DE2303118A1 - PROCESS FOR THE PRODUCTION OF STRAIGHT CHAIN FATTY ACIDS AND THEIR ESTERS - Google Patents

Description

P ^ tentassessor Hamburg, 1 January 1973

n _r .G.Schupfner ^φ 73003 (TV7P, 382- ^ ¹⁾

TWTTTSCHE TEXACO AG. -

2000 Hamburg 76
Sextuple gate 2

TEXACO OEVELOPMENT CORPORATION 135 East 42nd Street New York, N.Y. 10017 UNITED STATES.

Process for the production of straight-chain fatty acids and

their esters

The invention relates to a method for producing straight-chain Fatty acids and their esters. More specifically, the invention relates to a method for making straight chain Fatty acids or esters by carboxylation of <λ -olefins.

Among the well-known general processes for the production of saturated * Straight-chain carboxylic acids include the oxidation of primary alcohols or aldehydes, the catalytic ^ hydrolysis of nitriles and the conversion of Grignard reagents with COp. Special procedures for certain acids are e.g. Fermentation, the acetoacetic ester synthesis, the malonic ester synthesis and the Reformatzky's reaction.

In recent years O ^ olefins have been used in larger quantities are available relatively cheaply from paraffin cracking as a starting material for fatty acid synthesis recommended. "^ he carboxylation of olefins in the presence of metal carbonyls or carbonyl precursors for the production carbonic acids or esters have long been known, but the So disgusting and iron salts have their carbonyl precursors

309833/1168

some major drawbacks, such as high toxicity of the of, carbonyl type, the generation of a variety of undesirable By-products from polymerization, isomerization and reduction of the olefins and, most importantly, the production of large quantities of branched isomeric acids in addition to the desired one straight chain fatty acid product.

It is known that the formation of polymers, isomers and reduction products can be kept to a minimum by using alternative catalyst systems under mild reduction conditions, but none of the above-mentioned catalyst systems offers the desired combination of γοη excellent yield of straight-chain fatty acid products and high olefin conversion.

The invention is based on the object of providing a method create, according to which fatty acids or fatty acid esters can be obtained in good yields and in which practically none By-products arise.

The object is achieved by a process for the production of aliphatic straight-chain fatty acids and their esters, which is characterized in that (p ^ .one or more o ^ -olefins in the presence of a (b) homogeneous ligand-stabilized palladium - (H ) - or platinum - (H) -halogeniri and a halide of a metal pus of influenza IVB of the periodic table (PS), wherein the ligand contains a donor atom pus of group VB or VIB of the PS, with (c) an at least stoichiometric amount «* -Olefin related, a hydroxyl group-containing compound and (d) an at least stoichiometric amount, based on O ^ -olefin, heated carbon monoxide at elevated pressure. *) Catalyst, consisting of a

The term "Group IVB, VB and VIB" is used herein in accordance with that described by F.A. Cotton and G. Wilkinson in "Advanced Inorganic Chemistry "2ηη.Γ, ά. (1966) given definition used,

309 «33 / 1U3

Sgeriäsfien in the practice of the method provides ^for erfindun one linear paraffinic acids or Kster these acids with at least 4 0 atoms are prepared by one

a) each mole of ot-olefin to be carboxylated with at least a reactant containing hydroxyl groups (preferably water), at least a catalytic amount of a homogeneous, Tiigand-stabilized platinum (II) - or palladium (II) catalyst, which with an excess of a metal halide of a metal of the group ITB is complexed in an oxygen-free environment in a carbon monoxide atmosphere Pressure mixed, and.

b) the resulting pressurized reaction mixture hitzt preferably to a temperature of 25 to 12O ⁰ C ER> until the carboxy Ii augmentation of C ^ -Olefin.- the desired linear pa? affinischen carboxylated product has passed.

In the formation of the straight-chain fatty acids by the process described above, the one containing hydroxyl groups Reactant an at least stoichiometric amount of water. In the formation of the corresponding solid the straight-chain paraffinic Carboxylic acids is that. hydroxyl group denote-containing reactant an at least stoichiometric amount of one jsraffinian straight-chain or cyclic alkanol, glycol, polyol, phenol, substituted phenol or a mixture thereof.

l . Process sequence and modifications:

In general, the components of the carboxylation reaction mixture, consisting of an inert solvent to be used optionally, water or another one containing hydroxyl groups C o reactants, C ^ .- olefin and catalyst, can be added in any order desired while stirring is sufficient to form a homogeneous reaction mixture is guaranteed. For example:

1 . The catalyst can be preformed and then used for I-: i wOhunp-the other components are added to

309833/1168 - ⁴ ~

to form the reaction mixture.

2. To avoid stability problems with the Kntalypptor Keeping a minimum is preferred to be done by the K «t ° lysp.tor formed in situ, usually in the presence of an excess of the halide of the metal of Troop IYB, after which the ligand-stabilized plptin (TT) or palladium (II) salt is added to the reaction mixture to build.

3. After one of the two variants 1) or 2) has been applied, the reaction mixture containing the catalyst is with carbon monoxide, pressurized and heated. If water is present in the reaction mixture, is the main product; a straight chain fatty acid that has one more carbon atom than the OL-olefin. If an alkanol is present, the corresponding ester of the carboxylic acid is formed. The formation of the ester is twofold useful, on the one hand because of the purpose of the product and on the other hand because of its lightness, quickly obtain a chromatographic analysis.

4. After using one of the variants 1) or 2) the Catalyst solution containing the ot-01efin and either water or containing an alkanol, first heated in an inert atmosphere or under weak CO pressure (e.g. 0.7 - 7 atmospheres) and then pressurized to the desired extent with carbon monoxide to the desired straight chain fatty acid or the ester.

5. Optionally, after having the catalyst in situ in a solvent, the water or another Contains hydroxyl reactants, has formed, to the required temperature under inert .Heat atmosphere or under a lower CO pressure than required, and then the olefin and others Add carbon monoxide together and maintain the required CO pressure until the ester (or the free Acid) is formed.

