DE1963804A1 - Process for the preparation of esters of saturated alkanecarboxylic acids - Google Patents

Description

DR. M. KÖHLER DIPL.-ING. C GERNHARDT 1963 804

TELEGRAMS, KARPATENT NUSSBAUMSTRASSE Ϊ6

, December 19> 969

W. 14 397/69

Unilever N.V. Rotterdam (Netherlands)

Process for the preparation of esters of saturated alkanecarboxylic acids

The invention relates to a process for the preparation of esters of saturated alkanecarboxylic acids.

Alkanecarboxylic acids with an even number of carbon atoms are found in nature as components of oils and fats are found and as such are indispensable for monochromatic and animal nutrition. With consideration on the forecasts of the amount of fat to be produced annually and the shortage of fat, that already It is not surprising that consideration has been given to how to overcome this scarcity

009836/2209

BAD ORiGINAU

can or how to prevent this scarcity from increasing. In this context, it is desirable As much as possible the use of food, oils and edible fats for technical purposes, such as the production of fatty acids from them, e.g. for soap production, to avoid. This can-i.a. be realized by having the required alkanecarboxylic acids synthetically produced from other sources so that it is not necessary to deal with that of nature imposed limitation to be satisfied by essentially alkanecarboxylic acids with an even number of carbon atoms provides.

The invention provides a very satisfactory solution for the preparation of such alkanecarboxylic acids in the form of their esters.

Besides hydrolysis or saponification of oils and fats, there are also synthetic methods of production known from alkanecarboxylic acids. For example, it is possible to oxidize or to oxidize the corresponding alcohols dehydrate or remove the carboxyl group using organo-metal quenchers to introduce chemical working methods. With the help of manuals and technical literature, the list easily extended by possible methods.

Much attention has been paid to the various methods of preparing alkanecarboxylic acids and their esters has been dedicated to those known as the oxo reaction or hydroformylation. In this reaction become unsaturated organic alkene compounds with carbon monoxide and hydrogen converted to form aldehydes. If larger amounts of hydrogen are used, alcohols are formed} without hydrogen

0119836/2209

SAD

acids are obtained in the presence of water, and if alcohols are present, their esters are obtained (cf., for example, J. Falbe "Synthesen mit Kohlenmonöxyd" (1967) ¹ ). The corresponding acids can be obtained from the aldehydes or alcohols thus obtained by oxidation or dehydration. However, it is preferred to obtain acids in a one-step synthesis.

The reaction equation for Athens is as follows: CH ₂ = CH ₂ + CO + ROH > CH ₃ -CH ₂ -COOR.

For homologues from Athens it is a little more complicated because in addition to the acid or its ester with a straight chain also contains a large length of acid or ester is formed with a branched chain. According to the literature, approximately 50 $ of branched chain compounds formed (see E.R. Tucci "Industrial and Engineering Chemistry Research and Development", Vol. 7, Pages 32 to 38, (196Ö) especially page 35).

The investigations are generally limited to the closest homologues from Athens. It is established it has been suggested that the conversion decreases with increasing molecular weight of the starting alkenes, and in the case of Alkenes with more than 7 carbon atoms are the reaction rates and yields too low for a technically interesting process. Tucci I.e., page 35, For example, states that the rate of reaction for the oxonation of 1-hexene was slowed because of olefin conversions decrease to $ 47. The same was done by D.R. Levering and A.L. Glasebrook, J. Org. Chem. 23 »pages 1836 to 1839 (1958) and by W. Reppe and others in Ann. ' 582, pages 38 to 71 (1953).

0 0 9836/2209

Although hydrogen does not appear in the above reaction equation, it has been found that the formation of alkanecarboxylic acids oma their Eöter through small amounts of hydrogen are produced; this is attributable to the formation of the active catalyst.

The presence of pyridine and other bases has also been found to promote the reaction. It is to assume that the beneficial effect of salt formation or complex formation of the active catalyst with the organic Base is attributable. Akio Matsuda and Hiroshi Uchida (Bulletin Chem. Soc, Japan 58, pages 71o to 715 ' (1965)) converted propene by reaction with carbon monoxide and methanol in the presence of a small amount of Hydrogen and an excess of pyridine, calculated on the catalyst, to a mixture of methyl butanoate and methyl isobutanoate in fairly good yield and an initial rate of conversion as high as the initial rate of hydroformylation is. Other organic bases, namely pearethylaniline, Quinoline, 2-methylpyridine, triethylamine, piperidine and Benzylamine was found to be much less effective. On their best try, the aforementioned found Writer a conversion percentage of $ 92, and they isolated methyl butanoate and methyl methyl propanoate in a molecular ratio of approximately 78:22. Such a high ratio of straight chain compounds to branched-chain compounds also results from the conversion of alkenes with carbon monoxide and hydrogen to alcohols in the presence of phosphines (Tucci I.e., Page 35). However, there is no formation of acids in the presence observed of water when hydrogen is omitted in the latter conversion.

009.83 6 / 22.09

From the sharp drop in yield and speed eligibility of the hydroformylation reaction with increasing number of carbon atoms in the starting alkene can also have such a sharp drop in the hydrocarboxylation-hydroesterification process to be expected. For example, U.S. Patent 2,868,815 states that the conversion of 1-octene into the methyl esters of acids with one more carbon atom at 2o5 to 21o ° C and 3o6 to 34o atü only yields below $ 53, with one Reaction time of over 7 hours and a promoter is used, without such a promoter is a Get yield of only $ 6,

Surprisingly, it has now been found that higher alkenes rapidly increase in a high degree of conversion Esters of alkanecarboxylic acids can be converted, creating a higher percentage of straight chain isomers is formed by adding a small amount of both hydrogen and organic to the reaction mixture Base adds.

