DE1518236B2 - - Google Patents

Description

1 Ölö ZoO
3 4

b) in the case of hydroformylation, a tin (II) compound has not yet been found in the literature halide is reported. Your application therefore represents another

Formation of the present invention. This

where the complex compound of the general formula complex compounds of the formula (R ₃ Z) ₃ Rh ¹ X can-

5 nen are represented by taking an excess

L ₇₁ ] VPXj, of the tertiary phosphine, for example the 3- bis

ten times the stoichiometric amount, with one

has, in which L the ligand as defined above is rhodium trihalide in a solvent, M is platinum, rhodium or ruthenium, X is preferably an alcoholic solvent, such as a halogen atom or a pseudohalogen group dar- io z. B. ethanol, heated to reflux. During cooling, η is the number of ligands present - the complex compound often crystallizes from the molecules, y the number of halogen solutions present in a yield which is quantitative in terms of practically atoms and / or pseudohalogen groups. The crystals can be separated and and is at least 1, and ν is the valence state of the to remove the phosphine excess, which is the metal M and is equal to y , with the proviso that at 15 it can still adhere. After a M = Ru other methods, the complex compounds

ν the value 2 or 3 and η the value 3 or 4, are produced by the fact that the tertiary phosphorus

when M = Rh phine or arsine to displace other ligands

ν the value 1 or 3 and η the value 3 from the rhodium (I) complexes are used,

and at M = Pt. 20 The preferred catalysts of this type have

ν and η the value 2 the formula (R ^ P) ₃ Rh ¹ X ', wherein each R' is an aryl

to have. group, preferably phenyl, and each X '

The ligands which are included in the definition of a chlorine, bromine or iodine atom, preferably chlorine group a) include :. tertiary Phos- means. The complexes of the formula (R ₃ Z) ₃ Rh ¹ X phine and arsine, tertiary phosphite esters, phosphine 25 are particularly effective as hydrogenation catalysts and oxides and preferably more neutral compounds. B. tributyl or triphenylphosphine, tri-fast the reduction of acetylene compounds methyl, tributyl or triphenyl phosphite, dimethyl to the corresponding saturated compounds. With phenylarsine, triphenylarsine, triphenylphosphine oxide, this hydrogen pressure, they also produce phosphorus triisocyanate and phosphorus triisothiocyanate more easily. 30 the reduction of aldehydes to the corresponding

The complex compound used as the catalyst, primary alcohols than the other catalysts, must be electron-neutral, so that, in general, the reduction of the olefinic Halo formula must be ν = y. gene compounds, such as allyl bromide, only the CC

The preferred valence states of the metals of the double bond, but not the halogen substituents. Platinum groups in the complex are dependent on 35 The product formed by the process is therefore the metal used. For ruthenium this is the corresponding saturated halogen compound,
preferred valence state 2 or 3; for rhodium In preferred form for hydroformylation

1 or 3; and for platinum 2. The complex compound has the catalyst to be used normally has an octahedral structure, ie, the formula
the sum of η and y is 6 if the following 40

Metals are present in the following valence stage: q § _n q SnCl

Rh ^m , Ru ⁿ or Pt "", although the complex with \ / \ /

Ruthenium is a 5-coordinated quasi-octahedral * ^ ¹ V -x ^ ¹ ^

Structure. The Pt ⁿ complex compound Cl ₂ Sn ^κ Cl ⁷ ^ SnCl ₂

however, it is usually tetragonal in structure, 45
ie the sum of η and y is 4. If desired,

The complex solution can contain a little hydrochloric acid, albeit probably some of the stannic acid, which under certain circumstances solvates containing groups or is able to promote the stability of the complex in aqueous solution, hydrochloric acid solution as SnCl ₃ groups. The so.z. B., if chloride ions were necessary for connection with the 50 structures of the other rhodium (I) -tin (II) -halo complex, if this is a cation, genide complexes for use according to the invention although the complexes by the empirical formula are similar. Accordingly, if a Rho-L ₇₈ M ¹¹ Xy was designated, since this is the formula of the dium trihalide is used, the use of the complex reflects how it normally produces three times the molar amount of the tin (II) halide and in the liquid medium is necessary in order for this type of rhodium (I) complex to be able to form in the actual complex, which acts as a bond; one mole fraction acts as an active catalyst taking part in the reaction, reducing agent for the rhodium. In the other case, some of the ligand groups (L) can be replaced by hydrido or the rhodium (I) complex compound not fully carbonyl ligands. are constantly formed or is called a rho-