309833/1168

B. Day-end stabilized platinum (II) or palladium (II)

Catalyst complex:

The use of Τ, ΐρ- ^ nden-sta.-bilized is essential to the invention Platinum (II) or PalladiumuF> (TT) catalyst systems, complexed with a halide of a Group IYB metal. The donor elements of the ligands can be: nitrogen, arsenic, antimony, bismuth, sulfur, selenium and phosphorus. Examples of ligands used for Stabilizing catalysts that can be used are:

P (P-CH ₃ -C ₆ H ₄ ) ₃ , P (nC ₄ H ₉ ) ₃ , ₃₅₆₅₃ V2 »(G ₆ H ₅ ) ₂ As (CH ₂ ) ₂ As (CgH ₅ ) ₂ , P (OC ₆ H ₅ ) ₃ , S [OgH ₅ I ₂ , SefCgH (-} ₂ , pyridine, ethylenediamine and 1,1O-phenanthroline.

Examples of Group IVB halides stabilized with the ligand Platinum (II) or palladium (II) complex Can be bound to an active Cp.rboxylierungskatalysator to form are: tin (II) chloride, tin (II) bromide, Tin (II) iodide, tin (IV) chloride, lead chloride, Germanium (II) chloride, germanium (II) bromide and lead iodide.

C. Ligand Stabilized Platinum (II) or Palladium (II) Metal II of Group IVB Halide Catalyst Complex: The following complexes are some of the many ligand stabilized complexes which can be used in the process of the present invention : PtCl ₂ CAs (CgH ₅ ) ₃ } ₂ -SnCl ₂ , P
PtBr ₂ [As (CgH ₅ ) ₃ ] ₂ -SnBr ₂ ,
PtCl ₂ [Bi (CgH ₅ ) ₃ ] ₂ -SnCl ₂ , PtCl ₃ [P (g ₅ ^ PtCl ₂ [P (C ₂ H ₅ ) ₂ (CgH ₅ ) J-SnCl ₂ , PtCl ₂ [As (nC ₄ H ₉ ) ₃ ] ₂ -SnCl ₂ , PtCl ₂ [(CgH ₅ ) ₂ P (CH ₂ ) ₂ P (CgH ₅ ) ₂ ] -SnCl ₂ , PtCl ₃ [(C ₅ H ₅ ) ₂ As (CH] I PtCl ₂ (I, 10-phenanthroline) -SnCl ₂ ,

₂₄₉₃₃₅ PtCl _? [p (P-CH ^ .CgH ₄ ) J ₂ -SnCl ₂ , PtCl ₂ [NH ₂ (CH ₂ ) pNH ₂ ] -SnCl ₃ , ^ Clj ,, ""'""' _

309833/1168

as well as the corresponding stannoyl chloride or chloride complexes and certain germanium (II) chloride comr> lexes: PdCl _p CP (C ₆ H ₅ ) ₃ J ₂ -SnCl ₂ , PdCl ₂ [As (C ₆ H ₅ ) Ji ₉ -WiI ₇ ,

PdCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ -QeCl ₂ , PdCl ₂ CP (C ₂ H ₅

PdCl ₂ CP (P-CH ₃ .C ₆ H ₄ ) (C ₆ H ₅ ) P ₂ -SnCl ₂ , PdCl ₂ CP (P-CH ₃ .C ₆ H ₄ ) ₃ ] ₂ SnCl ₂ , PdClC () ( ) ()> PdCl ₂ CAs (CH ₃ Y _? C ₆ H ₅ Jp-SnCl ₂ or

_? C ₆ H ₅ Jp-SnCl ₂ or PdCl ₂ CP (CgH ₁₁

The ligand-atabilized platinum (II) metal of the group IVB halide complexes are known from the literature and methods for their preparation are described, for example, by ROCramber et al., J.Amer.Chem.Soc., 85., 169I, ( 1963). A convenient way to prepare them in situ is to mix a solution of a platinum (II) halide complex, such as PtCl ₂ CP (CgHc) ₃ J ₂ , or a palladium (II) halide complex, like PdCl ₂ CP (C ₆ H ₁ -) 3) 0 » ^m ^ a large molar excess of a halide. Metal from group IYB, preferably SnCl ₂ or GeCl ₀ . Although no structural formula is advocated nor the success of the catalyst presupposes a given structure, it is believed that a typical ligand-stabilized platinum (II) or palladium (II) stannous chloride complex, such as triphenylsrsine or triphenylphosphine complexes, can be reproduced as follows:

and
Ace '
wherein 0 is the symbol for C ₆ H ₅ -.

Ώ. Ratio of stannous halide to ligand-stabilized platinum (II) or palladium (II) catalyst: Although the molar ratio of stannous halide to ligand-stabilized platinum (TI) or Pp ".lladium (TI) halide is not

3098 33/1168

is critical, the practical work shows that at least one mole of stannous chloride per mole of platinum (IT) -hnlogenid complex or palladium (II) halide complex is required for reproducibility and good selectivity. A Ratio of 5 "to 10 moles of stannous chloride per mole of platinum (II) or palladium (II) complex is preferred to be a to obtain optimal amount of straight chain fatty acid ester. See Tables VI and VII.

E. Ratio of ligand stabilized platinum (IT) or Palladium (II) halide catalyst complex to the substrate <** -olefin:

Experimental work shows that a molar ratio of up to 500 moles or even 1000 moles of W-olefin per mole of platinum (II) or palladium (II) catalyst complex can be used in most cases in which <λ -olefin (e.g. 1-heptene) is used as a substrate. Much smaller ratios (ie, 25 moles of olefin substrate per mole of catalyst complex) are not harmful, but are less economical. For this reason, the preferred range achieved in Tables VI and VII is 50 to 200 moles of olefin TDroA catalyst complex.

Mole

F. Temperature required for carboxylation: The temperature that can be used for carboxylation is variable, depending on experimental factors, including the <K -olefin used, the carbon monoxide pressure used, the concentration and the particular catalyst chosen. If, for example, 1-heptene as oc olefin and PtCl (As (C ₆ H ₅₎ ^) ₂ -SnCl ₂ and PdCl ₂ ^ as typical catalysts, the applicable temperature range is from 25 to 125 ⁰ C, if at pressures from 141 atü is worked. A narrower range of 60 to 9O ⁰ C for platinum catalysts and from 60 to 80 ⁰ C for palladium catalysts represent the preferred temperature range, when the above-mentioned olefin at 141 atm is carboxylated using the catalyst systems described above. From table .XII

309833/1168

this narrow area can be seen.

