DE10220754A1 - 2,4-dialkyl branched aldehydes and derivatives which can be prepared therefrom - Google Patents

Abstract

The invention relates to 2,4-dialkyl branched aldehydes and derivatives which can be prepared therefrom, their use and a process for their preparation by aldol condensation.

Description

The invention relates to 2,4-dialkyl-branched aldehydes and from these derivatives that can be produced, their use and a method for their production through aldol condensation.

Branched alcohols, carboxylic acids and their derivatives show in comparison corresponding linear compounds of the same carbon number other physical properties. So usually decreases with increasing degree of branching the melting point as the viscosity increases. The low melting point is for many applications of particular importance, such as when the substances are not only liquid at low temperature, but also their physical state via one should not change a wide temperature range. To what extent the physical properties and in particular how individual parameters behave towards each other and be influenced by the nature of the branch is not predictable.

Some unsaturated fatty alcohols meet the "low melting point" criterion, however, the double bonds have the problem of being sensitive to oxidation be causing discoloration and other undesirable changes to the Products. Guerbet alcohols and acids (2- alkyl-branched alcohols or acids), which by means of the Guerbet reaction or subsequent alkali melt oxidation according to DE 195 21 900-A1 and by the company Sasol under the trade name ISOFOL or ISOCARB are distributed. Single branched long chain alcohols, Carboxylic acids, their derivatives and applications are e.g. B. Subject of A. J. O'Lennick, Jr., Journal of Surfactants and Detergents, Vol. 3, 2001, pp. 311-315.

As branched C18 alcohols or acids are isostearyl alcohol and Isostearic acid has technical importance. The isostearic acid is a co-product the oligomerization of oleic acid and is complicated by separation, Hardened and fractional crystallization worked up. The transfer to the corresponding alcohols runs through the production of the methyl ester and subsequent Hydrogenation. The end product has no uniform structure, lies as a mixture of positional isomers before and further contains z. T. considerable amounts of undesirable aromatic and cyclic compounds and lactones.

Furthermore, multiply branched aldehydes and alcohols are known, in their Manufacturing has undergone an oxo process. For example Isotridecanol is a multi-branched alcohol, which is produced by trimerization of butene or Tetramerization of propene and subsequent hydroformylation becomes. The regioselectivity of oxosynthesis can only be controlled to a limited extent and usually leads to a product mixture of positional isomers. WO 01/85651-A2 describes e.g. B. a process for the preparation of branched alcohols by oligomerization of 1-olefins and subsequent oxo synthesis. in this connection predominantly mono-branched alcohols are obtained.

Furthermore, DE 26 13 996-A1 (corresponds to GB 1 547 856) contains 2,4-dialkyl-branched aldehydes having 7 to 18 carbon atoms with the following structure


with x and y = 0 to 4 and R = C1- to C4-alkyl and from these accessible by reduction alcohols and their esters with dicarboxylic acids. The aldehydes are produced by double aldol condensation in aqueous alkali hydroxide solutions using a phase transfer catalyst. If a 2,4-dialky-branched aldehyde is produced by trimersizing linear aldehydes of the same carbon number, propanal to pentanal can generally be educts. Only butyraldehyde is described.

Furthermore, US Pat. No. 6,090,986 discloses 2,4-dialky-branched aldehydes with 9 carbon atoms, which are accessible by double aldol condensation from propanal in a basic aqueous environment. Their hydrogenation product (hydrogenation of the CC double bond) has the following structure

According to US 6,090,986, it is important to use aldol condensation to dispense with a phase transfer catalyst.

Disadvantage of the previously known production processes for 2,4-dialkyl branches Aldehydes, alcohols and acids is that these are only short chain products in acceptable Deliver yields and / or mixtures of positional isomers. The mixtures of Positional isomers require extensive cleaning and therefore lead to expensive products when high purity is required. The following invention now surprisingly offers access to defined branches in high yields Aldehydes and their secondary products with surprising product properties.

It has been shown in particular that the method according to US 6,090,986 and / or DE 26 13 996-A1 not for the preparation of 2,4-dialkyl branched Aldehydes with 18 and more carbon atoms are suitable and too low Yields.

