polyethylene glycol diether or ester, diphenyl ether, sulfolane, toluene, etc. may be mentioned. Preferably, the reaction is carried out in the absence of other solvents or diluents required to introduce the reactants or catalyst components.

The rhodium atomic concentration can vary over a wide range. A catalytic amount of rhodium must be present to catalyze the homologation reaction.

The molar ratio of rhodium to alcohol is 1:25 to 1:2,5
00, with a preferred range of about 1:5
0 to about 1:1500, with the most preferred range being about 1:1500.
100 to about 1i% OOO.

The molar ratio of Rh atoms:Ru atoms is about 1:10 to about 10:1
, preferably from about 6=1 to about 1:6, and most preferably from about 5=1 to about 1:3.

The Rh:I molar ratio is from about 1:500 to about 500:1, preferably from about 1:300 to about! +00:1, most preferably in the range of about 1:100 to about 100:1.

Rh:R2PXPRz molar ratio is 1:100-100:
1, preferably from 10:1 to about 1:10, most preferably from about 2=1 to about 1=2.

The reaction is carried out at a temperature of about 50°C to about 250°C or higher, preferably about 100°C to about 175°C, most preferably about 10°C.
0 to about 160'c.

The reaction pressure is about 100 to about 10. OOOpgig (7
~700 kg/art”G), preferably about 2
50 to about s,oo.

psig (9/clR”G from 18 to 350), jit
Also preferably 500 to about 2,500pmig (35 to
180 kg/an”G).

The molar ratio of Hz:CO in the syngas mixture is about 1:10~
The ratio can be 10:1, preferably in the range of about 1:5 to 5:1.

Reaction times will vary depending on the reaction parameters, reactor dimensions and charge materials, the individual components used, and the particular process conditions employed. The reaction can be a patch or continuous process reaction.

When the method is carried out as described herein, 4
Feasible ethanol conversion rates close to moles/liter/hour and selectivities to ethanol close to 85% are achieved by converting methanol to methanol at lower temperatures and pressures than conventionally required to achieve such values. This can be achieved by homologating to ethanol. In all reactions, the rhodium component, ligand, and methanol were initially charged to the reactor under nitrogen and stirred for about 5 minutes. The ruthenium component and methyl iodide were then added.

In this way, precoordination of rhodium and phosphorus ligands (
pr@-COordination).

A 10.0-barrel Hastelloy® autoclave is equipped with temperature and pressure sensing means, heating and cooling means, magnetically driven stirrer means, inlet and outlet means for introducing components and removing them from the reactor, in which e.g. and the experiments of Examples 1-8 were conducted. Autoclaves used in syngas reactions are well known in the art and can be used in the present method.

Before each experiment, autoclave at about 100℃ with methanol and syngas pressure about 500~101,000ps135~
The autoclave was drained, rinsed with dry acetone, and dried with nitrogen.

Charge the cleaned autoclave with liquid components, then all solid components, seal, and incubate with 400 pmig (28 kg 7 cm” G) of syngas of desired composition.
Pressure was applied. The reactor was held at 400 pmig for 10 minutes and checked for leaks. The contents of the autoclave are then heated with stirring to the selected temperature and pressurized with synthesis gas to 25 pit (18 kg) below the desired specific pressure.
/cm”) higher pressure.The pressure is 2 higher than the desired pressure.
Syngas was consumed by the reaction until it was down to 5 pmlg. Pressure was maintained within 25 psig plus or minus the operating pressure by repressurizing with syngas when necessary. One such cycle is 50 pmlg (!-5kg/cy”
) gas absorption or consumption.

At the end of the experiment, the reactor was cooled to 20° C., the pressure was vented, and the liquid product was collected in a chilled pressure bottle equipped with a septum seal. The reactor was solvent washed until the rinse solution appeared clear.

Analysis of liquid products was performed using an FID detector and Durabond 1.
It was performed using a Parian: Model 3700 capillary gas chromatograph equipped with a 701 50mX Q, 32ml capillary column.

The following examples serve to further illustrate the invention.

In examples, data is reported in area percent or mole percent unless otherwise indicated.