G. Pressure:

Pressures of at least 7 atu are required for a substantial implementation of the Qc. Olefin to the carboxylic acid (or ester) at temperatures from 25 to 120 ⁰ O using PtCl ^ s (CGH ₅₎ ^ ₂ - "n01 ₂ or PdCl ₂ CP (CGH ₅ J SnCl ₂ as the catalyst and 1-Heptei as OC-Olefin. Tables X and XI provide the experimental data showing that pressures of 281 atmospheres and above reduce the selectivity for the linear ester when platinum catalysts are used while palladium catalysts are used at. "Pressures decompose above 211 atmospheres, and the carboxylation is too slow in practice at pressures below 7 β tu

H. Required response times ;

As noted in the discussion of temperatures and • pressures above, the experimental variables are for the achievement of reaction speeds is important. In general, good conversions (70 '^ or above) the olefins to the straight-chain carboxylic acids .almost always be reached within .6 hours. The more common Response time is 2 to 4 hours.

I. Alpha (OC) olefins as substrates ;

• OV.-olefins with three to 40 carbon atoms can be used. Examples of straight-chain Ot olefins are: 1-propene, 1-butene, 1-pentene, 1-heptene, 1-Og th, 1-hone, 1-decene, 1-undecene, 1-tetradecene and its higher homologues such as 1-heptadecene, 1-octadecene, 1-eicosene, tricosene and 1-pentacosene. Branched OL olefins can also be carboxylated. Of course, these must have at least 4 carbon atoms to have. Examples of branched Otolefin substrates are 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene and ^, G ^ - ^ iöthyl-i-decen. These olefin substrates may include alone or in conjunction with one or more solvents such as saturated paraffins

309833/1168

lent pentanes, hexanes, heptanes and octanes and the like can be used. The W.-olefins can be in the form of individual, discrete compounds or in ^ orm of olefin niches. In the latter case, they are mixtures of C 1-10 olefins. Usually these mixtures have a range of 4 to 8 O atoms. Because of their relatively low cost, mixtures of OC olefins with 5 to 15 O atoms are suitable. Atoms and more are the preferred substrates for the carboxylation in which the ligand-stabilized homogeneous catalysts are used at sufficiently elevated temperatures and pressures.

J. Oo reactants containing hydroxyl groups:

As used herein, this term refers to water and other hydroxyl containing reactants which have at least one OH group that is labile enough to produce the desired carboxylated product during the carboxylation reaction. The physical state in which the hydroxyl group-containing reactant is present is not essential; it can be a liquid or a solid. The other essential criterion is that it be dispersible or soluble in the reaction mixture so that the carboxylated product can be formed. Suitable co-reactants containing hydroxyl groups are, for example, water, urinary and secondary alcohols, including methanol, ethanol, n-propanol, n-butanol, isopropanol, cyclohexanol / dodecanol, phenol and substituted phenols, substituted alcohols such as 2-chloroethanol and polyols including ethylene glycol, propylene glycol, glycerin, sorbitol and the like. In order to obtain the free acid, water must be used as the reactant containing hydroxyl groups in the process according to the invention. Hm to obtain the esters, have one or more paraffinic or ⁵ it are wetted aromatic alkanols, glycols and / or polyols as hydroxylgruppenaufweisender paraffinic reactant.

309833/1168

The amount of water or hydroxyl group sulfate for the reactant, which is required depends on the concentration of the olefin to be converted into a carboxylated product away. To achieve maximum yield, an at least stoichiometric amount of "hydroxyl" reactant (as above specified) »based on <*. -Olefinje be used. this excludes water as well as alcohols, glycols and polyols a.

The preferred and only suitable reactant for the generation of free acid is water; the preferred Hydroxyl-containing reactants for the production of esters are the lower alkanols, especially those with 1 to 12 carbon atoms »

K, carbon monoxide environment:

As far as it can be determined, the best selectivities and conversions of α-olefins to straight-chain fatty acids can be obtained within an acceptable time using a gas atmosphere consisting essentially of carbon monoxide. The carbon monoxide can, however, especially with continuous operation, in connection with about. 0 to 30

inert
Vol .-% of one or more nerve gases, such as nitrogen, argon, neon and the like are used without the yield and selectivity declining noticeably.

L. Inert solvents:

The carboxylation according to the invention is best described in Carried out in the presence of an inert diluent, e.g. an aromatic hydrocarbon such as benzene, toluene or xylene; an aromatic halogenated hydrocarbon, such as o-dichlorobenzene; of a ketone such as acetone or methyl isobutyl ketone, an ether such as dimethoxyethane or dioxane; or a halogenated paraffin, such as methylene chloride.

M. Selectivity:

309833/1168

This means how effectively a desired carboxylation reaction to the straight-chain fatty acid or ester is catalyzed relative to other undesirable carboxylation reactions. Selectivity is given in percentages and the amount of straight-chain carboxylated product formed divided by the total amount of carboxylated products formed and multiplied by 100 .

N. Sales:

This means the efficiency that cV, -olefin in transferring non-d-01efin products. Sales are also in ' Percent and is the amount of the

: oxylation of OV.-olefin consumed divided by the Amount of <Λ olefins originally used, multiplied with 100.

0.. Yield:

This is the performance, the desired carboxylation reaction to the straight-chain fatty acid or the ester ^{, preferred over all other undesirable reactants;} catalyze actions. The yield is given as a percentage and is the amount of straight-chain carboxylation product formed, divided by the amount of ■ «» • olefins used, multiplied by 100. * ·

P. By-products:
^: As far as it can be determined, the carboxylation of ot -olefins using the ligand-stabilizing-

_o only

th catalysts for the formation of two minor by-products. These are φ) olefins for which as a result Isomerization of the Ot olefin the double bond is moved inside, and b) branched (2-methyl) acids or Esters as a result of CO addition to the second carbon atom of the Ot-olefin. For experiments carried out under different conditions, the amount of by-products formed is (usually under 10 ^.) in the tables below below percent isomerization and percent more straight-chain

309833/1168

Ester (calculated from: total straight-chain ester / total straight-chain + branched ester).