The object of the present invention is therefore to overcome the disadvantages of To overcome the prior art and a method for producing 2,4- Provide dialky-branched unsaturated aldehydes that are in themselves functionalized in a known manner, approximately selectively to the corresponding saturated Aldehydes are hydrogenated, then oxidized to acids or reduced to alcohols can. The compounds according to the invention point towards the available ones branched multi-component / isomer mixtures of the prior art surprising Properties on.

The object is achieved according to the invention by saturated or monounsaturated 2,4-dialkyl branched compounds of the general formula


wherein
X -CHO, -COOH or their soaps, alkoxylates and esters and -CH ₂ O (C _x H _2x O) _n H or their esters, sulfates, ether carboxylic acids and phosphates with x = 2 to 4 and n = 0 to 100 is. The ester groups preferably have 1 to 32, particularly preferably 2 to 22, carbon atoms.
R ¹ and R ^{2 are} independently linear and branched, preferably linear, hydrocarbon groups having 4 to 14, preferably 4 to 8 carbon atoms, and
R ^{3 is} a linear hydrocarbon group with 5 to 15 carbon atoms, preferably 5 to 9.

In a preferred embodiment of the invention, R ^{1 is} equal to R ² and R ^{3 is} not equal to R ¹ and R ² , particularly preferably R ³ contains exactly one carbon atom more than R ² and R ³ .

R ¹ and R ² are advantageously saturated, linear hydrocarbon chains of the general formula

-C _a H _{2a + 1}

with a = number of carbon atoms

The invention also relates to 2,4-dialkyl branched carboxylic acids, i. H. Compounds in which X is a carboxyl group -COOH, in particular 2,4-dibutyldecanoic acid and their esters with z. B. C2 to C22 alcohols and 1 to 6 hydroxy groups. In particular, here are the esters of neopentyl polyols (such as trimethylolpropane, Neopentyl glycol, pentaerythritol), Guerbet alcohols, glycol, glycerin, hexyl, stearyl, Isostearyl, palmityl, isopropyl, and 2,4-dibutyldecyl alcohol called. Likewise are The invention 2,4-dialkyl branched alcohols and their esters, with z. B. C2 to C22 mono-, di- (e.g. phthalic acid, 1,4-cyclohexanedicarboxylic acid) and polycarboxylic acids (e.g. trimellitic acid or citric acid). Examples include monocarboxylic acid esters here the esters of Guerbet, Laurin, Myristin, Palmitin, Stearyl, Isostearyl and Oleic acid and the acetate, lactate, adipate, neopentanoate, acrylate and methacrylate called.

Furthermore, there are further secondary products of the 2,4-dialkyl branched alcohols Subject of the invention. The sulfates, ether sulfates, alkoxylates, especially ethoxylates and propoxylates, ether carboxylic acids and phosphates call.

• a) gemischte Aldolkondensation eines in 2-Stellung unverzweigten Aldehyds und eines in 2-Stellung verzweigten Aldehyds und
• b) ggf. selektive Hydrierung der C-C-Doppelbindung,
  • - wobei der in 2-Stellung nicht verzweigte Aldehyd 6 bis 14, vorzugsweise 6 bis 10 Kohlenstoffatome aufweist,
  • - die gemischte Aldolkondensation in Gegenwart einer Base
  • - eines oder mehrerer Lösemittel ausgewählt aus der Gruppe bestehend aus: Methanol, Ethanol, eines C2- bis C6-Polyols, einer Etherverbindung mit 2 bis 12, vorzugsweise 2 bis 6 Kohlenstoffatomen, 1 bis 3 Ethergruppen (-O-) und mindestens einer Hydroxygruppe, und
  • - kleiner 20 Gew.-%, vorzugsweise kleiner 10 Gew.-%, besonders bevorzugt kleiner 5 Gew.-%, Wasser, bezogen auf das Gewicht der eingesetzten Lösungsmittelmenge und abgesehen von dem sich bei der Kondensation bildenden Wasser, durchgeführt wird.