Example 1 In an autoclave, add 10dium dicarbonylacetylacetonate, Rh(COI) t acaes α52 (
2 mmol), ruthenium trichloride hydrate α82, 1.
3-bis(diphenylphosphino)propane α82g (
2 mmol), methyl iodide 2,5-(4Q, 1 mmol) and 40 mg methanol. Following the procedure described above, the reactor contents were heated to 140°C and H
Using a mixture with a molar ratio of t:CO of 2:1, the pressure was increased to 1. It was adjusted to OOOpslg (70kg/Yusetsu G). The reaction was carried out at 975±25 pmlg (68,6±t 8
kg/c
m"G) and then optionally stopped. The reactor was then cooled and the product recovered as described above. The recovered liquid product was analyzed for the formation and presence of the following compounds: Shown: Area percent ethanol: 27.5% acetaldehyde: 111% ethyl acetate
:10.2% methyl acetate: 11,5
% Acetic acid: 25% Dimethyl acetal: 15% Diethyl ether: 17% Dimethyl ether =
119% methanol; 115% methyl iodide: 2.9% The achievable selectivity to ethanol was 70.41% and the achievable ethanol production rate was 53 mol/liter/hour.

An example is a homogeneous catalyst system containing rhodium atoms, ruthenium atoms, iosite atoms, and a bis(diorganophosphino)alkane ligand [i.e., bis(diphenylphosphino)propane] that reacts at fast rates under mild reaction conditions. Demonstrates the feasibility of selectively producing ethanol.

Example 2 t3-bis(diphenylphosphino)furonozo7'L6
The reaction was carried out essentially as described in Example 1, except that 49 (4 mmol) was used. The reaction took 5.15 hours using synthesis gas. ．． 665p easy tg (257,6 to 9/cm”
G) was consumed and then stopped arbitrarily. Analysis of the recovered liquid product showed the formation and presence of the following compounds: Area percent ethanol: 290% acetaldehyde: 95% ethyl acetate: 90% methyl acetate 10.0% acetic acid: 27% dimethyl acetal: 0. 5% diethyl ether: 2.0% dimethyl ether = 11.0% methanol: 17.88% methyl iodide: 2.5% The achievable selectivity to ethanol was 72.75%.

Comparative Experiment A For comparison, reactions were carried out as described in Examples 1 and 2, except that the t3-bis(diphenylphosphino)propane ligand was not present. The reaction took place in 16 hours with synthesis gas 7
Consumes 71 paig (54,2'9/bi 2G),
At that time the reaction was extinguished and there was no evidence of further syngas consumption. This experiment shows that the presence of the bis(dialkyl-phosphino)alkane ligand is important for sustaining the reaction, and in its absence little, if any, ethanol is formed. Analysis of the recovered liquid product showed the formation and presence of the following compounds: Area percent ethanol = 107% acetaldehyde: 107% ethyl acetate
: 161% methyl acetate 7 35.4
0% vinegar @: 490% 90% diethyl ether: 115% methanol
: 3498% methyl iodide :
4.27% The selection rate for ether/-le is &99%
It was nothing more than

Example 3 The reaction was carried out under essentially the same conditions as Example 1 at 130'C. The materials initially charged into the reactor were rhodium dicarbonylacetylacetonate α529 (2 mmol) and ruthenium trichloride hydrate t259.1.5-bis(
Diphenylphosphino)propane was 649 (4 mmol), methyl iodide 25 (40.1 mmol) and methanol 40. Synthesis gas for reaction in 4.5 hours!
, consumed OS Bpmlg (2116 to 97 cm" G) and then optionally stopped. The recovered liquid product was analyzed and showed the formation and presence of the following compounds: The selectivity to ethanol was 8Q, 1% and the achievable ethanol production rate was 2.5 mol/liter/hour.

Example 4 The reaction was carried out under essentially the same conditions as described in Example 3.

The materials initially charged to the reactor were Rh(1,3-?:'s(diphenylphosphino)propane), C1, containing 1 mole of rhodium monochloride and 2 moles of 1,5-bis(diphenylphosphino)propane. complex of formula t959 (2 mmol),
Ruthenium trichloride hydrate t259, methyl iodide 2,5
m (411 mmol) and methanol 40-.

The reaction was carried out for 5.65 hours at 4064 psig of syngas (
285.8 to 97σ寞G) and then arbitrarily stopped. Analysis of the recovered liquid product showed the formation and presence of the following compounds.

Area percent Ethanol: 54.1% Acetaldehyde: 152% Ethyl acetate: 113% Methyl acetate: &4% Acetic acid:
52% diethyl ether: 107% dimethyl ether: 114% methanol = 11IL9% methyl iodide? The selectivity to 2,01% achievable ethanol was 8Q4% and the achievable ethanol production rate was 42 tons/liter/hour.

Example 5 The reaction was carried out under essentially the same conditions as described in Example 1.