A particularly effective class of catalysts formed dium (III) complex compounds which are reduced to the rhodium (I) complex compound of the present invention during the use according to the invention, in particular hydroformylation by the water present for use in the hydrogenation processes to give the rhodium (I) complex compound - will. Preferably, therefore, the tin (II) halogen, which is described by the formula (R ₃ Z) ₃ Rh ¹ X, and rhodium trihalide are in a molar, wherein the ligand R ₃ Z has a tertiary phosphine 65 ratio of essentially 3: 1 used,
or is arsine. So there is a 1: 3 molar complex- The production of the catalyst to be used-

Connection of a rhodium (I) halide with the complex compounds is done by expelled persons Ligands. About such complex mixing of the halide or the pseudohalide

i OiO ZJO

5 6

of a metal of the platinum group and the molecule, or an alcohol which is followed by which supplies the ligand, is obtained therefrom in the presence of a hydrogenation, suitable solvent essentially in accordance with measured stoichiometric amounts corresponding to the olefinic and acetymolecular amounts of the present invention Formula of the complex, whereby one hydrogenates to 5 lenic bonds, aldehydes, ketones or must take into account that a calculated excess of their thio analogs to the corresponding alcohols of the ligand may be necessary if this is also reduced or thiols or nitrile or Schiff bases as a reducing agent for the platinum group metal to be reduced to the amines. With such hyzu has to serve. Methods for producing some dration reactions can be used in the unsaturated reaction Complex compounds are, for example, participants which contain any substituents wise in J. Chem. Soc, 1964, 2508 to 2513, do not affect the course of the reaction. So can give. As a liquid reaction medium, a lower z. B. the reactant cycloaliphatic aryl alcohol, such as ethanol or methanol, suitable. or contain hydroxyl groups. The ethers of hydrogenation, such as diethyl ether or tetrahydrofuran, are reaction according to the invention is also special also useful. To other suitable solutions 15 effective for the reduction of aldehydes and agents and additional solvents, ketones belong to the corresponding alcohols, e.g. B. for aliphatic and aromatic hydrocarbons, such as the production of heptanol from heptaldehyde, Hexane and benzene. The composition of the gebil-2-butanol from methyl ethyl ketone, from cyclohexanol The complex compound can usually easily be cyclohexanone; and for the hydrogenation of olefin by conventional analytical methods detected 20 niche double bonds, e.g. B. for manufacturing will. In many cases, if desired, these can be derived from saturated fatty acids and their derivatives. Complex compound of suitable concentrated naturally occurring unsaturated acids, such as Solutions such as B. an alcoholic solution, oleic acid, linoleic acid or ricinoleic acid; and for the be crystallized. Hydrogenation of terpene-like double bonds, such as

Many ruthenium-containing complex compounds enable the production of menthol from isopulegol. Acetyl

gen, as described in general above, lenic compounds, such as. B. phenylacetylene and

are very particularly for hydrogenation reactions according to the invention, acetylenic alcohols are also

particularly suitable. It has been found, however, that if reduced, usually to a mixture of the

these complex compounds are often much less suitable corresponding alkene and alkane, being a

for hydroformylation reactions because a 3 ° hydroxyl group remains as such in the product.

Reaction with carbon monoxide occurs, leading to grain- 'The application of excess hydrogen

plex compounds leads to a large extent or results in a product which at the expense of the alkene

are completely insoluble in the reaction mixture. consists mainly of the alkane. It was too

Thus, the reaction mixture possibly contains found according to the invention that acetylenic alcohol

the soluble grains required as a catalyst are not significantly lighter than acetylenic carbon

plex compound, which reduces the substance yield in the case of hydrogen.

a hydroformylation process using the hydroformylation according to the invention Such a ruthenium complex can react accordingly with olefins or acetylenic carbons is decreased. Hydrogen are converted to aldehydes, which

When using the above-described grain 40 then according to the hydration according to the invention

plex compounds, especially those of the ruther process, can be reduced,

nium as catalysts, the presence of a The hydroformylation reaction according to the invention