The invention furthermore relates to a process for the preparation of 2,4-dialkyl-branched aldehydes of the general formula


wherein R ¹ , R ² and R ^{3 have} the meaning given above, characterized in that the method comprises the steps

• a) mixed aldol condensation of an unbranched aldehyde in the 2-position and an aldehyde branched in the 2-position and
• b) optionally selective hydrogenation of the CC double bond,
  • the aldehyde which is not branched in the 2-position has 6 to 14, preferably 6 to 10, carbon atoms,
  • - The mixed aldol condensation in the presence of a base
  • - One or more solvents selected from the group consisting of: methanol, ethanol, a C2 to C6 polyol, an ether compound having 2 to 12, preferably 2 to 6 carbon atoms, 1 to 3 ether groups (-O-) and at least one hydroxyl group , and
  • less than 20% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight, of water, based on the weight of the amount of solvent used and apart from the water which forms during the condensation.

Preparation of the aldehyde branched in the 2-position (reactant component)

The 2-branched aldehyde used in step (a) is, for. B. by Aldol condensation (also mixed aldol condensation) linear and / or branched, preferably linear, aldehydes, at least one aldehyde not being shown in the 2-position, to form an α, β-unsaturated aldehyde branched in the 2-position and subsequent catalytic hydrogenation of the double bond available. This is where the Aldol condensation preferably in a basic aqueous environment up to one Aldehyde chain length of C6 without alcoholic solubilizer, from C8, preferably in Presence of a solubilizer, preferably methanol or ethanol and further preferably without the addition of a phase transfer catalyst.

In the absence of a solubilizer, the reaction is preferably carried out at 100 ° C to 180 ° C, preferably at 120 ° C to 150 ° C, or in the presence of a Solubilizer, preferably from an aldehyde chain length of C8, at 50 ° C to 120 ° C, preferably 60 ° C to 80 ° C.

According to a further process, the aldehyde branched in the 2-position can pass through Dehydrogenation of a 2-alkyl branched alcohol, e.g. B. by means of a Guerbet reaction is accessible.

Preparation of the 2,4-dialkyl-branched aldehyde (step (a) and optionally step (b))

In contrast to the production of the branched educt aldehyde, the mixed one Aldol condensation of a linear, branched, unbranched in the 2-position, preferably linear, aldehyde and an aldehyde branched in the 2-position in Presence of the solvents described above, preferably methanol. Important is that the reaction takes place in a homogeneous reaction and essentially in Absence of (added) water. It is also important to ensure that about the base used, e.g. B. KOH (85%) or NaOH (99%) not too much water in the reaction mixture is entered. The water of condensation that forms still preferably carried out during the reaction. Implementation should be at 50 to 120 ° C, preferably at 60 to 80 ° C, are carried out.

The catalytic selective hydrogenation of the double bond of the unsaturated aldehyde can with hydrogen, preferably on a base-doped, supported Palladium catalyst and in batch or continuous mode in a fixed bed reactor be performed.

The reaction product of the aldol condensation can be purified by distillation or after the hydrogenation. However, the unsaturated aldehyde is preferred distilled before hydrogenation. However, the crude aldehydes can also be added directly to the Follow-up products are transferred.

The process according to the invention is described below using the example of hexanal:
The aldol condensation of hexanal proceeds with 0.9 molar aqueous potassium hydroxide solution in a batch mode or continuously at 150 ° C. with 80% conversion and> 99% selectivity. After phase separation, the product is distilled, the unreacted hexanal is returned to the first process step and the product, 2-butyloctenal over a supported base-doped palladium fixed bed catalyst at 80 to 100 ° C and 10 to 80 bar with 99% conversion and 99% selectivities to 2 - Butyl octanal hydrogenated.

Alternatively, the 2-butyloctanal is produced continuously by a Fixed bed gas phase dehydrogenation of 2-butyloctanol on a copper Catalyst, preferably a Cu catalyst supported on Aerosil, at 220 up to 260 ° C, with conversions from 30 to 60% and selectivities from 97 to 99%. Subsequent separation by distillation allows the alcohol in the first Process step are returned and you get 2-Butyloctanal.