The by-products can be of the desired p-chain Fatty acid or the ester by the usual chemical and physical techniques, such as distillation, solvent extraction, be separated.

example 1

1A A reactor with stirring, heating, cooling and pressure devices was charged with 100 grams of dimethoxyethane, 10 grams of methanol (313 moles) and 10 grams of 1-heptene (108 moles). The liquid mixture was degassed and then 2.24 grams (10 moles) of stannous chloride dihydrate and then 0.88 grams (1 mole) of bis (triphenylarsine) platinum (II) chloride were added with stirring. After all the solids had dissolved, the reactor was closed, brought to a pressure of 211 atmospheres with carbon monoxide and ^{heated to BO 0} C- for 3 hours. The reaction was terminated by cooling the reactor and venting the gases, after which the red solution was distilled to obtain methyl caprylate.

When the reaction is carried out as described above except that methanol is replaced by ethanol, isopropanol, Phenol, dipropylene glycol, 1-dodecanol, 2-chloroethanol or cyclohexanol, is replaced, the corresponding esters of caprylic acid are obtained.

1B The same procedure was repeated except that the catalyst (formed as in 1A in situ), the deaerated solvent of dimethoxyethane (100 grams) and methanol (10 grams), heated atm at 8O ⁰ C with stirring under a carbon monoxide pressure of 7 . The 1-heptene (10 grams) was then added to the catalyst-solvent mixture with stirring, the reactor sealed and pressurized to 211 atm with carbon monoxide.

The distilled product was methyl caprylate.

309833/1168

Example 2

2Λ A reactor was filled with 100 grams of methyl isobuty ¹ . ketone, 10 grams of methanol (313 mmol) and 10 grams * 1-Fepten (mmol). The liquid mixture was debris, then 2.24 grams (10 mmoles) of stannous chloride hydrate and then 0.70 grams (1 mmoles) of Bxs (trinhenylphosphine) palladium (IL) chloride were added with stirring. ITpchdem all solids had dissolved, the reactor was sealed and brought atmospheres gauge with carbon monoxide to a pressure of 141 and heated for 4 hours at 7O ⁰ C. The reaction was stopped by cooling the reactor and venting the gases, after which the red solution was distilled to give methyl caprylate, [ΟΗ, ίσ ^^ ΟΌΟΟΉΛ, in $ 93 (15.0 grams) yield.

2B The same procedure was repeated, except! that the catalyst (formed in situ as in'2A) and heating the deaerated solvent methyl isobutyl ketone (100'Gramm) and methanol (10 grams) at 70 ⁰ C with stirring under a slow C0 "0ruck (0.7 to 7 atmospheres gauge) , 1-heptene (10 grams) was added to the catalyst-solvent mixture with stirring, after which the reactor was tightly closed and pressurized to 141 atm with carbon monoxide. The distilled product was methyl caprylate.

Example 3

A The same procedure was used as in Figure 1A, except that 5 grams (280 moles) of water was used in place of 10 grams of methanol. The other peak Tanden, catalyst components and solvent were used in the same amounts as in 1Λ, sealed • the reaction mixture, gebrpcht atm to a pressure of 211 and heated for 3 hours at 90 ⁰ C. Dp's product was cpprylic acid, [θΗ, (σΗ ₂ ) ₆ σθΟ ^, contaminated with a small amount of 2-riethyl-heptanoic acid.

309833/1168

-H-

B 'The same procedure was used as in Example 1A, except that 5 grams (280 mmol) of water was used in place of methanol. The other reactants, catalyst components and solvents were used in the same amounts as in Example 1A, the reaction mixture was tightly sealed, brought to a pressure of H1 atm and ^{heated to 70 °} C. for 4 hours. The product was caprylic acid contaminated with a small amount of 2-methyl-heptanoic acid.

Example 4

The procedure according to Example 1A was repeated exactly, also the molar ratio of 1-heptene to catalyst v / ar the same, except that the stenum chloride component of the ligand-stabilized platinum (II) catalyst is gone 'was left. There was no methyl caprylate in the product solution to be established.

Similarly, the procedure of Example 2A was followed exactly, except that the stannous chloride component of the ligand-stabilized palladium (II) catalyst was omitted. The 1-heptene conversion was almost complete, but the product consisted of the 2-methyl-heptanoic acid methyl ester, CCH ₃ (CH ₂ ) .CH (CH,) COOCH ₃ ], (5.0 * grams, 31 $ yield) and methyl caprylate (6.77 grams, $ 42 yield).

Diea shows that the stannous chloride is an essential factor. is part of the catalysts according to the invention.

Examples 5 to 17

In Examples 5 to 12, the carboxylation was carried out on the listed olefins under the stated reaction conditions and using the in situ procedure according to Example 1A (ie at 141 atmospheric pressure, at 0O ⁰ C and using methyl isobutyl ketone as the solvent

and an excess of methanol). Examples 13 to 17

309833/1168

were, as described in Example 2Λ, carried out under a CO "pressure of 14-1 atm at 7O ⁰ C and methyl isobutyl ketone and excess methanol. Animal olefin conversion and the selectivities with regard to the ester products are given in Table I".

to see that straight-chain «L -olefins with at least 3 to 20 carbon atoms to the corresponding straight-chain fatty acid esters using the ligand-stabilized Complex catalysts can be carboxylated.

Certain branched olefins can also be carboxylated. For example, where the ov. -Olefin substituted in the 3-position is, as in 3-methyl-1-pentene, the corresponding acid ester (in this case 4-methyl-1-hexanoic acid methyl ester) obtained with very high selectivity .. Where, on the other hand, the 2-position was substituted, ^ as in 2,4,4-trimethyl-i-pentene failed to produce a carboxylation product to be established.