(C ₁ to C ^ alcoholic solvents their activity is particularly effective

increase. 'olefinic compound in the presence of a

If the reaction to be carried out is a hydrogenation catalyst according to the invention with a mixture reaction, whereby of course no carbon monoxide is converted into hydrogen and carbon monoxide, is turned, the said »unsaturated organic- Theoretically, this mixture should be equimolar, niche compound «a substance which has a multiple, but it is generally advantageous, an over-ply bond to have one carbon atom attached to carbon monoxide, their carbon atom or to an oxygen, 50 Normally hydrogen and carbon-sulfur or contains nitrogen atom. Is the through-monoxide in a molar ratio of 1: 1 to 1: 5 feeding reaction a hydroformylation reaction applied. In this way, the tion, which prevents the hydrogenation reaction competing with hydrogen. the as well as with carbon monoxide, it is the reaction temperature during the hydroformylation The "unsaturated organic compound" 55 is generally kept below 110 ° C, since the an olefinic substance, d. H. an ethy-hydrogenation reaction obviously above this lenisch-unsaturated or acetylenically-unsaturated temperature is favored, albeit in another Hydrocarbon or substituted hydrocarbons regard the temperature can be increased to 200 ° C material. The present substituents should be opposite to can. The yield of the aldehyde formed appears be inert to the reaction. Such substituents are often supposed to be actually quantitative. Preferably, for example halogen and hydroxy substituents. but not necessarily, it is olefinic The hydroformylation of acetylenic connec- tion a «-olefin, such as ethylene ^ fertilize which, as has been found, with the propylene, butene-1, hexene-1, octene-1, the higher inventive catalysts occurs, can as «-olefins, which by thermal cleavage of an initial hydrogenation to the corresponding paraffin wax can be obtained, and dienes such as butaethylenically unsaturated Connection to be considered (if normally only one of the double bonds, whereupon the hydroformylation of this counterpart reacts). As a substituted olefinic compound follows, so that the product can gene an aldehyde z. B. can be used: Allyl alcohol,

Methallyl alcohol, isopropenylbenzene, styrene, vinyl-crucial. However, it will be an amount from 0.1 to cyclohexene, cyclohexene or cyclooctene. 5 percent by weight, preferably 0.5 to 3 percent by weight

The aldehydes, which from the percent described above, based on the weight of the unsaturated hydroformylation reaction according to the invention, are normally used,
If the reaction is complete, the product is subjected to the subsequent hydrogenation reaction and the reaction mixture is separated off. This happens where the aldehydes to the corresponding usually by fractional distillation, with primary alcohols reduced, ie hydrogenated. this, if necessary, in a convenient manner under In general, a small one. Amount of de-reduced pressure can be carried out. The speaking alkane formed. In such a hy- ίο separation is preferably not so far the expression reaction can lead to the same or different that the entire solvent from the non-. Complex catalysts are applied as in volatile complex compound is removed. That of the hydroformylation reaction. So z. For example, the distillation "residue" containing the remaining hydrogenation reaction in a homogeneous reaction catalyst may then be re-mixing at a hydrogen pressure up to 60 i ₅ application at in a further inventive encryption and at temperatures up to about 120 ° C carried out drive, often after adding another amount of the be. Such a two-stage hydroformylation solvent can be used. Since the separation and subsequent hydrogenation process provides the product of excess pyridine or if the same complex as a catalyst cannot be carried out too easily, pyridine is used in any stage, a convenient synthe- ao for this reason Formation of the complex table way to obtain Tndecylalkohol for the inventive use less er-dodecene-1, nonanols from the corresponding desires.

Octenes and n-heptanol from "-hexene-1 represent. The invention is now illustrated by the following examples

Two-stage reaction using the invention games explained by Examples 1 to 3, 10 and corresponding complex as a catalyst in each version as 12 to 19 hydrogenation reactions and the examples The process stage can be conveniently carried out in a 4 to 9 and 11 hydroformylation reactions process step be carried out by purifying.