Initially, the reactor was charged with 52 g (2 mmol) of rhodium dicarbonylacetylacetonate α, 82 g (2 mmol) of ruthenium trichloride hydrate, and 0.959 (2.5 mmol) t3-bis(isobutylphenylphosphino)furonoξ. ), methyl iodide 2.5m (40.1 mmol) and methanol 40-. The reaction was carried out with 1.600 pmlg of synthesis gas (9/-G in ii5) for 2 hours;
It was then stopped arbitrarily. Analysis of the recovered liquid product showed the formation and presence of the following compounds: Ethanol: 165% Acetaldehyde: 121% Ethyl Acetate: 66% Methylacetate: 11, 1% Acetic Acid
: 15% dimethyl acetal 259% diethyl ether : 14% dimethyl ether : 12.5% methanol
:27.4% methyl iodide :
The selectivity to 535% ethanol is 63%.
Met.

Example 6 A series of reactions were conducted to evaluate the effect of the length of the -X- group in the R2PXPR2 ligand. The reaction was carried out in the same manner as in Example 1, except that in experiments A and B, a ratio of H:C0=1:1 was used. Reaction time, syngas consumed pmig.

The catalyst composition and selectivity to ethanol that can be achieved is summarized in Table I.

Example 7 In this series, the I'11:Co molar ratio was 2:1. In this group, changes in the Rh:Rtx:ligand molar ratio were investigated. The reaction was carried out as described in Example 1. Table ■ summarizes the reactant ratio, reaction time, and gas quenched St amount or absorption;
The selectivity to (enates) is summarized as area percent. In all cases, the molar ratio of the charged material is Rh
Based on an initial charge of 2 mmol of (CO)1 acme, 40 methanol was initially charged.

The data showed that in the absence of the ligand, the ethanol selectivity was very low, and some metal components were also observed to precipitate. A comparison of experiments (b) and (e) shows the increase in selectivity to ethanol and the 5.5-fold increase in gas absorption that can be achieved when doubling the Ru concentration. It has also been found that the best results are usually obtained at a ub:cu=t molar ratio of 1:20.

Table ■ Comparative experiment A 1 1 0 20 α6
771(54,2) Comparative experiment B 1 2 0
20 α75 926(65,1)&
12 α5 20 A2B 694(48,8)b
11120t22950(668) c 1 2 1 20 2,8 5350(2
35,6) d 1 2 2 20 5 2 5
665 (257,6)・1 2 2 40
1,3 1277 (89,80) x 1 2
1 10 to 119B(84,25)g
1 2 1 40 o, 62358
(1,8)h 1g 1 20ts
sz777 (19s, s) l 1 i 2 2
0 2,0 2540(178,6)5 1
g 5 20 2,2 2422 (170,5)k
1, 5 40! h, 252250 (
158,2) L=1.5-bis(diphenylphosphino)propane Experiments (c) and (d) in Examples 1 and 2 respectively
It is.

Example 8 The effect of temperature changes was studied. The reaction was carried out as described in Example 7. Table 1 summarizes the reaction temperatures, reactant ratios and other reaction conditions used, and Table V summarizes the results achieved in weight percentages. The data show that the achievable ethanol selectivity increases as the temperature decreases.

Table ■ a 11120135 as5617 (454) b1
1120140t22950(648)c 1522
0150 to 2436(171,3)d 152
201402,02540(178,6)・1522
01304.5305B (2156) L = Bis(diphenylphosphino) tetrapane experiment = Example 7b; Experiment d = Example 71; Experiment 62 Example 3゜ Table V Compound, area % Ethanol 586 &2 17.4 248
34.0 Acetaldehyde 2,84 1 6
．． 2 &42 9.0 Ethyl acetate α5
8 1,3 Melon 6 i 6.5 Methyl acetate 117 12,0 19.3 12,1
a.

Acetic acid toe to 532,21, O
Dimethyl acetal 7.2 &5 17
2,2t.

diethyl ether t14 to 2,1
t4 2,0 di fiq-ILt aete pv
11, 4 11IL5 9.7 9.5 1
1, O methanol 5 [13447,524,02&3
24.0 Methyl iodide 4.09 4.1
2,75 t9 t8 smoke selectivity achievable ethanol 4188 47.48 551
69.82 80.11 Other oxygen additives 59.1
252,52 46.85α18 1989 Example 9 The experiment of Example 9 was conducted in a 500-Hastelloy:magnetic m-dynamic autoclave, which was processed in the same manner as the smaller autoclave. In these experiments, the procedure followed was essentially the same using syngas with a H,:CO molar ratio of 2:1 and a methanol charge of 150-, and the pressure was repressurized as necessary to 20- o pmi
g (14 Iai/aa"G). All experiments were carried out for 3 hours. After the experiments were completed, the reactor was cooled to below 20° C. and gas samples were taken.

The reactor was slowly vented and the product was collected in a crown cap bottle at 0°C. Gas analysis was performed on a Karl Analyti gas chromatograph, series S.