The step of mixed aldol condensation is different from Method of US 6,090,986 according to the present invention in a homogeneous phase, about by using a sodium methoxide solution in methanol as Reaction medium and in the absence of water to a large extent.

If 2-butyl octanal and hexanal are used in accordance with the process of US Pat. No. 6,090,986 um, only traces of the desired product are obtained. Likewise, at the Use of a phase transfer catalyst (for example according to the method of DE 26 13 996) only achieved a yield of 21.5%, while according to the invention at the trimerization step far higher yields, e.g. B. 45% yield becomes.

The trimeraldehydes - formally made from three molecules of hexanal - can according to the invention can be processed directly without purification by distillation. This is important because aldehydes decompose easily under thermal stress. This occurs particularly in the distillation of long-chain, high-boiling aldehydes easy to decarbonylation reactions to form paraffins.

The selective hydrogenation of 2,4-dibutyldecenal to 2,4-dibutyldecanal proceeds similar to the hydrogenation of 2-butyloctenal, the reaction parameters pressure, However, the temperature or dwell time should generally be increased somewhat.

• - Oxidation des Aldehyds zur dialkylverzweigten Carbonsäuren der allgemeinen Formel
  
  
  

oder
Hydrierung des Aldehyds zum 2,4-dialkylverzweigten Alkohol der allgemeinen Formel


oder
Alkalischmelzenoxidation des 2,4-dialkylverzweigten Alkohols zur entsprechenden 2,4-dialkylverzweigten Carbonsäure
worin R¹, R² und R³ die oben angegebene Bedeutung haben. The aldehyde compounds according to the invention, in particular the saturated ones, can be derivatized as shown below:

• - Oxidation of the aldehyde to the dialkyl-branched carboxylic acids of the general formula
  
  
  

or
Hydrogenation of the aldehyde to the 2,4-dialkyl branched alcohol of the general formula


or
Alkaline melt oxidation of the 2,4-dialkyl branched alcohol to the corresponding 2,4-dialkyl branched carboxylic acid
wherein R ¹ , R ² and R ^{3 have} the meaning given above.

The derivatization of 2,4-dibutyldecanal is exemplarily general in the following described.

To produce 2,4-dibutyldecanal, the 2,4- Dibutyldecanal according to the prior art methods for 2,4- Dibutyldecanol, preferably on nickel, cobalt, platinum, copper and / or Molybdenum-containing catalysts, hydrogenated. Preference is given to temperatures of 80 up to 140 ° C and at an increased hydrogen pressure of 10 to 100 bar continuously hydrogenated over a fixed bed.

The 2,4-dibutyldecanal can also be oxidized to 2,4-dibutyldecanoic acid. The oxidation is carried out in batch mode or continuously, preferably with Oxygen or oxygen-containing gas mixtures and preferably in the presence a basic catalyst, for example alkali metal hydroxides, or corresponding alkali metal soaps of 2,4-dibutyldecanoic acid, preferably at Temperatures between 10 to 50 C. The 2,4-dibutyldecanoic acid can from basic catalyst are separated by distillation, the catalyst can be in the Process can be traced.

The preparation of 2,4-dibutyldecanoic acid can also be carried out by Alkaline melt oxidation of 2,4-dibutyldecanol was successful. For this, the alcohol is in one Stirred autoclaves, preferably with a 1.1 to 1.3-fold molar excess KOH for 1 to 5 h, heated to 300 ° C. The resulting potassium soap is washed with a Neutralized acid, for example 10% sulfuric acid, washed and distilled if necessary. Alternatively, the alkali melt oxidation can also be carried out continuously according to DE 195 21 900 A1 can be carried out in a reaction extruder.

It has also been found that multi-branched alcohols are by-products arise in the method described in DE 197 34 673 A1, since the base-catalyzed dimerization using the Guerbet method Trimers cannot be avoided completely. Depending on the reaction conditions (Temperature, residence time, degree of conversion) the content can be varied slightly, so about 3 to 7% trimers can be obtained by hydrogenation and distillation.