higher reaction temperatures, e.g. 90 to 120 ° C, BeisDiell

and uses a longer response time so that the

Hydrogenation reaction in the same reaction zone 30. η-hexene from hexene-1

after the hydroformylation reaction take place A complex compound of the formula

^can (CK Λ Ri ₁ Pi

. The hydroformylation reactions gave in ^ _e xa ₅ ; ₃ x ^ uv_i3

primarily a product which was obtained by α-addition initially by mixing 3 molar others Elements of formaldehyde or formic acid 35 share triphenylphosphine with 1 molar proportion of rhoane the olefinic bond, d. H. made by anti-mudium trichloride in ethanol. To a Lökownikow addition, is formed. However, it occurs in solution of 0.25 g of this complex compound as Katageringem Extent also / 3-addition, so that the lysator in 30 ml of ethanol were 20 ml of benzene and Product generally a mixture of isomeric 10 ml of hexene-1 is added. Then water aldehydes or carboxylic acids. But this is often introduced into the solution and the complex is not real disadvantage, as the mixture is often used as a compound at 25 ° C for 20 hours in such a place can be used e.g. B. held for the preparation closed vessel, the manometer of Alcohols for use in the manufacture of pressure was 0.5 at. The distillation of the reaction of Plasticizers or for the preparation of acids mixture yielded η-hexane in 95% strength. Yield.-for the application in paint drying substances where 45

Mixtures of substances are not detrimental, examples

Optionally, the mixture can be separated. _TT ■ ·, ■ _ _T , ·,,

The process is carried out in a liquid reaction- n-heptanol from n-heptaldehyde

medium carried out, which generally added to the solution of 0.1 g of the in Example 1

Solvent or additional solvent for 50 catalyst complex compounds in 2 ml containing the catalyst complex compound, but also ethanol, 2 ml of benzene and 3 ml of n-heptaldehyde were added from the unsaturated organic reaction part. Hydrogen was introduced into the solution of the recipient or the complex compound which formed in the course of the reaction and which can exist in a product that is formed. The complex ^ closed vessel at HO ⁰ C for 12 hours with a connection must in the liquid reaction medium 55 manometer pressure of 60 at was maintained. Which be solved. The reaction is preferably carried out with moderate distillation of the reaction mixture yielded n-heptanol at elevated temperatures and pressures, in 95% yield,
so are z. B. Temperatures from 50 to 150 ° C, especially from 60 to 100 ° C, and pressures from 5 to 100 at B is ρ ie 1 3 'very suitable. The conditions are said to be 60 hydrogenation of hexyne-1 '
be that the reaction mixture remains liquid during the entire course of the reaction. Itself It became a complex of the formula
developing pressure is therefore suitably t / q jj \ ^ _g i Rj ₁ Q
applied. The progress of the reaction can be ^{β 3 3}
in the usual way by observing the consumption 65 by mixing 3 moles of triphenylarsine and one of hydrogen and / or carbon monoxide followed by moles of rhodium trichloride in ethanol, being prepared. the complex compound crystallizes out of the solution

The amount of catalyst present is not sated. 4 mg of this complex compound were used as

9 10

Catalyst dissolved in 4 ml of benzene and 3.2 g of hexyne-1 the reaction mixture in an autoclave for 12 hours

admitted. In this mixture in an autoclave at 65 ° C under a hydrogen pressure of 40 at

was heated at room temperature hydrogen with 65 at and a carbon monoxide pressure of 60 at.

Initiated 12 hours. The distillation of the reac- The separation of the reaction products by fract-

tion mixture gave η-hexane in quantitative Aus 5 tioned distillation gave n-heptaldehyde in 40%

prey. Yield and 2-methylcaproaldehyde in 25%

Example 4 yield.

Hydroformylation of Hexene-1 Example 8

G To a solution of 0.15 in Example 1 manufacturers xo hydroformylation of octene-1

Asked complex compounds as a catalyst in It became a catalyst complex compound

a mixture of 2 ml of ethanol and 2 ml of benzene by dissolving 0.125 g of rhodium trichloride tri-

4 ml of hexene-1 was given. In an autohydrate and 0.27 g of tin (II) chloride in 4 ml of ethanol

Sluggish reaction mixture was prepared for 12 hours. 4 ml were added to the catalyst solution

Hydrogen and carbon monoxide are added separately at a 15 octene-1 and the mixture in one

Manometer pressure of 40 or 50 atm was initiated, while autoclave was under hydrogen pressure for 16 hours

rend the temperature of the reaction mixture at 55 ° C of 40 at and a carbon monoxide pressure of 50 at

was held. Subsequent distillation of the reac heated to 65 ° C. The distillation of the obtained

tion mixture gave n-heptaldehyde in 70% solution gave a mixture of C ₉ aldehydes in

Yield and 2-methylcaproaldehyde in 15% total yield of approximately 50%. The Ver-

prey, the latter connection being made up of the ratio of straight-chain to branched-chain alde ^ -

β- addition of the elements of formaldehyde in the hyden was 2: 1. - ^ ₁

Hydroformylation reaction had arisen. . . V *

. : .ii ■ -.... - Example 9 ...:.