Examples 18 to 36

In these examples, the carboxylation on T-Heptii using various homogeneous catalysts at constant temperatures, pressures and molar ratios of Run substrate to catalyst. Methyl isobutyl ketone was used as the solvent in all experiments. As can be seen from the data in Tables II and III below, a variety of ligands can be used, including ligands that act as donor atom nitrogen, Contain phosphorus, arsenic, sulfur, selenium or antimony. These ligands can be monodentate or multidentate (monodentate or multidentate) and can contain the alkyl and aryl, aryloxy and substituted aryl groups.

Oute 1-heptene sales and octanoic acid methyl ester yields * -

309833/1168 '

were with bis (tri-phenylarsine) -platinum (II) chloride-tin (II) chloride catalyst obtained (see example 18). The highest selectivity for straight chain esters (i.e. Mo! ratio of straight-chain esters to straight-chain + branched esters) was made with bis- (triphenylphosphite) -platinum- (ΪΙ) -chloride-tin- (II) -chloride catalysts obtain.

Good 1-HeT) th sales and methyl octanoate yields even. .

Behavior with the catalysts: bis- (triphenylphosphine) -palladium - ^ (II) -chloride-tin- (II) -chloride, Bis (triphenylphosphine) palladium (II) chloride g-ermanium (H) chloride and bis- (tri-p-tolylphosphine) -palladium- (II) -chloride-tin- (II ) chloride (Examples 29, 30 and 33).

For any catalyst, the two major side reactions are :

a) Isomerization of 1-heptene to isomers with internal Double bond, mainly to cis- and trans-2-heptenes (see Table II, column 5).

b) The formation of a branched (OL-methyl) fatty acid ester (see Table II, column 6). In these experiments the by-product was 2-methyl-heptanoic acid ester. The data in Table TI for the ligand-stabilized platinum (II) -tin (II) catalysts are in contrast to those for the analogous ligand-stabilized palladium- (II) -tin- (II) -chloride-Op. Carbonation catalysts in Table III, where the complexes for PdCl ₂ (As (Gg H ^) ₅ ) ₂ -SnCl ₂ and PdCl ₂ (Sb (C ₆ H ₅ ) j) ₂ --.Is showed inactive under the same experimental conditions.

The palladium complexes, e.g. the germanium (II) complexes PdCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ -GeCl ₂ and Pd01 ₂ (As (C ₆ H ₅ ) ₃ ) ₂ -GeCl ₂ are; both active under carboxylation conditions, while the analogous platinum (II) complexes are inactive under the same conditions. On the other hand, the palladium (II) arsine stannous chloride complex shows PdCl ₂ [As (C ₆ H ^) ^] ₂ -SnCl ₂

mm I (-

309833/1168

and the iodine homologs PDJ CAa ₂ (C ₆ H ₅₎ J _{2 2} -SnJ no activity, while the same platinum (II) complexes excellent catalysts. Indeed, PTGL ₂ ^[1 As (C ₆ H ₅₎ J _{2 2} -SnCl the preferred Platinkatalysafor for the conversion of olefins in the fatty acid ester. Comparative data for the platinum and palladium catalysts are shown in Table IV.

Examples 37 to 42

In these examples, the carboxylation of 1-heptene was carried out using various combinations of triphenylarsine-platinum (II) -h-plogenide with a halide of a Group IVB and VB metal under constant temperatures, pressures and substrate to catalyst molar ratios. The values given in Table V show that stanno iodide, stanni and plumbo salts can replace the otannochloride, while (PtCl ₂ (As (C ₆ H ₅ ) ^) ₂ ) in conjunction with germanium - (II) chloride is catalytically inactive.

Examples 43 to 57

In this group of examples, 1-heptene was again identified as **. -Olefin used, and PtCl ₂ JAs (C ₆ H ₅ ) J ₂ -SnCl ₂ and PdCl ₂ [P (C ₆ H ₅ ),} ₂ -SnCl ₂ were used as catalysts. The most favorable molar ratios of stannous chloride and olefin to ligand-stabilized platinum or palladium halide with the reaction conditions kept constant can be determined by checking the following Tables VI and VII. ·

From the data provided there it can be seen that the MoI ratios from stennochloride to ligand-stabilized Platinum or palladium halide can be increased to at least 1 in 30. "The preferred range of Sn: Pt or Sn: Pd is a molar ratio of 5 to 10. The molar ratio from <*. -Olefin to catalyst can be between 25 and 1000 can be varied. The preferred range is

309833/1168 - ~ ¹⁸ "

between 50 and 200.

Examples 58 to 61

In this series of examples, 1-heptene and methanol were again used as reactants. and PtCl ₂ (As (CgH ^), J ₉ - ¹ ^ nGIp as an alcalator. The molar ratio of methanol to 1-heptene was varied between 0.5 and 25 while the reaction conditions were kept constant.

From Table VIII it can be seen that at least 1 molar equivalent of methanol to Ot-olefin is required to ensure good yields of straight-chain fatty acid esters.

It has been found that the same is true when water is used instead of methanol in the reaction mixture .wird is used to produce the straight-chain fatty acid.

Similar results were obtained with both water ^ Is also with methanol as PdCl ₂ CP (C ₆ H ₅₎ J ₂ -SnCl ₂ * ls Kataly-.sator was used as in Examples 6? through 65 listed in Table IX can be seen.

Examples 66 to 72 .

This was done using those disclosed in Example 1A Techniques and keeping the reaction temperature constant have the effect of varying carbon monoxide pressure the pentadecanoic acid methyl ester selectivity and the 1-tetradecene conversion certainly. As the data in Table X below show, the course of the carboxylation is slowly at carbon monoxide pressures below 49.2 atm, while the methyl pentadecanoate selectivity (i.e. the Ratio straight-chain / straight-chain + branched-chain, column -7) at carbon monoxide pressures of 281 atmospheres or above - as a result of the formation of further branched (2-methyl) fatty acid esters falls off. "This loss of selectivity can be partially be compensated by working at lower temperatures (Example 72). Oer preferred carbon monoxide

309833/1168

oxide printing range, based on the cheapest. Bf>ir> nce between conversion, selectivity and reaction time ⁴ -, is therefore between 141 and 281 atm. *

Examples 73 "to 78

In these examples, the techniques disclosed in Example 2 were used and the reaction time was kept constant. The influence of varying CO pressure on the yield of methyl octanoate and the 1-heptene conversion was determined certainly. As the values in Table XI show, the course of carboxylation is below 35.2 at CO pressures atüllow, while wedge noticeable advantage when working can be determined under CO pressures of 281 atmospheres and above. The preferred CO pressure range is therefore between 70 and 211 atü.