The invention can be used as a method of manufacture of esters of saturated alkanecarboxylic acids have been described, with the alkenes of the general formula

R ¹ -CH = CH-R ² (I)

in which R is hydrogen or an unbranched aliphatic ^

■ 2
Is a hydrocarbon group and R is a hydrocarbon

1 2

represents a group, where R and R together are 5 to 18 carbon have atoms, through reaction with carbon monoxide and a monohydric primary or secondary alcohol using a cobalt compound as a catalyst in the presence of an amount of hydrogen from o, ol to o, 125 mol per mole of carbon monoxide and at least one organic base

009836/2209

the general formula

R ⁴ ""

Έί ^ο - O

I (ID

HIGH

3 4 5

in which R, R and R ^ either all represent hydrogen or one or more of them an aliphatic alkyl group with 1 to 4 carbon atoms, a phenyl or a Benzy! group, while the remaining symbols are hydrogen, or two adjacent symbols are a benzene ring or a hydrogenated benzene ring together with the two carbon atoms of the pyridine ring, to which they are bound, can represent, the remaining symbol being hydrogen or an alkyl group with 1 to 4 charcoal ns to-f fat omen is at one temperature between Ho and 22o ° Ö and with a pressure not below 5ο be converted at.

Purely technical purposes it is advantageous from a

Mixture of isomeric alkenes, preferably 1-alkenes

starting from the general formula OH ₂ = OH-R. It can be seen that one can also start from a mixture of homologous alkenes.

It has been found that according to the process according to the invention using small amounts of hydrogen and pyridine and homologues with two free 2-positions of both 1-alkenes and a mixture of is.omeric alkenes, a reaction product is obtained, the one high percentage, meieteng over $ 7o _? of esters

009836/2209

.on contains straight-chain acids, while if the organiache Base is omitted, this percentage a lot

· * ■ ν is lower (about 50 $).

In this context, straight-chain acids mean-. hang understood an acid in which the carboxylic acid group is on an -OHp group. If the carbon monoxide and the alcohol is attached to the terminal carbon atom of the group R or of the 1-alkene (where R = H) , esters of straight-chain acids according to the above definition are obtained, regardless of the type

ρ
the R group, which is retained. Evidently there is a migration of the double bond during the reaction and carbon monoxide and the alcohol are preferentially deposited in the terminal carbon atom. The conversion of isomeric alkenes is slower. Isomerization is apparently the factor that determines the rate of conversion.

The conversion of 1-alkenes with chain lengths of 7 to 14 carbon atoms is going on at a comparable rate. The conversion of 1-heptadecene goes on at a slower pace; but this is still the same as that of a mixture of isomers Alkenes comparable. The conversion of 1-eicosene occurs at a markedly slower rate. In all. Cases, the process according to the invention gives products which have a higher percentage of straight-chain Connections included. The invention is also characterized in that a mixture of esters of straight chain and branched chain alkanecarboxylic acids containing at least 70 straight chain esters.

0ΌΒ836 / 2209

- ⁸ - 1863804

The process according to the invention can be carried out with various monohydric alcohols: primary alcohols such as methanol, ethanol, butanol, 1-octanol, 2 ⁱ -ethylhexanol or phenylmethanol, and secondary alcohols such as isopropanol, 2-octanol and cyclohexanol. The . secondary alcohols react somewhat more slowly, but the results are comparable. Substituted alcohols such as 2-methoxyethanol are also suitable for use. Methanol is preferably used. Polyvalent alcohols such as glycol and glycerine hardly react.

The molecular ratio of alcohol to alkene can be varied within wide limits, for example between 8: 1 and 1: 1. The speed of the reaction is only somewhat dependent on the concentration of the alcohol. Even less alcohol can be used, but then the theoretical yield is of course determined by the amount of alcohol. If the alkenes are to be converted almost quantitatively, it is advantageous to use an excess of alcohol. The reaction mixture can · contain a small percentage of water, which is either already caused by the reactions occurring, such as ζ, .Β. . Esterification of the acids formed from the cobalt salts or acetalization of the aldehydes formed as a by-product is present, or which can be introduced by the alcohol or the pyridine base. For example, up to $ 5 of water in the methanol does not affect the results much. It can even be closed from ¹ to experiments that a small amount of water in the reaction mixture has a beneficial effect.

Suitable catalysts are derived from cobalt.

It can be assumed that carbonyl cobalt compounds are formed from the carbonyl compounds during the reaction}

009836 /? 209

it is therefore advantageous to start from a carbonyl cobalt compound. ,

The catalyst preferably consists of octacarbonyldicobalt, which is presumably in hydrogen tetracarbonylcobalt is converted during the reaction due to the presence of hydrogen. In addition, octacarbonyldicobalt can also cobalt (II) salts, such as naphthenate, acetate and octanoate; the decenoate, the stearate and the carbonate were added will. Although in the presence of such cobalt compounds the reactants with a somewhat low-

faster than in the presence of octacarbonyldicobalt react, the same results are produced. This is also the case with cobalt (III) oxide, but with An induction period has been observed in this reactant. Other common cobalt-containing oxo catalysts however, they are also suitable in the same way. Cobalt salts of organic acids such as cyanides, sulfates and nitrates, are less suitable because they are by-products that either attack the apparatus or disrupt the transformation.

It has been found that the catalyst does not form upon heating during work-up decomposed by cobalt metal. The cobalt compounds can be removed by washing with acid, whereby the o-rga- niache, Base is removed at the same time. It is also possible to distill the reaction mixture as a whole. After the pyridine has been driven out, the cobalt compounds are converted into the cobalt salts of the acid formed and remain as such in the distillation residue. They can then be used again as catalysts. This provides opportunities for the process to be carried out continuously, with the cobalt compounds in

003836/2209

BATH ORIGINAL

- Io -

This continuous process is carried out in the cycle will"

The amount of catalyst, expressed in moles of cobalt per mole of alkene, should preferably be between 0.04 and 0.064 Moles / moles.