DB1701 3 coupled to flame ionization detector
The liquid product was analyzed using a Hewlett Packard HP5890A gas chromatograph equipped with a 0 m x 0.32 mm capillary column. The product was quantified using acetonitrile as an internal standard.

The reactants, reaction conditions and results are summarized in Table 1. The ligand used was t3-bis(diphenylphosphino)propane.

Example 1 A series of reactions were carried out as described in Example 9 at 140° C. using synthesis gas with a H,:CO molar ratio of 3:1. The pressure is 2000 psig (140'9/
cm”G), Experiment (b) Te 1200pmig (8
4'? /am”G), 1600 pml in experiment (c)
g (ii019/3”G).

The rate to ethanol and equivalents was found to be lower than in a similar experiment using 2:1 syngas (experiment (1) of Example 9). It is believed that part of the reason for this slow rate may lie in the rapid build-up of methane.

The rate of conversion to methane increases as the raw material with a higher synthesis gas ratio is used.
It got expensive. The three reactions used 2 mmol of rhodium dicarbonylacetylacetonate, 6 mmol of ruthenium trichloride trihydrate, 6 mmol of t3-bis(diphenylphosphino)propane, and 40 mmol of methyl iodide. The results are summarized in Table ■.

Table ■ Compound, IIXji 1% ethanol α47 2-9r: J 5
．． 52 Acetaldehyde 596 05 2,9
2 ethyl acetate 2,1 154 2,01
Methyl acetate 0.0 αO (LO acetic acid
2,04 4.52 543 Dimethyl acetal α11 α0 α05 Diethyl ether α70 504 410 Dimethyl ether 5480 7t98 62,10 Methanol t87 t97 2,11 Methyl iodide rate, M/hour to ethanol α35 α19 Q, 1
To 6-tanol equivalent 0.37 α25 α
34 To other oxygen additives α10 α05
(To LO8 methane Q, 70 α30
α41 selectivity, M% Realizable ethanol 9Q, 5 89.2 8
&? Other oxygen additives 9.7 1 (L8 11
, 1-bis(diorganophosphino)alkanes are known, but they are poorly commercially available. Therefore, many were made according to published procedures and as shown in the experimental scheme below. Reactions were carried out under dry nitrogen and using dry solvents. C7
is cyclohexyl and ph is phenyl.

Scheme I pcy (ph) under nitrogen in a 250-proof round bottom flask.

10g of CH,C1250-
I put it in. Br(Cut)sBr 19- was slowly added dropwise and the mixture was then refluxed under nitrogen for 11 hours.

“P nmr analysis of the product shows the desired salt ((Ph)zC7
It showed incomplete conversion to P(CHz)sPCy(Ph)t:1Br2. Therefore, CH, C1, were removed under reduced pressure, and 100-benzene was added. The mixture was refluxed for 5 hours and Pnmr was ((Ph)ICyP(CHz)sPC
It showed complete conversion to 7(Ph)z)Brz. 3
150 minutes of 0% aqueous sodium hydroxide solution was added and the mixture was refluxed in air for 6 hours to completely (Ph)CyP(
0) (CHz)sP(0)Cy(Ph). The dioxide was extracted into CH,C1, and the solution was dried over magnesium sulfate and filtered. After adding triethylamine 24.5- to dry CH,C1, H8I
CH, CI after degassing C1g 17.5-.

Add slowly into 40sd. The mixture was refluxed for 4 hours, cooled, filtered and the solvent removed under reduced pressure. CIhCl*25- was then added to the resulting material, followed by the slow addition of 30% sodium hydroxide 150- with vigorous stirring. The organic layer was separated, dried and Cy(Ph)P(CHt) 5P(Ph)C7 was recovered after removing the solvent.

1 ml dry tetrahydrofuran 4 into a 500-ml round bottom flask
00- was added, followed by 20.081 moles of HPPh. The mixture was cooled to 0°C and n-butyllithium 1
081 mol was added slowly to form LiPPh snow.

This was slowly warmed to room temperature and stirred for about 1 hour. The solution was transferred to a dropping funnel and added dropwise to a flask containing 100% of 1,3-dicyclopropane dissolved in 100% of diethyl ether. The mixture was stirred overnight and then hydrolyzed with water. The organic layer was separated and the solvent was removed under reduced pressure to leave PhzP(CHz)scl, which was purified under nitrogen as Kc! ? Stored until needed.

Following the procedure described above, C7(Ph)PH was reacted with n-butyllithium to make C7(Ph)PLi. P
27 mmol of h2P(CHz)scl was dissolved in tetrahydrone 100°C, cooled to 0°C, and C7(P
h) 27 mmol of PLl was added dropwise. - After stirring overnight, remove the tetrahydrone and 10 hexane
Added 0d. The mixture was refluxed for 1 hour and filtered hot. With the exception of hexane, the product Cy (Ph) P
(CHz)xPPh The goose remained.