■ '... :. B e i s ρ i e 1 5. 25 ". .

. .. hydroformylation of hexene-1 with.

Hydroformylation of hexene-1 followed by hydrogenation

A complex of the formula A complex was formed in which 0.25 g

UC HS AslPtri rhodium trichloride trihydrate and 0.54 g stannous chloride

l ^ nsh ^ itr ^ h _{30 were dissolved in 20 ml of} ethanol. -To this solution

by mixing 3 moles of triphenylarsine and platinum, 10 ml of hexene-1. added, and the reaction

chloride (PtCl ₄ ) in ethanol and the crystallization mixture was then stored in an autoclave for 16 hours.

posed. 100 mg of this complex compound were the under a hydrogen pressure of 30 at and one

in. 4 ml of benzene, dissolved and added 3.2 g of hexene-1. Carbon monoxide pressure from 45 at. Heated to ... 90 ° C.

This mixture was placed in an autoclave at a temperature of 35 under these conditions of high temperature and

Hydrogen pressure from. 40 at and one carbon- extended reaction time occurred in 2 stages-

monoxide pressure of 45 at 12 hours at 7O ⁰ C heated. consecutive. Hydroformylation hydrogenation

Fractional distillation of the reaction mixture reacts, and n-heptanol in 30% strength

revealed. n-heptaldehyde and 2-methylcaproaldehyde in yield and 2-methylhexanol in 15% yield

• 8: 5 ratio obtained with a 40 total aldehyde yield. ,. . . · .. ·.

95% of theory. ..... Example 10

B e i s D i e 1 6 hydrogenation of acetylenic compounds

Hvdroformvlierune von Hexen-1 ^{A 3: 1 molar} complex of triphenyl- ( _K

nyaroiormyiierung of "exen ι ^ _{phosphine and Rhodiumtr} i _ch i _ORID. ((Ph ₃ P) ₃ RhmCl _a )

A complex compound of the formula as _a catalyst by suspending 2.0 g of fine

IYPh KtP ^ R7i ri in * i ground rhodium trichloride trihydrate and 12 g

L <rn ₂ / «r,> _e * u ₂ ^ i3. | ^ J triphenylphosphine in 40 ml. Methanol, stirring the

was made from an ethanolic mixture of 4 moles of mixture at room temperature for. 90 minutes,

Ethyldiphenylphosphine and 1 mol of rutheniumtrl · · 50 then filter off the brownish product

Chloride crystallized out. To a. Mixture of precipitate of the complex and washing with

50 mg of this complex compound as a catalyst, 50 ml of ethanol and 50 ml of diethyl ether for removal

dissolved in 2 ml of ethanol and 2 ml of benzene, were produced by unreacted reactants.

4 ml of hexene-1 at 70 ° C under hydrogen pressure No further purification was necessary,

of 40 at and a carbon monoxide pressure of 40 at 55. 0.25 g of catalyst were added to 25 ml of benzene

admitted. The distillation of the reaction mixture, dissolved 30 to 50 ° C and added 25 ml of ethanol,

yielded n-heptaldehyde and 2-methylcaproaldehyde in and then 0.1 mol of the following

Ratio 8: 5 with a total aldehyde yield of th acetylenic compound. Out of the solution

95% of theory. . . The air was removed by a stream of nitrogen

^ Ph = C ₆ H ₅ JjAt = C ₂ H ₅ . 60 and hydrogen in the reaction system with a

'"■ total pressure of about 50 cm of mercury introduced,

Example 7 while stirring the mixture. After about

_TT j. ■,. _{TT Λ} .12 hours, there was no further absorption of

Hydroformylation of hexene-1 hydrogen. The mixture obtained was chromato-

! A complex compound was graphically analyzed by dissolving 65 and it was found that

ivon 0.25g rhodium trichloride trihydrate and 0.54g .the acetylenic compound to a mixture of

Tin (II) chloride in 20 ml. Ethanol as a catalyst, corresponding olefinic and saturated carbon

; formed .. To this 8 ml of hexene-1 were added and .hydrogen had been reduced. The reaction

mixture could be separated by fractional distillation.