It has been found that the presence of a small amount of hydrogen in addition to the organic Base promotes both a high degree of conversion and a high percentage of straight chain esters in the reaction product. Under a small amount in this' In connection with this, an amount of not more than 0.25 moles of hydrogen per mole of carbon monoxide is understood.

The presence of hydrogen also gives rise to the main by-products: aldehydes and theirs Acetals. The formation of these by-products is caused by the Suppressed addition of pyridine bases and their amount never exceeds a percentage of $ 5 and amounts to in the main thing is $ 1 to $ 3. For a technical process such percentages are acceptable. '-

The amount of hydrogen should preferably be approximately 0.02 to 0.010 moles per mole of carbon monoxide. Under otherwise identical conditions (ITo ⁰ O, 0.06 mol of pyridine, total pressure 14o at ^f ) was found, for example, in the conversion of 1-decene with carbon monoxide and methanol;

3833/2203

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Table I.

'Hydrogen converted (at) decene (#)

Ester (mol %

straight ester _k # of esters)

O 69 VJl 68.4 70 8.5 88 82.6 70 20 * " 85, 4th "75.2 69 "

It has been found that useful organic bases, besides pyridine, homologues of pyridine and compounds with fused pyridine rings, such as isoquinoline and its homologues, are equally useful, provided that both 2-positions are not substituted.

Suitable bases in addition to pyridine are e.g. 3-alkylpyridines, 4-alkylpyridines, 4-phenylpyridines, 4-benzylpyridines, 3,4-Malkylpyridines, 3 »5-3) ialkylpyridines, 3,4,5-trialkylp.yridines, isoquinoline, 4-alkylisoquinolines and alkylisoquinolines having an alkyl group substituted on the benzene nucleus. Mixtures of the active bases, how they are technically available can be used. For example sird3-methylpyridine, 4-methylpyridine, 3-ethylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-isopropylpyridine, 4-butylpyridine, 4-tert.-butylpyridine, 3,4-dimethylpyridine in, 3,5-dimethylpyridine, 3-methyl-4-ethylpyridine, 4-methyl-3-ethylpyridine or 3,4,5-trimethylpyridine suitable organic bases for the process according to the invention.

, 'Pyridine bases that do not contain two free 2 groups, do not promote the conversion and are not

009836/2209

suitable for use in the method according to the invention; moreover, the percentage of esters of straight-chain acids does not differ much from that of can be obtained with already known methods (under $ 60) can. Such less active bases are 2,2'-bipyridyl, 2-methylpyridine, quinoline, biquinolyl. It is also noteworthy that 3-chloro- and 3-bromopyridine do the conversion do not promote, although they have free 2 positions; so they are not suitable for use either, others too Nitrogen compounds such as 1,4-diazine, lOrmamide, dimethylformamide and acetonitrile are less active. However, it has been found that the presence of, for example, 2-methylpyridine a technical pyridine base which contains the bases according to the invention does not have its promoting effect disturbs.

It has been found that in the conversion of 1-decene with carbon monoxide and methanol using Octacarbonyldikbbalt as a catalyst 3- and 4-alkyl or -aryl-substituted pyridines are better promoters or promoters than pyridine. In an attempt 'in which the same maximum rate of 1-decene conversion "was observed less 4-methylpyridine than pyridine was required, to get that maximum speed. From the composition of samples taken during the reaction were drawn was calculated to be the initial rate of reaction using pyridine

-3-1 (Example 1) was equal to K = 5.1 σ Io min, while using 4-methylpyridine (Example 15) this reaction rate is much higher: K = 12.1 χ Io min ^-1 . -

The promoter activity of 4-methylpyridine ¹ is slightly higher than that of 2-methylpyridine.

009836/2209

ORIGINAL INSPECTED

1363804

3-ethyl-, 4-benzyl- and 4-phenylpyridine are in theirs Activity equal to that of 3-methylpyridine; 4-ethyl ~, Are 4-propyl-, 4-tert-butyl- and 3,5-dimethylpyridine equal to that of 4-methylpyridine. The 3j4-disubstituted Pyridine has a somewhat higher activity than the monosubstituted pyridines.

The total conversion depends on the amount of pyridine base; the optimum can be determined by the expert in can be easily determined.

Preferably the amount of pyridine base should be between 4 and 100 moles per mole of cobalt present in the catalyst is, amount.

The temperature should be between Ho and 22o G. Beyond the lower limit, the rate of reaction increases too much, while beyond the higher limit the catalyst decomposes (if not extremely high Carbon monoxide pressures are applied) - and the rate of reaction also decreases. The temperature is preferably between 130 and 200 ° C, "in this" range the catalyst stable enough and the reaction rate high enough to produce sufficient amounts of product to result in a reasonable period of time.

The total pressure can be varied within wide limits. It has been found that the higher the carbon monoxide pressure is, the faster the reaction rate becomes, but the higher the pressure is not noticeable Effect on the percentage of straight-chain formed Boarding or on the percentage of by-products it has. The total pressure should not be less than 50 at and vorzugoweioe are above 125 at «An upper limit can be

009836/2209

cannot be specified, but is a practical limit usually given by the technical system for pressures in this range; it is not necessary to have one technical plant used for extremely high pressures

suitable is. "j

The process can be carried out batchwise, semicontinuously, or continuously. As stated,; after the alcohol has been distilled off, the bases,! the unconverted alkene and die'Alkancarbonsäure- I ester and the remaining cobalt salts are reused. It is therefore advantageous to use the alkenes in the. | to the highest possible degree, but for economic reasons it may be appropriate to convert the reaction interrupt if more than $ 55 i preferably more than $ 85, alkene are converted, or mixtures from a continuous process to remove that is still up to $ 45, preferably up to $ 15, contain unconverted alkene ".! for the highest possible conversion the reaction time is preferably less than 1 hour; it is preferred for economic reasons no longer than 5 hours. ·· *; *.