Following the procedures described in Schemes I and 1, the following bis(diorganophosphino)furonones were prepared and used in the methanol homologation process of the present invention.

Class 1 R2P (CH2)s PRz R=methyl, ethyl, cyclohexyl, phenyl Class 2 R(Ph)P(CHz)sP(Ph)RR=hydrogen, methyl, ethyl, amyl, cyclohexyl Class 3 )3PPh, R=ethyl, amyl class 4 R(Ph)P(CHz)sPPh2 R=methyl, n
-Propyl, n-octyl, cyclohexyl In the above formula, ph represents a substituted or unsubstituted phenyl group.

Example 11 Methanol was homogenized following the procedure described in Example 1 using the above ligand. These reactions are summarized in Table VIK. The ligands are identified as: h, 1s-bis(dimethylphosphino)propane B, 1,3-bis(diethylphosphino)propane C, $5-bis(dicyclohexylphosphino)propane D, 1.5-bis(phenylphosphino)propane w,
ts-bis(methylphenylphosphino)propane v, I3-bis(ethylphenylphosphino)propane G, 1,5-bis(amyl7elphosphino)propane H, zs-bis(cyclohexylphenylphosphino)
Propane ■ 1-diethylphosphino-5-diphenylphosphinopropane J, 1-cyamylphosphino-3-diphenylphosphinopropane, 1-methylphenylphosphino-5-diphenylphosphinopropane L, 1-( It-propylphenylphosphino)-3-
Diphenylphosphinopropane M, 1-(n-octylphenylphosphine/)-3-diphenylphosphinopropane N, 1-cyclohexylphenylphosphino-5-
Diphenylphosphine/Propane Example 12 This series of reactions investigated the effect of solvents on the reaction. It was observed that the solvent caused a decrease in the selectivity of ethanol. Surprisingly the addition of 1 dimethylformamide did not result in the formation of ethanol.

The reaction was carried out as described in Example 1. In each reaction, the following reactants were used: Rh(Co)2 ma
te 2 mmol RuCl trihydrate Q
, 829 Ligand 4 mmol CH3I 40 mmol Methanol 20- Solvent 20 m The ligand is 1,3-bis(diphenylphosphino)propane, the reaction time is 2 hours, the temperature is 140°C, the pressure is 97 S ps1g±25 pmig (6
8,6±18 to 9/cIn2G). Table I shows the results.
Summary of XK.

Table ■ a None 5000 (210)
7iC Diglym* 2030 (
145) 719d 1,4-dioxane
380(27)14.9・Diphenyl ether
1720(121)545fN-methylpyrrolidinone 1000(70) 45.7g Toluene
1490(105) 44.4h Dimethylformamide 520(23) 0 Example 13 The effect of the presence of a second ligand on the process of the invention is studied and reported in this example by carrying out a series of reactions. In some cases, adding a second ligand to the catalyst mixture has been found to increase activity, ethanol selectivity, and catalyst lifetime.

The reaction was carried out as described in Example 1. Experiment (a)
-(f) the following reactants were used: Rh(Co
)2 acme 2 mmol Ru CI H
Water distribution Q, 829 ligand (L)
4 mmol secondary ligand (SL) CH3I as shown
4 mmol methanol
40mg Ligand: 13-bis(diphenylphosphino)prone (dppp) gZffd position: A=)diphenylphosphinoB=)lycyclohexylphosphine real*i (r;I In ~(h), Rh( CO)2a
A complex of cme and 1,3-bis(diphenylphosphine)propane was used. The complex was prepared as described in Example 4. The results are summarized in Table XK.

Table X a A 2:12888 (21151) 75.7
b A 2:22770 (194,8) 74.9
e B 2: α35581 (zsta) 8&1
a B 2:141so(2pta) 718e
B 2:52945(207,1) 8Q, 5f”
B 21 2500 (17NB) 85.
8g” B 2:5 2792 (1943)
846h” B 2:4 2400 (8 to 161
) 8 (L9★Rb is Rh ["ls-bis(diphenylphosphino)propane) and C12.0 mmol [
I loaded it.