In a further variant, the process further comprises the reaction step of simultaneously hydrogenating the olefinic double bond and the aldehyde to give the 2,4-dialkyl-branched alcohol of the general formula


wherein R ¹ , R ² and R ^{3 have} the meaning given above.

The 2,4-dialkyl branched unsaturated aldehydes can according to the prior art Technology common hydrogenation methods for 2,4-dialkyl branched alcohol, preferably containing nickel, cobalt, platinum, copper and / or molybdenum Catalysts are hydrogenated. Preferably in temperature ranges from 80 to 140 ° C and at an increased hydrogen pressure of 10 to 100 bar continuously a fixed bed hydrogenated. In contrast to the two-stage hydrogenation, must be stronger Adequate heat dissipation must be ensured since the hydrogenation reactions run exothermic. In general, however, selective for both reaction steps and complete hydrogenation, the same reactor can be used, whereby in particular, the selectivity catalyst is crucial. The Reaction conditions to increase selectivity must be the respective catalyst system be adjusted.

The compounds according to the invention have a very wide range of uses. In cosmetic formulations, the alcohols can be used as consistency enhancers, used in particular to modify the spreading behavior of a formulation become. Furthermore, the branched alcohols can be used especially in the fields are used in which high oxidation stability and low melting point low volatility at the same time. For example, such Alcohols used in printing inks, in metalworking, as Find coating resins and systems for automotive and industrial applications. Furthermore for coating plastics, as hydraulic oils and Heat transfer fluids, oil production aids, textile auxiliaries and Lubricant range, e.g. B. as synthetic 2-stroke and 4-stroke engine oils or Lubricant additives.

The acids or soaps with a branched structure can be bioresistant Surfactants and corrosion inhibitors in water-based metalworking fluids be used. The use of branched acids or soaps is also in water-based paints and varnishes for metal coatings possible.

The 2,4-dialkylcarboxylic acids can e.g. B. as an additive to cosmetic Compositions are used, it being assumed that these are antibacterial, act antimycotic and / or antiviral.

In addition to alcohol and acids, there are also their secondary products, such as for example sulfates, ether sulfates, alkoxylates, in particular ethoxylates and propoxylates, Ether carboxylic acids and phosphates as anionic or nonionic surfactants and Emulsifiers of particular interest.

The properties of 2,4-dibutyl decanol are compared in the following tables with some commercially available branched C18 alcohols and secondary products. ISOFOL 18T is a Guerbet alcohol made by dimerizing a mixture of octanol and decanol:
Speziol® C18 ISO C is an isostearyl alcohol from Cognis. ISOFOL® 18T is a Guerbet alcohol from SASOL. The purity of 2,4-dibutyldecanol was 98.0% by weight. Table 1 Physical properties of branched C18 alcohols

Table 2 below shows some commercially available isosteric acids and the ISOCARB® 18T (SASOL) of the 2,4- Dibutyldecaric acid compared. ISOCARB® 18T is a Guerbet acid that by Guerbet reaction of a mixture of octanol and decanol and subsequent oxidation is produced. Prisorine® 3505 (company Uniquema) and Emersol® 874 (Cognis) are isostearic acids. The 2,4-dibutyldecanoic acid was in a purity of 97.5%.

The esters of branched alcohols and / or acids are also of particular interest as lubricants. Because of the excellent low-temperature properties, the low vapor pressure, the good hydrolysis and oxidation stability of the esters on the one hand and the possibility to precisely adjust the required properties, such as viscosity, by selecting the associated alcohol or acid component, this enables Manufacturer of lubricants a wide range of applications. The extremely low melting point is also observed with other derivatives. Table 2 Physical properties of branched C18 acids

Table 3 shows the physical properties of 2,4-dibutyldecyl isostearate, prepared from 2,4-dibutyldecanol and isostearic acid (UCH 3505).