Almost quantitative conversion is achieved by a process in which 1-alkenes are converted into a mixture of esters of straight and branched chain acids, the acid portion of which has 8 to 18 carbon atoms, containing at least 70 esters of straight chain acids by reaction with carbon monoxide and a monohydric primary alcohol using a cobalt compound as a catalyst in the presence of an amount of hydrogen that is not o, o5 moles per mole of carbon monoxide exceeds, and at least one organic base of the general formula (II) in I6O to 18o ° C and at 21o to 23o at ¹ for 2 to 5 hours »after which the

00 9 836/2209

ORIGINAL INSPECTED

The reaction mixture is distilled and the esters are separated from the excess alcohol and the base and the remaining cobalt salts are recycled again, converted .

The products obtained by the process according to the invention have at most only a pale yellow color, however, most of the time they are white.

If desired, the straight-chain esters can be separated from the branched-chain esters by known processes, for example by the known urea separation. Both the mixture and the straight- chain and branched-chain esters are each of great technical value.

The mixture obtained can e.g. be converted into soap or monoglycerides, which act as emulsifiers or cold-resistant plasticizers can be used; other esters can be used as additives. "for mineral oils and used as ester lubricants. Branched-chain esters can be used, for example, as plasticizers will.

The invention is explained in more detail below with the aid of examples. The one given in the examples Pressure. Refers to positive atmospheric pressure (atü).

example 1

The experiments were in .einem 3oo ml autoclave with adjustable stirring device and the necessary equipment, means for cooling and pipes for gas inlet to maintain the desired temperature and outlet as well as for sampling.

Q0983B / 2209

1863604

The autoclave was filled with 70 g (0.5 mol) of 1-decene (which contained more than 95% of this compound), 64 g. (2 mol) of methanol, 1> 4 g (0.04 mol) of octacarbonyldicobalt and 4.7 g (0.06 mol) of pyridine filled. Hydrogen was then admitted until the pressure was 8.5 atmospheres, and carbon monoxide was also introduced to 140 atmospheres. The contents of the autoclave were heated to 170 ° C. for 6 l / 4 hours with stirring, while the pressure was kept at 14 ° by introducing additional carbon monoxide. At times given in Table II, samples were taken and analyzed by gas chromatography at 12o to 14o ° 0 (column 2oo χ ο.4 cm, filling material silica gel with lofo polyglycol, average molecular weight 2o,000, charged), after which the catalyst was removed from the cooled sample by washing with 4N hydrochloric acid. The following compounds were found to be present: decene, decane, undecanal, 1,1-dimethoxyundecane and the methyl esters of undeic acid, 2-, 3-, 4- and 5-decanecarboxylic acids. The composition of the samples (in mol $ based on converted decene) is given in Table II.

Table II & quot ^{; v}

Time Decen Undecan-
acid Methyl ester of 3 decancar
bona acid 4 + 5-De-
cancar-
boric acid (min) 34 2 decancar
boric acid 1.9 2.6 3o 5o 44 7.4 2.7 3.9 9o 35 51 9.3 3.7 6.1 195 25th 57 11.7 4.5 7.7 375
I.
1 12th 13.2

009836/2209

ORIGINAL INSPECTED

After 6 1/4 hours the reaction was through-cool, development of the reaction product and depressurization. The reaction mixture was mit'Wasser and with Washed 4N hydrochloric acid, whereby methanol, pyridine and the cobalt compound were removed. . . '

The reaction mixture was then saponified; the j

Fatty acids were removed from the soaps thus formed by adding! Acidification 'released. The yield was 72 grams per composition (determined by gas chromatography according to Conversion of the sample into dimethyl ester) was as follows! 71 $ undecanoic acid, 15.5 $ 2-decanoic acid, 5 »7 $ 3-De- '■ cancarboxylic acid, $ 5.24-decanecarboxylic acid and $ 1.85-decanecarboxylic acid.

Example 2

(A) The same "autoclave as is described in Example 1, with 70 g (0.5 moles) of 1-decene, 32 g (1 mole) of methanol, 2.82 g of cobalt (II) octanoate - was used in a technical manner Quality (with a content of 0.008 mol of cobalt) and 20 g (0.25 mol) of pyridine. Then hydrogen ₁ was admitted to a pressure of 8.5 atmospheres and then 'carbon monocyte' to a pressure of 130 atmospheres. The reaction mixture was admitted Heated with stirring to 170 ° C for 6 hours, the pressure being maintained at 14o atm by supplying carbon monoxide. After cooling and relieving the pressure, the autoclave contained, as was found, 132 g of reaction product; in a device for fractional distillation 10 5 g of this reaction product was separated off, the following fractions being collected »

(a) 65 to 82 ° / 76o mm (little) (b) 37 ° / 22 mm, (pyridine)

009836/2209

(c) 60 to 125 ° / 22 mm (little)

(d) 125 to 137 ° / 22.mm (Ester, 68 g. =

Fraction (d) had the following composition as determined by gas chromatographic analysis:

82.4 fo methyl undecanoate 11.1 $ methyl 2-decanecarboxylate

2.1 % methyl 3-decanecarboxylate 1.7 io methyl 4-decanecarboxylate 1.4% methyl 5-decanecarboxylate

1.2 io aldehyde acetals.

(B) The still bottoms were the purple color of cobalt soaps. It was reinserted in the autoclave, after which 70 g of l-decene, 32 g of methanol and 20 g of pyridine were added again, while hydrogen to a pressure of 6 atmospheres and carbon monoxide to a pressure of 130 atmospheres were admitted in succession. The reaction mixture was heated at 170 ° C. for 5 hours while the pressure was maintained at 130 atmospheres by the addition of carbon monoxide. According to gas chromatographic analysis of a sample, the reaction mixture has been found to have the following composition (in mol%, based on converted decene): i

unconverted decene 16 ^ Ester 82 #

just esters 79 f ° of a total

of esters

Acetals 2 #.