Examples 79 to 89

The techniques of Example 1A were used in these examples; the catalyst complex in Examples 79 to 84 was PtCl ₂ [As (C ₆ H ₅ ) ^] ₂ -SnCl ₂ and in Examples 85 to 89 PdCl ₂ [P (CgH ₅ ^] ₂ -SnCl ₂ held hl atm to determine the effect of varying reaction temperature on 1-heptene-Umsate and to determine octanoate selectivity. the solvent was methyl isobutyl ketone. As can be seen from Table XII, the reactions run at 6O ⁰ G slowly while check the catalyst decomposes at operating temperatures above 90 ⁰ C. The best ratios of conversion, selectivity and response time were measured at Garboxylierungsversuchen with platinum catalysts at temperatures between 60 and 90 ⁰ C and obtained with palladium catalysts at temperatures between 60 and 8O ⁰ C.

Examples 90 to 97

Here, the techniques as disclosed in Example IA were used, PtCl ₂ [As (C ₆ H ₅ ) ₅ ] ₂ -SnCl ₂ as the catalyst

309833/1168

.- 20 -

used and temperatures and CO pressures kept constant and the effect of the change in the solvent on the activity of the platinum catalyst ". How the data in Table XIII show, the oarboxyly- » tion of CL olefins stabilized by ligands Platinum (II) -tin (II) complexes catalyzed, can be run in a variety of solvents, including Ketones, such as acetone and methyl isobutyl ketone, ethers, such as dirnethoxyethane and dioxane, alcohols, aromatics and halogenated solvents such as methylene chloride.

The same results were obtained when the test series using PdCl ₂ [P (CgH ₅ ) J ₂ -SnCl ₂ as a catalyst

₂ g ₅₂₂

sator at a temperature of 70 ° and a CO pressure of .141 atü was executed.

Examples 98-103

The same procedure as described in Example 2A was used in these examples. Various <λ olefins, including 1-heptene, 1-pentene, and propylene, have been carboxylated in the presence of typical alcohols, cyclic alcohols, substituted alcohols, and polyols. The other amounts of reactants, catalyst and solvent were unchanged. The reaction mixture was tightly sealed in each pail, brought to a pressure of 141 atm and ^{heated to 70 °} C. for 6 hours.

The main products were straight-chain fatty acid esters (see Table XIV).

309833/1168

O example , Alkene Try at: 50 Table I ' Solvent., Methanol in excess 30th Methyl ester io selective. I. IO
β » with: 1-1- 50 80 ⁰ C, CO pressure 141 atm React. 7, eit alkene carboxyl, carboxylated products 51 Butyric acid 76 <*> ς Propylene Molverh. 100 Methyl isobutyl ketone as .Pd (min.) (Fo sales) 34 Octanolic acid 95 85 ' 6th 1-heptene Alkene / Pt or 100 360 29 Pentadecanoic acid 88 91 - * 7th 1-tetradecene 100 100. 360 74 *
Heneicosanoic acid > 95 90 · «D 8th 1-eicoses 100. 100 360 50 4-methyl-hexane. > 99 91 • 9 100 3-methyl-1-pentene 100 300 55 '5-methyl-hexane. 97 95 10 50 480 ¹ react. 5 ♦ 5-dimethyl-He- to - 11 3-methyl-i-pentene 50 360 90 xanoic acid Ca)
O 12th 4-methyl-1-pentene 50 360 00 Butyric acid 13th 4,4-dimethyl-i . 360 none 00 Octanoic acid 14th 2 ^ f ⁿ Trimethy 180 20th ^ entadecanoic acid 15th flew 210 1 00 Heneicosanoic acid 16 1-heptene 300 1 4-methyl-hexanes .- * 17th 1-tetradecene < 360 1-eicoses 360 1 • - "ti
**. ·

example

18 19 20 21 22 23 24 25 26 27 28

Table II '

Experimental conditions: 80 ⁰ C, a CO pressure of 211 atm, 1-heptene / Pt = 100, Methpnol / heptene = 7.6: 1 Reaction time: 360 min, Sn / Pt = 10 degrees.

catalyst

PtOl ₂ (As (C ₆ H ₅ ) ₃ ) 2-PtJ., (As (C ₆ H ₅ ) ₃ ) ₂ -SnCJ

1-heptene turnover, %

95

8.9 18 12 38

41

PtCIp (DIARS * J-SnCl ₂ PtCl ₂ (DIPHOS ** J-SnCl ₂ PtCl ₂ (1,10-PHEN *** J-SnCl ₂ - ^ tCl ₂ (P (P-CH ^ C ₆ H ₄ J ₃ J ₂ -SnCl ₂ PtCl ₂ (P (OC ₆ H ₅ J ₃ J ₂ -SnCl ₂ PtCl ₂ (P (nC ₄ Hg) ₃ J ₂ -SnCl ₂ <10 PtCl ₂ (S (C ₆ H ₅ J ₂ J ₂ -SnCl ₂ .