Many acetylenic compounds were subjected to the above procedure. It was found that they were reduced in the following order as the reaction rate decreased:

3-methyl-3-hydroxy-butyne-1;
S-methyl-S-hydroxy-pentine-1;
Hexyne-1-ethinyl-1-hydroxy-cyclohexane;
1,5-dihydroxypentin-2 and acetylene.

It was also found that a higher hydrogen pressure could conveniently be used, e.g. B. a pressure of 50 to 100 atmospheres, and that when using excess hydrogen the reduced end products is essentially the saturated hydrocarbon. The hydrogenations yielded almost quantitative yields (95 to 100% of theory) of the reduced end products.

B is ρ ie 1 11
Hydroformylation of hexyne-1

0.1 g of the catalyst prepared in Example 10 was dissolved in 4 ml of benzene and 4 ml of hexyne-1 were added. The solution was placed in a small autoclave which was filled with a mixture of hydrogen and carbon monoxide (molar ratio 1: 4) at a total pressure of 120 atmospheres. The reaction had ended after 16 hours at HO ^{0 C.} From the reaction product, n-heptaldehyde was isolated in a yield of 10% and 2-methylcaproaldehyde in a yield of 10%.

B e i s ρ i e 1 12

Reduction of hexene-1 with (Ph ₃ P) ₃ Rh ¹ Cl catalyst

Triphenylphosphine and rhodium trichloride were refluxed in a molar ratio of approximately 5: 1 in ethanol for 2 to 3 hours. Upon cooling, purple crystals of the complex (Ph ₃ P) ₃ Rh ¹ Cl were obtained in an actual quantitative yield based on the rhodium value. The crystals were separated off, washed with a little cold ethanol to remove the excess triphenylphosphine and dried.

0.25 g of the catalyst was dissolved in 25 ml of benzene and 25 ml of ethanol, and 5 ml of hexene-1 to the mixture given. The solution became air

ίο removed by evacuation and hydrogen introduced into the system at a pressure of 50 cm mercury. It was observed a uniform uptake of hydrogen, and this was essentially complete after 2 hours at 2O ⁰ C. It was found that the resulting solution contained η-hexane in an almost 100% yield.

Example 13

_ao reduction of allyl bromide with (Ph ₃ P) ₃ Rh ¹ Cl catalyst

The procedure of Example 12 was repeated using 12.1 grams of allyl bromide in place of hexene-1. Hydrogen uptake was as complete after 6 hours at 2O ⁰ C, and it was found that the resulting solution containing 1-bromopropane as a result of quantitative hydrogen uptake in nearly 100% yield.

B e i s ρ i e 1 e 14 to 19

Hydrogenations containing ruthenium
Complexes

A solution of a complex of the formula given in Table I below in a mixture of

Ethanol and benzene in amounts as also indicated in the table, with 4 ml of hexene-1 in one Given a stainless steel autoclave. The autoclave was then given the indicated value with hydrogen Pressure charged, and after the specified time at room temperature, the respective contents of the Analyzed autoclave and the percentage of hexene-1, which had been hydrogenated to hexane, determined.

Formula of the complex complex solution
Ethanol resources
benzene water Reak Around example (s) (ml) (ml) material
pressure ions
Time Wall
lung Ru (Ph ₃ P) ₂ Cl ₃ · MeOH *) (a) 0.1 2 2 (Atm.) (Hours) (%) 14th [Ru (Ph ₂ EtP) ₁ Cl ₃ ] Cl **) (b) 0.1 3 3 55 15th 70 15th Ru (Ph ₃ P) ₃ Cl ₃ 0.05 2 2 90 15th 90 16 Ru (Ph ₃ P) ₄ Cl ₂ 0.1 4th 2 60 18th 95 17th RutPhaPCHijCHaPPh ^ Cli, (b) 0.05 2 2 80 15th 100 18th Ru (Ph ₃ As) ₂ Cl ₃ MeOH *) 0.05 2 2 60 18th 65 19th 70 15th 60

*) "Me" = CH ₃ , "Ph" = C ₆ H ₅ -.
**) "Et" = ethyl.

(a) Complex prepared by the method of V a s k o (Chem. & Ind., 1961, 1402).

(b) Complex prepared by the method of C h a 11 and H a y t e r (J. Chem. Soc, 1961, 896).