Examples 3 to

In the same way as described in Example 1, the following experiments were carried out,

009836/2209 SAD original

in which the hydrogen pressure, the amount of pyridine and the temperature were varied. In all cases the autoclave was filled with 70 g (0.5 mol) of 1-decene, 6 * 4 g (2 mol) of methane oil and 1.4 g of octacarbonyldicobalt (with a content of 4 ml, lol cobalt); other details and the results after 6 hours are shown in Table III (for purposes of comparison, the values of Example 1 have been included in Table III, while Examples A, B and C, in which both the hydrogen and the pyridine, respectively the pyridine or hydrogen omitted do not fall within the scope of the invention).

Table III

at
game Temp "
(° o) Pyri
din
(Mole) water
material
<atü) vice
change
tes
Decen
(rtf \ Ester
(Mol
*) just
Ester ($
from
Esters) A. 17o 0 0 26th 24 · ' 52 B. 17o 0 8.5 74 62 55 G 17o 0.06 0 ■ ι 7o < • 68 • 7o 1 17 ο 0.06 8.5 94 9o 7o 3 17o 0.06 20th 83 75 69 4 ' 17 ο "0.12 8.5 96 92 73 , 5 ' 17o 0.24 8.5 ■ 98 94 77 ! 6- 135 0 ^ 06 8.5 93 89 78 V; 135 0.12 8.5 96 95 76 8th 21o 0.06 8.5 63 61 73

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- 2ο -

Examples 9 to 12

In the manner described in Example 2A, the effect of the amount of hydrogen was determined in experiments in which 70 g (0.5 moles) of 1-decene, 32 g (1 mole) of methanol and carbon monoxide (to 130 atmospheres) at 17o ° 0 in the presence of 2.82 g of cobalt (II) octanoate (with a content of 8 mmol of cobalt), 20 g (0.25 mol) of pyridine and the in-the Table IV amounts of hydrogen were reacted. After o, 25 * o, 75, 2 and 5 hours samples were taken drawn and analyzed. The results are given in Table IV.

Table IV

at
game Time
(Hours) I. I. 2 water
material
(atü) converted
deltes
Decen
(*) Ester
(Mole fo) straight chain
ge ester
{io of
Esters) 9 o, 25 1.5 3o ■ 29 ' 83 Io 3 33
I 4 .32 82 * 11th 6th 44 42 83 12th 5 12th 44 4o 81 9 o, 75 1.5 48 47 83 Io 3 49 48 82 11th 6th • 55 53 '81 12th 12th 62 59 82 9 1.5 67 63 79 Io 3 75 74 81 11th 6th 7o 67 8o 12th 12th 79 74 8o 9, ' 1.5 91 9o, 5 79 Io 3 92 9o 8o 11th .6 93 9o 79 12th 12th 93 88 8o 009836 / 2209

ORIGINAL INSPECTED

Examples 13 .Ms 29

Following the procedure of Example 2 (A) ¹ , experiments were carried out in which 70 g (0.5 mol) of 1-decene, 32 g (1 mol) of methanol and carbon monoxide (to 130 atmospheres) at 170 ° C. in the presence of 2 , 82 g of cobalt (II) octanoate (with a content of 8 mmol of cobalt) at 8.5 atmospheres hydrogen and in the presence of an organic base, the type and amount of which is given in Table V, reacted. With the exception of the technical pyridine (bp loo to 15o C), which consisted of lo $ pyridine, 32 $ 2-methylpyridine, 20 $ 3-methylpyridine, 25 $ 4-methylpyridine and 12 $ dimethylpyridines, all bases had a purity of 95 to 99 $ '$ P 4-phenylpyridine 75.5 to 77 ° C. Further details and the results are given in Table V.

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ORIGINAL INSPECTED Table V

CD CO CO IO

σ> to

KJ O

co

2 ω

m D

at
spat
le Organic base Pyridine ■ lot (Mole) Converted
(fo) after Hour
o, 75 * De c en Ester
(MoI %
after
5 hours straight chain
ge ester
Xio from
Esters) 11th Art technical pyridine (ä) o, 25 Hour
o, 25 7o Hour
5 85 79 13th 3-methylpyridine 2o ' 44 - 63 93 85 81 14th • 4 * -Methylpyridine 2o ο ·, 11 32 71 89 95 73 15 * 4-methylpyridine iq- '. Ojo6 39 66 96 95 73 16 4-methylpyridine, techn .. 5.6 ο, ΙΙ 8o 99 93 • · 8ο 17th 3-ethyl pyridine Iq ο, ΙΙ 49 79 97 91 82 · 18th 4-1thylpyridine Io ο, ΙΙ 52 76 95 ·· 92 8o 19th 4-Prο pylpyri din 13.6 ο, ΙΙ .45 · 82 97 92 82 2o 4-tert-butylpyridine 13.6 ο, ΙΙ 54 78 96 92 82 21 4-phenylpyridine 15.3 ο, ΙΙ 54 78 • 96 91 "82 22nd 4-benzylpyridine "17.1 ο, ΙΙ 51 71 93 9o • .81 23 3,4-dimethylpyridine .19.6 ο, ΙΙ 41 75 92 9o • 8o 24 3,4-dimethylpyridine 21.4 o, o55 46 67 94 92 ■ -. 82 25th 3,5-dimethylpyri din 6.8 ο, ΙΙ 42 82 95 86 84 26th 3-methyl-4-ethylpyridine 13.6 ο, ΙΙ 5o 83 89 92 82 27 4-methyl-3-ethylpyridine 13.6 ο, ΙΙ '54 82 95 87 84 28 Isoquinoline 15.3 ο, ΙΙ 53 -.84 89 87 83 29 15.3 o, o4 51 9o 56 75 5, o 59

ro iv;

CD Cl CO OO O

*) In this experiment, 64 g (2 mol) of methanol, 6 atmospheres of hydrogen and 1.4 g of Ootaoarbonyldicobalt were (with a content of 4 mmol cobalt) as a catalyst applied.