DIARS: bis- (1,2-diphenylarsino) -ethane DIPFOS: bis- (1,2-diphenylphosphinoJ-ethane

Ootans.-methyl ester
(Yield %)

86
3.4 '

ο ■

,,
H

7.5
32

8.4
28

4th
52

Hepten

Isomeris,
96

10

4.9
15th

<1
4.2

< 1
8.0

< 1
8.5

1,1O-PHEN: 1,1O-phenanthroline

straight chain ester

98

92> 90

90

96> 90

ro ca ο

co

OO

Table ITI example

29 30 31

33 34 35 36

- ■

catalyst

PdCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ -SnCl ₂

1-heptene sales ('/>)

100 100

PdCl ₂ (As (C ₆ H ₅ ) ₃ ) ₂ -GeCl ₂

• (p-CH ^ C ₆ H ₄ ) ₃ ) ₂ -SnCl ₂ H ₅ -C ₆ H ₄ ) (C ₆ H ₅ ) ^) ₂ H ₅ ) ₃ ) ₂ -SnCl ₂ 3.0

PcICl ₂ (P (C ₆ H ₁ ^ ₃ J ₂ -SnCl ₂ PdCl ₂ (P (CH ₃ J ₂ (C ₆ H ₅ J) ₂ -SnCl ₂

Octnns.-

Methyl ester (yield ^C 4

72

73

23

78

70?, 8 2.2

52

Hepten

Igomeris.
%

4.1
3.7
2

'. 4.7
4.7

5.8

$ straight chain ester

90

90

76

90

90

90

90

89

ΙΌ CJ O CO

OO

Table IV

A comparison between platinum and palls.dium carboxylation catalysts Test conditions: 1-heptene / M (molar ratio) = 100 Solvent: methyl isobutyl ketone

Sn / M (molar ratio) =. 10 Temperature: 8O ⁰ C

CO pressure: 211 atm; Time: 360 min.

catalyst

MCl ₂ (P (C ₆ H ₅ ) ₃ ) ₂ -SnCl

KJ ₂ (As (C ₆ H ₅ ) ₃ ) ₂ -SnJ ₂ KCl

, (Aa (C ₆ H ₅ ) ₃ ) ₂ -GeCl ₂

M = Pd

active

Inactive

Inactive

Inak-fciv

Inactive

active

active

M = Pt

Active Active Active Active Active weakly active Inactive

Table V example

37 38 39 40 41 42

Test conditions: 80 ⁰ C, CO pressure 211 atii, 1-heptene / Pt = 100,

Methanol / heptene = 7.6r1, reaction time: 360 min., '* Group IVB or VB metal / Pt =

catalyst

Pt01 ₂ (As (C ₆ H ₅ ) ₃ ) ₂ -

V3 '

1-heptene
Sales ($)
_Ι3 * ιΛ1 QC
—Onuχ2 j? , 3 Octane.
Methyl ester
(Yield %)
86 Hepten
Isomeris.
10 ^ straighter
Ester
93 —ΙτβΟχ-, *% c. , 6 - <1 " - -PbCl ₂ 7 49 <1 > 90 -SbCl, 2 , 0 - <1 - -SnCl ₄ 52 44 <3 9? SnI ₀ .. 7 3.7 <1 > 90

ro vn

CO CD CO

CO

Table VI

Example molar ratios of 1-heptene

PtCl ₂ (As0,) ₂ : SnCl ₂ : 1-Kepten conversion

43 1 44 1 45 1 30 98 46 1 e *> 47 1 "V" 48 1 σ>
OO 49 1 50 1

1 100 20th VJl 100 ■ 63 10 100 95 30th 100 • 64 10 1000 VJI 10 500 11 10 250 34 10 • 25 100

Octans .-- · Heptenes- $ straight-chain

^ ethyl ester isomeris. Ester (yield fi) #

15th
56
86
35

<5
6.0
15th
61

<1

5.9

> 90

92

93

92

90

> 90

> 90

88

sse from
: SnCl _n : 1-heptene abelle VII Octane.
Methyl ester
(Yield #) Hepten
Isomeris.
* #straight chain
Ester rhaltni 1 , 00 1-heptene
Sales (#) 35 1 86 1 5 100 ■ 43 > 90 3.3 89 1 10 100 1-00 92 7.1 . .91 1 30th 100 100 82 9.5 * 89 1 10 1000 85 36 2 93 «
ι 1 10 200 40 93 7.1 I.
93 1 100

Example Hol
PaC

53
254
^ω 55 ■

»57 1 10 25 100 '92 · 7.7 85

. Experimental conditions: CO-Oruck 141 atm, reaction time 360 minutes, reaction temperature 70 - 8O ⁰ C.

Table YIII 'Yersuchsbedingungen: 80 ⁰ C, a CO pressure of 211 atm, Beaktionszeit 360 min.

Example: 1-heptene-oct'-ns, - ^ straight-chain ratio

PtCl ₉ UsJZL) _? : SnCl ₉ : 1-heptene: methanol conversion (ti) methyl ester ester "" (yield $>) ■

58 1 10 100 2500 93 84 91

£ 59 1 10 100 750 95 86 93

03 60 1 10 100 100 ■ 93 81 94

It 61 1 10 100 50 100 34 95

00.

Example

62

H 65

Table IX
Test conditions: 7O ⁰ C, 141 atm, reaction time 360 min '.

Fiolverh ^ ltniswe von 1-Hepten- Octp.ns.-

PdOl ₀ (PjZL) ₀ : SnCl ₀ : 1-heptene: methanol conversion (^) methyl ester · ² (yield ¥>]

100
100
100
100

2500

750

100

50

100 100 100 > 9O

^ dkettiger

"Magpie

91 91 89 88

CO

O GO

OO

Table X

O CD OD

example

66 67 68

69 70

ο

72

1-tetradecene dimethoxyethane

Olefin Solvent Reaction CO-Print Tetradecene Carboxyl

temperature, C atu, Jo turnover

93 '7. <1

93 49.2 *)

93 70.3 21

93 141 '■ 31

93 211 37

93 281 41

80 352 54

1-Today pentadecane.