It is clear from Table 4 that much shorter wetting times are observed for 2,4-dibutyldecanoloxethylates than for other branched C18 oxethylates. Table 3 Physical properties of 2,4-dibutyldecyl isostearate, made from 2,4-dibutyldecanol and isostearic acid (UCH 3505) Hydroxyl number [mg KOH / g] 1.24 Acid number [mg KOH / g] 0.10 Saponification number [mg KOH / g] 105.40 Iodine number [mg I / 100 mg] 0.89 Water content [%] 0.02 Color APHA [Hazen] 41,00 dynamic viscosity [mPa] 58.30 Kin. Ubelohde viscosity 20 ° C [cST] 67.60 Kin. Ubelohde viscosity 40 ° C [cST] 28,00 Kin. Ubelohde viscosity 95 ° C [cST] 5.33 viscosity Index 126.00 Pourpoint n. Herzog [° C] <-60.00 Flash point [° C] 244.00 Table 4 Physical properties of branched C18 oxyethylates

Experimental part example 1 Aldol condensation of hexanal, without solubilizer

In a 300 ml pair autoclave with a hollow shaft stirrer, 65 ml (54 g, 0.54 mol, 96.5%) hexanal and 65 ml of a 0.5 molar aqueous KOH solution 1400 rpm heated to 150 ° C. After the reaction temperature was reached stirred for a further 60 min and then cooled. Received after phase separation a crude product containing 86.3% 2-butyloctenal and 10.5% hexanal. To Working up by distillation gave the 2-butyloctenal in 99.2% purity.

Example 2 Aldol condensation of dodecanal, with solubilizer

In a 100 ml flask were 30 ml (25 g, 0.14 mol, 98.2%) dodecanal, 7 ml a 0.9 molar aqueous KOH solution and 23 ml of ethanol with stirring for 60 min heated under reflux. After cooling, the phases were separated and the Solvent mediator distilled off. The crude product contained 87.6% 2-decyltetradecenal, 4.4% isomerized 2-decyltetradecenal and 5.1% dodecanal.

Example 3 Continuous selective hydrogenation of 2-butyloctenal to 2- Butyloctanal

In a tubular reactor (d = 25 mm, l = 400 mm), 3 ml / min of 2-butyloctenal (Content 99.2%) with 60 l / h hydrogen at 55 bar and 90 ° C over a base-doped palladium catalyst passed. A crude product consisting of 97.5% 2-butyloctanal, 0.7% 2-butyloctenal and 1.1% 2-butyloctanol. This corresponds to a conversion of 99.3% and a selectivity of 98.9%.

Example 4 Dehydrogenation of 2-butyl octanol to 2-butyl octanal

In a tubular reactor (d = 25 mm, l = 400 mm) 4 g / min were at 240 ° C and 77 mbar (0.02 mol) gaseous 2-butyl octanol over a supported Copper catalyst dehydrated to 2-butyl octanal. Based on a 2- Butyl octanol content of 99.1%, a crude product mixture consisting of 52.3% 2- Butyl octanal, 46.1% 2-butyl octanol, 0.3% 2-butyl octyl 2-butyl octanoate and 0.1% Undecane. This corresponds to a turnover of 53.5% and a selectivity of 98.7%.

Example 5 Comparative Example 1 based on US 6,090,986, mixed Aldol condensation of 2-butyl octanal with hexanal without solvent and without PTK

36.1 g of an aqueous 1 molar sodium hydroxide solution were in one 300 ml PARR autoclaves heated to 125 ° C. At 1250 rpm was inside a mixture of 11 g (0.109 mol) hexanal, 92 g (0.5 mol) 2- Butyl octanal and 1.36 g (0.008 mol) dodecane pumped in. After cooling down The crude product was washed at 20 ° C. with water. gas chromatography only 1.5% of the condensation product of hexanal (2-butyloctenal) and no conversion of 2-butyloctanal to 2,4-dibutyldecenal was found.

Example 6 Comparative Example 2 based on US 6,090,986, Mixed Aldol condensation of 2-butyl octanal with hexanal without solvent and without PTK

The reaction was carried out as in Comparative Example 1, but at 150 ° C. The hexanal was converted to 81% to 2-butyloctenal and it was only 0.2% 2,4-dibutyldecenal detected in the crude product.