Example 14 Rh (Co)acac (15
29 (2 mmol), ruthenium trichloride hydrate 1829
, t3-bis(di-p-
Tolylphosphine/)ivsA7Q, 949 (2 mmol), methyl iodide 2,sIlg (40 mmol) and methanol 40- were charged. Following the procedure described in Example 1, the expander contents were heated to 40'c and Hl:
Pressure 975 ± 25 in a mixture with C0 molar ratio 2:1
pmlg (68,6±t 8J9151”G)
It was adjusted to Gas absorption ends after 1 hour of this period,
Synthesis gas 1200 pmig (84 to 9/es”G
) was consumed. Cool the autoclave to 19°C,
The pressure was lowered to Opsig. An aliquot of the liquid product was removed from the reactor and analysis showed the formation and presence of the following compounds: Ethanol ° 12.2% Acetaldehyde: 5.2% Ethyl acetate: 14% Methyl acetate: 1α6% Acetic acid 12% Dimethyl Acetal: 2.5% Diethyl ether: α2% Dimethyl ether: 112% Methanol ° 49.9% Methyl iodide ° S, 6% The selectivity to ethanol that could be achieved was 53%.

The autoclave was then charged with 20 m of methanol and 20 mmol of methyl iodide in addition to the original reactor contents. The reactor contents were heated to 140°C and Ht:
Pressure 975 ± 25 in a mixture with Co molar ratio 2:1
pmig (6F3.6±t 8 kg/es”G
). Gas absorption ends after t3 hours, and during this period 1786 pmLt of synthesis gas (125,6 to 9/
lvm” G) was consumed. Autoclave at 19°C.
Cool to temperature and reduce pressure to Opsig. An aliquot of the liquid product was withdrawn from the reactor and analysis showed the formation and presence of the following compounds: Area percent ethanol ° 24.0% Acetaldehyde: 69% Ethyl acetate = 4.8% Methyl acetate: 12.1% Vinegar [58% dimethyl acetal; α4% diethyl ether: Q, 6% dimethyl ether = 92% methanol ° 342% methyl iodide ° 2,8% The selectivity to ethanol that could be achieved was 61%.

The reactor contents were heated again to 140°C and H,/CO
Pressure 975 ± 25 p with a mixture having a molar ratio of 2:1
mlg (61LS±t8'9/cm"G)K adjusted.

The reaction was continued for 2.5 hours, during which time 1339 of the synthesis gas
psig (94,16 kg/m"G) was consumed and then the reaction was optionally stopped. The autoclave was
Cool to 9° C. and reduce pressure to Op@ig. An aliquot of the liquid product was removed from the reactor and analysis showed the formation and presence of the following compounds: Ethanol 296% Acetaldehyde 8.7% Ethyl acetate: 15.9% Methyl acetate: 7% Acetic acid 151 % Dimethyl acetal: 102% Diethyl ether: 2.2% Dimethyl ether: 6.1% Methanol ° 1α 8% Methyl iodide ° 14% Then add methanol 20- and iodide to the original reactor contents in the autoclave. 20 mmol of methyl was charged. Heat the reactor contents to 140°C and Hx:
Pressure 975 ± 25 in a mixture with CO molar ratio 2;1
pmig (613,6 ± 18'9/z"G). The reaction was continued for 2.8 hours, during which time syngas 1
052 psig (72,57'?/m" G) was consumed, then the reaction was optionally stopped. The autoclave was cooled to 19° C. and the pressure was lowered to 0.052 psig (72,57'?/m" G). An aliquot of the liquid product was removed from the reactor. Removal and analysis showed the formation and presence of the following compounds.

Area percent ethanol ° 22.6% acetaldehyde: 14.3% ethyl acetate
M I&7% Methyl acetate: &4% Acetic acid 14.2% Dimethyl acetal: 0.00% Diethyl ether: 4.3% Dimethyl ether: 19% Methanol ° 5.9% Methyl iodide: 2,5% To ethanol feasible The selectivity was 61%.

"Pnmr analysis of the catalyst residue showed that the group was coordinated to rhodium. This example shows that rhodium atoms, ruthenium atoms, iosito atoms and bis(diorganophosphino)alkane ligands (i.e. , ll5-bis(j-p-)lylphosphino)propane) to selectively produce viable ethanol under miscible reaction conditions.

This example also shows that these catalysts have good stability and can be used repeatedly without loss of selectivity.

Example 15 Rh(Co)2 aeae 0.52 in autoclave
9 (2 mmol), Ruthenium trichloride hydrate Q, 82
g, 13-bis(diphenylphosphine/)propane 0.
82 g (2 mmol), methyl iodide 2,5-(404
17 moles) and 40 moles of methanol were charged. Following the procedure described in Example 1, the reactor contents were heated to 140°C and the pressure was increased to 975±25 pmig (d&6±t 8 kg/a) with a mixture having a H,:CO molar ratio of 2:1.
m” G) K if!.The reaction was continued for zs hours m, during which time 2833 pslg (199
, 2 to 9/-G) was consumed and then the reaction was optionally stopped. Cool the autoclave to 19°C and turn the pressure off.
aig K lowered. The liquid product Arifut was removed from the reactor and analysis showed the formation and presence of the following compounds: Area percent ethanol 37.0% Acetaldehyde: 69% Ethyl acetate: 40% Methyl acetate: 5.8% Acetic acid 2, 2% dimethyl acetal: Q, 2% diethyl ether: t3% Dimethyl ether: 6.8% Methanol 291% Methyl iodide 19% Ki and 20 mmol of methanol and 20 mmol of methyl tatsuka were charged. The reactor contents were heated to 140°C and the pressure was increased to 97°C with a mixture having a H2:CO molar ratio of 2:1.
5±25p Hataketg (?S &6±t8'9/cm"G
). The reaction was continued for 175 hours, during which time 1482 psig (104,2J19/m) of synthesis gas was
G) was consumed and then the reaction was optionally stopped.