Examples 3o to 4o

Following the procedure as described in Example 1, tests were carried out in which the nature of the alkenes was varied. The results shown in Table VI, 1-alkenes had a purity of at least 95 $ i the · ■ mixture of g & Mäss Example 36 using 1-alkenes containing 92 $ l-alkenes and consisted of 2 $ decene, 23 $ undecene, 23 $ dodecene, 24 $ Tridecene, $ 25 tetradecene, and $ 3 pentadecene; the 2- and 3-heptenes (Examples 37 and 38) were mixtures of the cis and trans isomers containing $ 95. heptene; the mixture of the alkenes used in Example 39 contained less than 5 $ 1-alkenes and consisted of 1 $ decene, 3.6 $ undecene, 41 $ dodecene, 20 $ tridecene and 2 $ tetradecene.

The alkene was mixed with 64 g (2 mol) of methanol (in Examples 3o, 37, 38 and 4o with 77 g = 2.4 mol) and carbon monoxide (to 13o atü) in the presence of. 1.4 g octacarbonyldicobalt (with a content of 4 mmol cobalt) (in Examples 3o, 37, 38 and 4o with 1.68 g = 4.8 mmol of cobalt), 2o g (0.25 mol) of pyridine (in Examples 3o, 37, 38 and 4o with 24 g = 0.3 mol, in example 5 with 19 g = 0.34 mol) and 8.5 atmospheres of hydrogen (in example 4o: 7 atm) at 170 * 0 for 5 hours (in example 5: 6 hours) brought to reaction.

0 0 9836/2209

INSPECTED

In Table VI are the type and amount of alkenes and the following results were obtained:

Table VI

at
spat
le Alkene; Art lot
(G? converted
delte
lot
(*) Ester
(Mole #) _straight-
chain
Ester
(tfo from
Esters) 3o
5
"31
32
33
34
35
36
37
38
39!
4o 1-heptene
1-decene
1-TJn de c en
1-dodecene
1-tridecene
1-heptadecene '
1-eicoses. .
Mixture of «
1-alkenes
2-heptene
3-heptene
Mix of
Alkenes
4-methyl-1-pentene 59
7o
7o
7o
7o
7o
7o
• 7o
59
59
7o ^M
51 95
98
·. 99
98
96
92
79
98
92
91
'89 ■ '
89 . 94
94
96
92
92
86
76
. 95
9o
9o
87 ·
89 83
77
75
73
72
71
-71
74
82
, 78
7o
76

The composition of the esters from Experiments 36 and 39 is given in Table VII, where in The percentage of straight-chain esters was reported in brackets.

009836/2209

ORIGINAL INSPECTED Table VII

^! At- O 11th composition (74)
(71) ⁰ I. (*) 5 25,
19 ⁰ y L4 ° 15 4 (75)
5 ^G 16 ¹ game
ί 1
1 , 5
, 5 ^C 12 24, ο
42.5 (75)
(66) 6th
6th (71)
(71) 22
1, 4.9 56
59
1 25.6
55.5

Examples 41 to 45

As in Examples 50, 57 and 58, 70 g of heptene were obtained under otherwise identical conditions, with the exception that 9 g (o, ll mol) of pyridine were used, converted at 155 ° C. The results after 5 hours are in given in Table VII.

Table VIII

■ At i-
; game Alkenes converted
te alkenes (<fo)
■ ι * ■ Ester
(Mole $>) straight chain
ge ester
Xfo from
Esters) 41
42
: ⁴⁵ 1-heptene
2-heptene
5-heptene 91
47
51 88
44
5o 8o
71
66

In order to obtain comparable results, a higher reaction temperature should preferably be used for the conversion chosen from alkenes; be that none or hardly any have terminal double bond.

009836/2209

ORIGINAL INSPECTED Examples 44 '·' to ·· 5o

Experiments similar to those described in Example 1 were carried out with various alcohols carried out, whereby the amounts of 1-decene, as given in Table IX, with the given Amount of alcohol and carbon monoxide (to 13o atü) in the presence of 2.83 g of cobalt (II) octanoate (with a content of 8 mmol of cobalt), · 2o g (0.25 mol) of pyridine and 6 atm Hydrogen at 170 ° C for 5 hours. The results are given in Table IX.

Table -IX

at
game alcohol 1-decene lot
(G) lot
(β) vice
wan
delt.
(*) · Ester
(Mole £ straight
chain
Ester
{ia from
Esters) 11th
44
45
46
47
48
49
5o Art
¹ / 32
46 ■
56
64
85
85
58
65 7o
7o ^%
65
6o
46
46
63
6o 93
87
56
77
63
56
63
87 91
^V 83 '
55
74
6o
52
62
86 , 79
77
71
75
71
73
74
77 Methanol
Ethanol
Isopropanol
Butanol
1-octanol
2-octanol
2-ethylhexanol
2-methoxyethanol

0098 3 6/2209

OBlGiNAL

1863804

Examples 5Ϊ to 54

Experiments similar to those described in Example 1 were carried out, varying the amount of methanol as shown in Table X. 7 o g (0.5 mol) of 1-decene (in Example 52: 66 g = 0.42 mol) were mixed with methanol and carbon monoxide (to 130 atm) in the presence of 2.82 g of cobalt (II) octanoate ⁱ (with a content of 8 mmol of cobalt), 2o g "(0.25 mol) of pyridine and 6 atm. hydrogen converted at 170 ° 0 for 5 hours» Table X shows the results.