Example 7 Comparative Example 3 based on US 6,090,986, Mixed Aldol condensation of 2-butyl octanal with hexanal without solvent and without PTK

The reaction was as in Comparative Example 2, but with 2 molar Sodium hydroxide solution performed. Over 74% of the hexanal was Butyloctenal implemented and there were only 0.4% 2,4-dibutyldecenal demonstrated.

Example 8 Comparative Example 4 based on US 2,852,563, Mixed Aldol condensation of 2-butyl octanal with hexanal without solvent and without PTK

46.3 g of an aqueous 2% potassium hydroxide solution were placed in a 300 ml PARR autoclaves heated to 94 ° C. At 1300 rpm, within 70 min a mixture of 50 g (0.5 mol) hexanal and 58 g (0.32 mol) 2-butyl octanal pumped. After cooling to 20 ° C, the phases were separated and that Washed raw product with water. No 2,4- Dibutyldecenal, but 13.7% 2-butyloctenal can be detected.

Example 9 Comparative Example 5 based on DE 26 13 996, Mixed Aldol condensation of 2-butyl octanal with hexanal with PTK

3.5 g (0.086 mol) sodium hydroxide, 32 g water, 2.35 g aliquat 336 (Tricaprylmethyl-ammonium chloride) and 92 g (0.5 mol) of 2-butyloctanal were combined in one Submitted flask and dropwise at 95 ° C within 5 h with 25 g (0.25 mol) Hexanal offset. It was found that only 3.2% of the 2-butyloctanal had reacted. The main product is the 2-butyloctenal formed by the condensation of hexanal.

Example 10 Comparative Example 6 based on DE 26 13 996, Mixed Aldol condensation of 2-butyl octanal with hexanal with PTK

3.5 g (0.086 mol) of sodium hydroxide, 8.25 g of water and 2.35 g of Aliquat 336 were added placed in a flask and added dropwise with a mixture within 1 h from 18 g (0.18 mol) of hexanal and 64 g (0.35 mol) of 2-butyloctanal. It showed that 19.8% of the 2-butyloctanal had reacted and that 59% of the reacted 2-Butyloctanals implemented in the desired product, 2,4-dibutyldecenal were.

Example 11 Comparative Example 7, Mixed aldol condensation of 2-butyloctanal with Hexanal with solubilizer

The reaction was carried out as in Example 6, but instead of Phase transfer catalyst (PTK) 40 ml of methanol added. It turned out that only 14.4% of the 2-butyloctanal had reacted, and that 37.6% of the reacted 2- Butyloctanals were converted into the desired product, 2,4-dibutyldecenal.

Example 12 Mixed aldol condensation of 2-butyl octanal with hexanal Solvency mediators and PTK

3.5 g (0.086 mol) sodium hydroxide, 8.25 g water, 2.35 g Aliquat® 336 and 40 ml Methanol was placed in a flask and refluxed within 1 h dropwise with a mixture of 50 g (0.5 mol) hexanal and 92 g (0.5 mol) 2- Butyl octanal added. It was found that 30% of the 2-butyloctanal had reacted and that 81% of the 2-butyloctanal reacted into the desired product, 2,4- Dibutyldecenal, were implemented.

Example 13 Mixed aldol condensation of 2-butyl octanal with hexanal methanolic NaOH solution

112 g (2.8 mol) of sodium hydroxide and 1280 ml of methanol were in a flask submitted and under reflux within 4 h dropwise with a mixture 400 g (4 mol) of hexanal and 736 g (4 mol) of 2-butyl octanal. It showed found that 77.9% of the 2-butyloctanal had reacted and that 57.7% of the reacted 2-Butyloctanals implemented in the desired product, 2,4-dibutyldecenal were. Gas chromatography indicated in the reaction product about 46.3% double branched C18 connections an additional 32.8% single branched C12 Connections demonstrated.