Cool the autoclave to 19°C and increase the pressure to Opsig.
K lowered. An aliquot of the liquid product was removed from the reactor and analysis showed the formation and presence of the following compounds: Area percent ethanol ° 32.8% Acetaldehyde: 10.2% Ethyl acetate: 4.6% Methyl acetate: 67 % Acetic acid 59% Dimethyl acetal: 12% Diethyl ether: 7% Dimethyl ether: 93% Methanol 25.2% Methyl iodide ° 2.5% The selectivity to ethanol that could be achieved was 75%.

The reactor contents were charged with an additional 20 g of methanol, heated again to 140 °C, and brought to a pressure of 975 ± 25 pmig (6 & 6 ± t
8'9/IyR"
12,9 kg/cm"G) was consumed and then the reaction was optionally stopped. The autoclave was cooled to 19 °C and the pressure was reduced to Opsig. An aliquot of the liquid product was removed from the reactor and analyzed as follows. It showed the formation and presence of the following compounds: Ethanol ° 3tO% Acetaldehyde: 15.9% Ethyl acetate: Z2% Methyl acetatetonia, 0% Acetic acid 4.0% Dimethyl acetal = Q, 1% Dimethyl ether: 50% Dimethyl ether: 115% methanol ° 1&9% methyl iodide ° 18% The selectivity to ethanol that could be achieved was 75%.

The autoclave contents were then emptied into the flask and the volatiles were stripped off under reduced pressure.

The solid content produced was then returned to the autoclave, and the autoclave was also charged with 40 ml of methanol and 2 ml of methyl iodide.
, 5d (40 mmol). The reactor contents were heated to 140 °C and the pressure was increased to 975 ± 25 pmig (68,6 ± t
a kg/cm”G).The reaction was
During this period, 2589 pslg of syngas (
168,0 kV/cm" G) was consumed and then the reaction was optionally stopped. The autoclave was cooled to 19° C. and the pressure was reduced to Opaig. An aliquot of the liquid product was removed from the reactor and analyzed as described below. showed the formation and existence of the compound.

area percent Ethanol　　　　　　2a7% Acetaldehyde: 9.7% Ethyl acetate: 58% Methyl acetate: 75% Acetic acid 2.0% Dimethyl acetal: 13% Diethyl ether = to% Dimethyl ether: 97% Methanol　　　　　　2&7% Methyl iodide ° 56% The selectivity to ethanol that could be achieved was 73%.

The P nmr of the catalyst residue showed that the ligand was coordinated to rhodium. This example also shows that these catalysts have good stability and are capable of producing ethanol selectively under mild reaction conditions. This shows that it has a high selectivity and can be used repeatedly without losing selectivity.

Claims (1)