Table X

at
game Methanol converted
deltes
Decen (#) Ester
(Mole fo) straight chain
Ester do
of esters) 51
52
11th
53
54 (Mole) Molver-i-
never lasts
to Decen 72
93
93 '
85
88 . 66 · '
91
"91
82
86 75
79
'79
8o.
78 4th 8: 1
2 4: 1
1 2: 1
o.65 1.3: 1
o, 5 .1: 1

Examples 55 to 59

The effect of various cobalt compounds shown in Table XI was tested in similar experiments as the tests described in Example 1, determined. The amount of the cobalt compound was such that 8 mmoles of cobalt (in Beiepsl 5 »4 mmoles), calculated as cobalt metal, were present. The salts are all derived from divalent cobalt. In the examples

009836/2209

ORIGINAL INSPECTED

the 66 g (ο, 42 mol) 1-decene (in example 5: 70 g = 0.5 mol) with 6o g (1.9 mol) of methanol (in Example 5 * 64 g = 2 mol, in the examples 58 Wd 59: 50 g "= 0.94 mol) and carbon monoxide (to 13o atü) (in example 5 to 14o atü) in the presence of the cobalt compound, 20 g (0.25 mol) of pyridine (in Example 5: 19 g = 0.24 mol) and 7 atmospheres of hydrogen (in Example 5: 8.5 atmospheres) at 17o ° 0 for 5 hours (in Example 5J 6 hours) implemented. Table XI there the results again.

Table XI

at link Art io Co t ¹ 17 -converted Ester straight game Go ₂ (CO) ₈ '6' tes 1-decene
(*) (Mol
*) term esters
{io of
Esters) VJI OctanoaV 8th 97.5 94.4 77 52 Decenoate 9.4., 93 91 79 55 Decenoate 47 88 85 77 56 Stearate 89 ' 86 77 57 basic
Carbonate 89 .. 87 ¹ 78 58 Trioxide 94 91 81 59 95 93 81

Examples 6o to 61

The effect of the catalyst concentration is from experiments similar to those of Example 2 (A) below Use of cobalt (II) octanoate as a catalyst can be seen. In these experiments 70 g (0.5 mol) of 1-decene, 32 g (1 mol) of methanol and carbon monoxide (on 13o atü) at 17o ° C in the presence of the cobalt (II) octanoate of 20 g (0.25 mol) of pyridine and 6 atm hydrogen during

009836/2209

ORfGlNAL INSPECTED

5 hours implemented. The amount of. Catalyst and the results are shown in Table XII.

Table XII

at
game catalyst '(g) (Mol Co) converted
deltes
Decen ($) Eater
(Mol
fo) straight
term esters
(# from
Esters) 6o
11th
61 1.41
2.82
5.64 o, oo4
o, oo8
o, ol6 75
93
95 74
91
92 8o
79
79

Examples 62 to 63

The influence of small amounts of water in the reaction mixture was investigated in experiments carried out with Example

^x ι

1 were comparable, - examined, whereby 70 g (0.5 mol) 1-decene at 17o ° C with carbon monoxide (at ^ L3o atü) and 32 g (1 mol) of methanol, to which a little water was added, in the presence of 6 atmospheres of hydrogen, 2.82 g of cobalt (II) octanoate (with a content of 8 mmol of cobalt) and 2o g (0.25 mol) of pyridine were converted over 5 hours, Table XIII shows the results obtained.

Table XIII

at
game Water in
Methanol converted
tes 1-decane
. <*) ' Ester
(Mol <f) straight chain
ge ester ($
of esters) 11th
62,
63 0
2
5 93
97
/ 96 91
94
91 79
81
82

009836/2209

ORIGINAL INSPECTED

In Example 63, a few percent higher products were made established.

Examples 64- Ms 68

The influence of the total pressure was studied in experiments similar to Example 1, using 70 g (0.5 mol) of 1-decene with carbon monoxide and 32 g (1 mol) of methanol in the presence of 2.82 g of cobalt (II) octanoate (containing 8 mmoles of cobalt) and 2o g (0.25 moles) of pyridine. After hydrogen was added to the autoclave to a pressure of 6 atmospheres, carbon monoxide was added to a pressure as shown in Table XIV. The contents of the autoclave was then heated to 17O ⁰ C or 19o ° C while the pressure was maintained mentioned, and its composition was analyzed after 2 and 5 hours. At a pressure of 60 atmospheres, an induction period of about 15 minutes was observed. Table XIV shows the results obtained.

009836/2209 omr, «*.

OBiGiNAL INSPECTED Table XIV

at
game Temp.
^(o C) pressure
(atü) converted
1-decene (° / o) Ester
(Mol %) straight chain
Ester (fo of
Esters) To ; I hours 64 17o 6o 4o 36 83 65 17 ο loo 65 61 81 11th 17o 13o 7o 67 . 8o 66 17o 22o 87 85 81 67 19o 13o 65 62 78 68 19o 22o 86 82 79 After [ ? hours 64 17 ο 6o 62 59 82 65 17o loo 88 85 81 11th 17 ο 13o 93 91 79 66 17o 22o 98 95 8o 67 19o 13o 87 85 75 68 19o 22o 97 94 78.

Examples 69 to 8o

The optimal amount of 4-methylpyridine was investigated in experiments similar to the experiment described in Example 2 (A): 70 g (0.5 mol) of 1-decene were treated with carbon monoxide and 32 g (1 mol) of methanol in the presence of cobalt ( II) octanoate as a catalyst, 8.5 atmospheres of hydrogen and 4-methylpyridine under conditions (temperature, total pressure, amount of 4-methylpyridine and catalyst) as given in Table XV. Table XV also shows the results obtained. Example 82 is of completeness
given for the sake of it. In Example 69, 1.4 g of ostacarbonyldicobalt was used as the catalyst.