Claims (3)

Catalysts, such as ζ. B. copper chromite or mixed claims:. Oxide catalysts, for hydrogenation, however, is due to the need for frequent replenishment 1. Process for homogeneous catalytic and, if this is practicable, rehydration or hydroformylation of unsaturated 5 generation of the spent catalyst for the Reuse of organic compounds in the liquid state is disadvantageous. It therefore existed with hydrogen or hydrogen and carbon, respectively, for a catalyst that does the hydrogenation monoxide in the presence of a solvent and such unsaturated organic compounds a complex compound of a metal that allows low temperatures and pressures Group VIII of the periodic table as a catalyst 10 and where the catalyst is homogeneous in the reaction characterized in that the medium is present. the catalyst used is a complex compound from French patent 1,300,404 a platinum, rhodium or ruthenium halo is also known that hydroformylation reactions genid and at least one ligand used at moderate temperatures and pressures in other 15 essence of a complex can be carried out as a catalyst, which in the molecule an over- a) in the case of hydrogenation, an organic transition metal with an atomic number of 23 to 32, 40 to bond is a phosphorus or arsenic 51 or 57 to 84 and at least one molecule of one atom with a lone pair of electrons biphyllic ligand (J. Am. Chem. Soc. 82, 1960, contains, or so p. 787) with trivalent phosphorus, arsenic or b) in the case of hydroformylation a tin (II) - ^has ^ ™ ^can J> ^ ^but shows are halide ^{"is a} ^ ^cne complexes not Dikobaltocta- carbonyl and a phosphine or arsine ligand wherein the complex compounds are formed the general for the acceleration of a hydro-formula . 25 formylation reaction are ineffective. L _B M "Xi / Furthermore are from the German interpretative document 1146 485 complexes of dicobalt octacarbonyl and has, in which L the ligand, as defined above as a catalyst for an aromatic phosphite, M platinum, rhodium or ruthenium, hydroformylation reactions are known, but X represents a halogen atom or a pseudohalogen group requiring relatively high temperatures and pressures, η the number of existing and relatively easily poisoned. In the case of hydro-ligand molecules, y the number of formylation of olefins present, it is often desirable to obtain high halogen atoms and / or pseudohalogen groups proportions of straight-chain and low proportions of branched ones and is at least 1, and ν is the valence isomeric hydroformylation products, state of the metal M and y is equal to 35. In this regard, the known complexes leave something to be desired when M = Ru. ν the value 2 or 3 and η the value 3 or 4, It has now surprisingly been found that when M = Rh certain easily producible soluble halogen or ν the value 1 or 3 and η the value 3 Pseudohalogen-containing complexes of halogen and at M = Pt 4 ° the or pseudo halides of platinum, rhodium ν and η the value 2 or ruthenium as catalysts for both to have. Hydrogenation of unsaturated organic bonds 2. The method according to claim 1, characterized in that a catalyst for the generalization of olefins is effective when it is used in one of my formula (R ₃ Z) ₃ Rh-X, in which 45 homogeneous, liquid reaction medium applied R ₃ Z a tertiary organic phosphine or arsine. They are suitable for carrying out hydrogenations at and X is a halogen atom or a pseudohalogen room temperature. With hydroformy group means. lations become surprisingly high ratios 3. The method according to claim 1, characterized by straight-chain to branched isomeric hydrographs, that the catalyst obtained the formula 5 ° formylation products. [Rh ₂ Sn ₄ Cl ₁₀ ]. The “halide” used here is preferably Chlo ride, bromide or iodide and called "pseudohalides" cyanides, cyanates and thiocyanates. The inventive method for homogeneous . 55 catalytic hydrogenation or hydroformylation unsaturated organic compounds in the liquid The invention relates to a method for the homo- state with hydrogen or hydrogen and Kohgene catalytic hydrogenation or hydroformylene monoxide in the presence of a solvent and lation of unsaturated organic compounds. a complex compound of a metal of the group It is known from British patent specification 942 435-60 VIII of the periodic system, hydrogenatable organic compounds in the fact that the catalyst used is a complex presence of certain complex compounds from a compound of a platinum, rhodium or dicobalt octacarbonyl and organic phosphine - To hydrogenate ruthenium halide and at least one ligand or arsine compound as a catalyst. used that either
The use of these catalysts often requires 65 a considerable hydrogen pressure and increased a) in the case of hydrogenation an organic compound temperature, and in many cases the catalysis is made up of a phosphorus or arsenic atom Sator poisoned quickly. The application of heterogeneous contains a lone pair of electrons, or