Methyl ester selectivity ° fo

> 9β 93 90 88 76 92

could not be determined CO O CO

Table XI

Test conditions: 1-heptene / Pd = 100 reaction temperature: 70 ⁰ O

Ethanol / heptene = 7.6 ". Time: 360 min./24 ^ßtd · Bn / Pd = 10

Example CO pressure 1-heptene-octanoic acid-heptene- ^ straight-chain atü sales ($) methyl ester isomerization ester

(Yield #) $>

73 1 68 13th 3091 74 35.2 72 45 GD 75 70.3 99 81 - ** 76 141 100 92 σ » 77 211 100 76

37 76 16 89 9.6 91 10 91 3.6 90

281 97 70 1.8 90

• Example reaction

Table XII CO-Oruck 1-Olefin- Octanoic Acid-

temperature, G

25th

80 60 81 ' 80 82 90 83 105 84 120 85 25th 86. 60 87 70 88 80

120

not determined

atü

141 211 141 141 141 141 141 141 141 141 141

sales

<

41

67

65

58

50

9.4 100 100

61 2.9

methyl ester (yield)

<

31

48

44

8.7 <5 1

93 x 92 60 1 isomerization ^ straight chain

Ester

<1

8.6
15th
25th
'18

8.7
10
1

97

87

91

> 90

90

92 91 91

Table XIII

Carboxylation of 1-tetradecene using bis (triphenylarsine) -I ⁾ latin (II) chloride-tin (II) chloride and various solvents

Test conditions: 90 G, CO pressure 211 atm, reaction time 360 min.

Example

90

309833, 91
92 ^ «» 93 OO ■ 94 95 96 97

solvent

acetone

Me thyIi s obutylke clay

tetrahydrofuran

p-dioxane

Dirnethoxyethane

Benzene / methanol

Methylene chloride

Dinethylformamide

Tetradecene carboxylation

fo sales

38 34 20 21 37 27 48 <2

Methyl penta decsnoate selectivity

87

88
84 • 2303 I.
VM
VM
I. 88 87 92 87

Tabel XIV

Carboxylation of * .- olefins with various alcohols

Ver. = Mchsbedingungen: <* .- 01efin / Pd = 100 CO pressure: Hl a tu

Alcohol / Λ-olefin = 3 reaction time: 360 min. Sn / Pd = 10

example ^ - olefin Alcohol OC-Olefin-Carb i> sales 100 co
O 98 1-heptene Isopropanol 100 co
OO
e. \ 99 Il Ethanol 100 13/1 100 I! 2-chloroethanol 100 168 101 1-pentene 1-dodecanol 11 102 It phenol 12th 103 Propylene Diproylene glycol

Main prboxylation product ^e Identity Selectivity %

Isopropylic acid
ester 88 Ethyl octanoic acid
ester 91 2-0hlor-ootan-
acid ethyl ester 87 Hexane acid-d or e-
cyl ester 83 Hexanoic acid-phe-
nylester 71 Butyric acid gly-
kolester 81

CD CO

OO

Claims (13)

Claims ■ Λ . ! Process for the production of straight-chain saturated ^ - ^ carboxylated products, characterized in that one a) one or more * c -olefins in the presence b) a homogeneous catalyst consisting of a ligand stabilized en palladium (II) - or platinum (II) halide and a halide of a metal from the Group IVB of the Periodic Table (PS), where the ligand is a donor atom. of group VB or VIB, with c) one, based on oC -olefin, at least stoichbmetrischen amount of a hydroxyl group-containing νβΛΐηαμί ^ and d) an at least stoichiometric one, based on the £ -olefin Amount of carbon monoxide heated at elevated pressure. 2. The method according to claim 1, thereby geken'n- ., Draws that a catalyst is used which a Ligaaden-stabilized palladium (II) metal of the ^ Group IVB halide, being the donor atom of the ligand Nitrogen, phosphorus, arsenic, antimony, vismuth, sulfur or selenium. 3. The method according to claim 1 or 2, characterized in that draws that a catalyst is used which consists of a ligand-stabilized palladium (II) complex the formula and a Group IVB metal halide of the formula in which - 309833/1168 E one or more atoms of groups VB or VIB, · -. R phenyl, alkyl! Phenyl, substituted phenyl, alkyl, substituted Alkyl, halogen or phenoxy,. ■ X chlorine, bromine or iodine ,. - * m, η and y whole positive numbers and - e 2 or Λ mean "*. - is manufactured. -. " 4 ·. Method according to "Claim 1, d a d u r c h g e k .e η η - , draws that a catalyst is used which a ligand-stabilized platinum (II) metal of the group TVB halide, where the 'donor atom of the ligand is nitrogen, Phosphorus,. Arsenic, antimony, bismuth, sulfur or selenium is. · ■ _ - 5. Method according to claim /! -, characterized in that g e 'k e η η' that a catalyst is used which consists of'einem'ligand-stabilized platinum (II) complex of Formula "■ '- - ■ -.-- ■"'. · " and a halide of a group IVB hotall of the in which .. E one or more atoms of groups VB or VIB, '■ ■ R phenyl, alkylphenyl, substituted phenyl, alkyl, substituted alkyl, halogen, or phenoxy, ·' ~ X chlorine, bromine or iodine ,.
m ",. n and y whole positive numbers · · "" mean β- 2 ^ or 4. 6. The method according to one of the preceding claims, d a - "characterized by that as hydroxyl groups "Co-Rnaktand Wasser used \ d.rd. 309833/1163, ■ ·· '- 7. The method according to any one of the preceding claims, characterized in that '. <? ηΠ ·. air containing hydroxyl groups Co-reactant a saturated straight-chain or cyclic alkenol, ■ a glycol ', · a polyol, phenol or a substituted phenol or a mixture thereof is used. , ·. 8. The method according to any one of the preceding claims, characterized. net that as X -olefin a straight-chain oC -olefin with 3 to 40 C-atoms is used will. . ·· ■ '■'. 9. · The method according to any one of the preceding claims, thereby * '· geke η η ζ eich η e' t · that a branched-chain o ^ -olefin with 4 · to 4-0 carbon atoms is a ^{0 ^ -olefin} -. is set. 10. The method according to any one of the preceding claims, characterized in that the catalyst Contains 5 to 10 moles of Group IVB metal halide per mole of palladium or platinum halide. -. , ■ " ΛΛ. Process according to one of the preceding claims, characterized in that the olefin and catalyst are used in a molar ratio of 50: 1 to 200: 1. _ 12. The method according to any one of the preceding claims, characterized in that the reaction in the temperature range from 25 to 120 ⁰ C is carried out .. 13. The method according to any one of the preceding claims, characterized in that the method is carried out in an inert solvent. . , I.