009836/2209

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Ο) O CD •H ro ro in O O in O O H O O O O O EH pi OJ CM in H H in H H OJ OJ H H H H I.
H CQ H H H H KN H H H H O <r] in in in O O in O O OJ O O O O O +3 H H H H KN H H H H OJ CM I. VD * J- cn O H CM KN VD in C- C- OT CNJ cn O I. VD C- C- C- t— H C- C- C- ro C- ω • Η O) pq

ORIGINAL INSPECTED

009836/2209

Example 81

70 g (0.5 mol) 1-decene, 32 g (1 mol) methanol, 5.6 g cobalt (II) octanoate (with a content of 16 mmol Cobalt) and 20 g (0.25 mol) of pyridine were introduced into the autoclave as described in Example 1. hydrogen was introduced until a pressure of 6 atmospheres was reached, and then carbon monoxide was allowed, until the pressure was 220 atmospheres.

The reaction mixture was heated to 17o ° C with stirring for 5 hours, the pressure to 22o atü was kept by the introduction of carbon monoxide.

Samples taken during this experiment had the composition shown in Table XVI.

Table XVI

Reaction converted Ester straight chain time (hours) 1-decene ($) (Mole fo) Ester (# of
Esters) o, 25 62 6o 83 o, 75 81 79 82 2 96 94 81 5 99 97 81

The process can therefore be regulated in such a way that the alkene is almost completely converted becomes, which is very advantageous for a continuous process, since then a recycle of unconverted Alkene is not necessary.

009 836/2209

INSPECTED

V \

Example 82

As described in Example 1, 70 g (0.5
Mol) 1-decene, 32 g (1 mol) methanol, 5.64 g cobalt (II) octanoate (with a content of 16 mmol. Cobalt) and
Place 10 g (0.1 moles) of 4-methylpyridine in an autoclave
introduced, hydrogen was introduced to a pressure of 8.5 atmospheres and then carbon monoxide was admitted until the pressure was 220 atmospheres. The reaction mixture was heated to 170 ° 0 with stirring for 5 'hours, the pressure being reduced by the introduction of
Carbon monoxide was maintained

Samples drawn during this experiment had the composition shown in Table XVII.

Table XVII

Reaction
time (hours) converted
1-decene ($) Ester
(Mole $>) straight chain
Ester (# of
Esters) o, 25
o, 75
1.75
5 61
78
91
95 59
76
89
93 88
85
83
8o

009836 / 22O9

Claims (18)

Claims soldering process for the production of esters of saturated Alkane carboxylic acids, characterized »that one alkenes of the general formula R ¹ -OH = OH- R ² (I) in which R is hydrogen or an unbranched aliphatic hydrocarbon group and. R is a hydrocarbon 1 2 represents a group, where R and R together are 5 to 18 hydrocarbons have atoms, with carbon monoxide and one monohydric primary or secondary alcohol in the presence of a cobalt compound as a catalyst, an amount of hydrogen, which is about 0.01 to 0.125 hol per mole of carbon monoxide is, and at least one organic base of the general formula (II) J ' in which R ⁵ , R ^ and R ⁵ either all represent hydrogen or one or more of them represent a hydrocarbon group, such as an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl or a benzyl group, while the other symbols represent hydrogen or two adjacent symbols of them represent a benzene ring or a hydrogenated benzene ring together with the two carbon atoms of the pyridine ring B to which they are attached, while 009836/2209 ORIGINAL INSPECTED the remaining symbol consists of hydrogen or a hydrocarbon group, at a temperature between about 110 and 220 ⁰ G and a pressure which is at least about 50 atm. 2. The method according to claim 1, characterized in that 1-alkenes of the general formula OH ₂ = CH-R ² implemented. 3. The method according to claim 1 or 2, characterized in that the monohydric alcohol is made from methanol consists. 4. The method according to any one of claims 1 to 3, characterized in that the catalyst consists of a carbonyl cobalt compound consists. 5. The method according to claim 4, characterized in that the carbonyl cobalt compound ge * forms is. 6. The method according to any one of claims 1 to 5 »thereby characterized in that the amount of catalyst used, calculated as moles of cobalt, per mole of alkene 0.004 to 0.064. 7. The method according to any one of claims 1 to 6, characterized in that the amount of hydrogen is between Is 0.02 and 0.10 moles per mole of carbon monoxide. 8. The method according to any one of claims 1 to 7, characterized in that the organic base comprises a methyl pyridine. 009836/2209 9. The method according to claim 8, characterized in that the organic base consists of 4-methylpyridine. 10. Yerfahren according to any one of claims 1 to 9, characterized in that the amount of organic base between 4 and 100 moles per mole of catalyst, calculated as Cobalt. 11. Yerfahren according to any one of claims 1 to 10, dage
amounts to. characterized in that the temperature is 130 to 200 ° C 12. The method according to any one of claims 1 to 11, characterized in that the pressure is higher than 125 at is. 13. The method according to any one of claims 1 to 12, characterized in that a mixture of esters of straight- and branched-chain alkanecarboxylic acids are formed containing at least 70 # esters of straight chain acids. 14 * Process according to one of Claims 1 to 13, characterized in that more than 55 % of alkene are converted. 15. The method according to claim 14, characterized in that more than 85% alkene are converted. 16. The method according to any one of claims 1 to 15, characterized in that the implementation time at least 1 hour. 17. The method according to any one of claims 1 to 16, characterized in that the conversion time is less than 5 hours. 009836/2209 18. The method according to any one of claims 1 to 17, characterized in that 1-alkenes in a mixture of straight and branched alkanecarboxylic acids with 8 to 18 carbon atoms with at least 70 % esters of straight-chain acids by reaction with carbon monoxide and a monohydric primary alcohol, using a cobalt compound as a catalyst and in the presence of an amount of hydrogen which does not exceed 0.03 mol per mol of carbon monoxide, and at least one organic base of the general formula (II) of claim 1 at a temperature of 160 to 180 ° 0 and at one Pressure from 210 to 230 atm can be converted over 2 to 5 hours, after which the reaction mixture is distilled and the remaining cobalt salts are recycled. 009836/2209 ORIGINAL