[Claims] 1. General formula: R'OH (wherein R' is (i) an alkyl group having 1 to 20 carbon atoms, (ii) an alkenyl group having 2 to 20 carbon atoms, or ( iii) selectively producing viable alkanols by reacting with synthesis gas alkanols in which the aryl moiety is phenyl or naphthyl and the alkyl moiety is a monovalent hydrocarbyl of an aralkyl group having 1 to 10 carbon atoms; A method, wherein the synthesis gas is H_2:C
O having a molar ratio of 1:10 to 10:1 and a temperature of 50°C to 25°C
0℃ and pressure 7~700kg/cm^2G (100~1
0,000 pmig), a rhodium atom, a ruthenium atom, an iodine atom and the general formula: R_2PXPR_2 (wherein, X is a linear or branched alkyl, alkenyl, or a cyclic divalent bridge connecting two P atoms; , the terminal bonds of the bridge are 1 to 10 carbon atoms apart, and R is (i) a hydrogen atom, provided that no more than 1 hydrogen atom is attached to the P atom, or (ii) a carbon bis( carried out in contact with a rhodium-based catalyst containing diorganophosphino)alkane ligands, the molar ratio of rhodium to alkanol is from 1:25 to 1:2500, and the molar ratio of rhodium to ruthenium is from 1:10 to 10
:1, and the molar ratio of rhodium to iodine is 1:500~
500:1 and the molar ratio of rhodium to R_2PXPR_2 is from 1:100 to 100:1. 2. The temperature is 100-160℃ and the pressure is 35-1
80 kg/cm^2G (500-2500 pmig) and the H_2:CO molar ratio is 1:5-5:1. 3. The method according to claim 1, wherein R'OH is an aliphatic alkanol having 1 to 4 carbon atoms. 4. The method according to claim 3, wherein the alkanol is methanol. 5. A patent claim in which the bis(diorganophosphino)alkane is a bis(dialkylphosphino)alkane (the alkyl group contains 1 to 10 carbon atoms and the bridging alkane group contains 2 to 6 carbon atoms) The method described in item 1. 6. The bis(diorganophosphino)alkane is a bis(diarylphosphino)alkane (the aryl group is a phenyl group and the bridging alkane group is a carbon atom of 2
6). The method according to claim 1. 7. The bis(diorganophosphino)alkane is a bis(alkylarylphosphino)alkane (the alkyl group contains 2 to 5 carbon atoms, the aryl group is a phenyl group, and the bridging alkane group contains 2 to 5 carbon atoms). 6). The method according to claim 1. 8. The molar ratio of rhodium to ruthenium is 1:10 to 10:
1 and the molar ratio of rhodium to R_2PXPR_2 is from 1:100 to 100:1. 9. The method according to claim 1, wherein a second ligand is also present during the homologation. 10. Methanol and H_2:CO molar ratio 1:5 to 5:1
Synthesis gas with a temperature of 110°C to 160°C and a pressure of 3
5~180kg/cm^2 (500~2,500psi
2. A process according to claim 1, wherein the 1,3-bis(diorganophosphino)alkane reacted in g) is 1,3-bis(diorganophosphino)propane. 11. Claim 10, wherein the 1,3-bis(diorganophosphino)propane is bis(diphenylphosphino)propane and the rhodium compound charged is rhodium dicarbonylacetylacetonate. Method. 12. The method according to claim 10, wherein the 1,3-bis(diorganophosphino)propane is Rh[1,3-bis(diphenylphosphino)propane]_2Cl. 13. The method according to claim 10, wherein the 1,3-bis(diorganophosphino)propane is 1,3-bis[di(isobutylphenylphosphino)propane. 14. The method according to claim 10. The method according to claim 1, wherein the bis(diorganophosphino)alkane is 1,3-bis(diarylphosphino)propane. 15. The 1,3-bis(diarylphosphino)propane is 1, The method according to claim 14, wherein the alcohol is methanol. 17. The method according to claim 14, wherein the alcohol is methanol. 17. The method according to claim 14, wherein the alcohol is methanol. ) Alkane is a rhodium compound and 1,3-bis(diarylphosphino)
The method according to claim 1, which is a complex with propane. 18. Claim 1, wherein the complex is Rh[1,3-bis(diphenylphosphino)propane]_2Cl
The method described in Section 7. 19, the bis(diorganophosphino)alkane is 1
, 3-bis[di(arylalkylphosphino)]propane. 20. The method of claim 17, wherein the 1,3-bis[di(arylalkylphosphine)]propane is 1,3-bis(isobutylphenylphosphino)propane. 21. Claim 1, wherein the bis(diorganophosphino)alkane is represented by the following formula: R_2P(CH_2)_3PR_2 (wherein R is as defined in Claim 1) Method described. 22. The method of claim 21, wherein R is a member of the group consisting of methyl, ethyl, cyclohexyl or phenyl. 23, the bis(diorganophosphino)alkane has the following formula: R(Ph)P(CH_2)_3P(Ph)R (wherein P
h is phenyl and R is as defined in claim 1. 2. The method according to claim 1, wherein R is not a phenyl group. 24. The method of claim 23, wherein R is a member of the group consisting of hydrogen, methyl, ethyl, amyl or cyclohexyl. 25, the bis(diorganophosphino)alkane has the following formula: R_2P(CH_2)_3PPh_2 (wherein Ph is phenyl and R is as defined in claim 1, provided that R is phenyl 2. The method according to claim 1, wherein the method is represented by: 26. The method of claim 25, wherein R is a member of the group consisting of ethyl or amyl. 27, the bis(diorganophosphino)alkane has the following formula: R(Ph)P(CH_2)_3PPh_2 (wherein Ph is phenyl and R is as defined in claim 1). (provided that R is not a phenyl group). 28. The method of claim 27, wherein R is a member of the group consisting of methyl, n-propyl, n-octyl or cyclohexyl.