Example 14 Mixed aldol condensation of 2-butyl octanal with hexanal methanolic NaOH solution

7 g (0.18 mol) of sodium hydroxide and 80 ml of methanol were in a flask submitted and under reflux (74 ° C) dropwise within 90 min with a Mixture of 25 g (0.25 mol) of hexanal and 92 g (0.5 mol) of 2-butyl octanal was added. It was found that 56.9% of the 2-butyloctanal had reacted and that 57.1% the reacted 2-butyloctanal into the desired product, 2,4-dibutyldecenal, have been implemented. 38.5% were determined by gas chromatography in the crude reaction product double branched C18 compounds detected.

Example 15 Selective hydrogenation of 2,4-dibutyldecenal to 2,4-dibutyldecanal

1085 g of a mixture containing 54.3% 2,4-dibutyldecenal were at 90 ° C and hydrogenated 60 bar for 24 h over a base-doped palladium catalyst. To after cooling to room temperature, the catalyst is filtered off. The Crude product contained 48.9% 2,4-dibutyldecanal, 2.7% 2,4-dibutyldecanol, 2.6% 2,4- Dibutyldecenol and 1.2% 2,4-dibutyldecenal. This corresponds to an implementation of 97.8% and a selectivity of 92.1%. With the secondary components of The starting and end products are predominantly dimeric and tetrameric Products.

Example 16 Complete hydrogenation of 2,4-dibutyldecenal to 2,4- Dibutyldecanol

1000 g of the crude product from the mixed aldol condensation, containing 42.8% 2,4-dibutyldecenal and 1.7% 2,4-dibutyldecadienal were added to 50 g of Raney Nickel, made from 100 g nickel alloy, at 2 bar hydrogen pressure and Hydrogenated at 20 ° C. A crude product was obtained from 36.8% of 2,4-dibutyldecanol, 5.1% 2,4-dibutyldecanal and 0.7% 2,4-dibutyldecane. Other components were according to the composition of the starting material predominantly dimeric and higher condensed alcohols.

Example 17 Hydrogenation of the Guerbet trimer sump to 2,4-dibutyldecanol

1200 g of the bottom product of the Guerbet reaction with the hexanol procedure were hydrogenated at 90 ° C and 60 bar over a nickel catalyst. In the raw product 59.6% of 2,4-dibutyldecanol were detected. By subsequent The product was isolated by distillation in a purity of 98%. In one Another attempt could be made continuously at 125 ° C and 18 bar above the nickel Catalyst are hydrogenated with the same result.

Example 18 Oxidation of 2,4-dibutyldecanal to 2,4-dibutyldecanoic acid

320 g of a mixture containing 48.9% 2,4-dibutyldecanal was added with 1.03 g (0.016 mol) 85% KOH added, cooled to 15 ° C and with a Provide a nitrogen pressure of 3 bar. Then 13.4 l / h of oxygen in the Reactor passed until there was a pressure rise to 8 bar. After relaxing the A crude product with the following composition was obtained in the reactor: Dibutyldecanoic acid 42.4%, 2,4-dibutyldecanal 4.9%. This corresponds to one Conversion of 90% and a selectivity of 96.4%. With the secondary components of The starting and end products are predominantly dimeric and tetrameric Condensation products.

Example 19 Alkaline melt oxidation of 2,4-dibutyloctanol to 2,4- Dibutyldecansäure

3 kg (11.1 mol) of 2,4-dibutyldecanol (92.7%) and 880 g (13.4 mol) were in heated to 300 ° C in an autoclave within 5 h. Then 60 min kept at this temperature and after cooling with 10% Neutralized sulfuric acid at 90 ° C. The 2,4-dibutyldecanoic acid was obtained in a purity of 93.3%.

Example 20 Esterification of 2,4-dibutyldecanol with isostearic acid

5 mol 2,4-dibutyldecanol, 5.25 mol isostearic acid, 0.15% by weight Methanesulfonic acid and 150 ml of cyclohexane were refluxed for 6 hours on a water separator heated. The temperature rose from 11 ° C to 140 ° C. After cooling was the acid excess at 8 mbar and a jacket temperature of 175 ° C on Short path evaporator separated.

Example 21 Esterification of 2,4-dibutyldecanoic acid with 2-octyldodecanol, ISOFOL 20

5 mol 2,4-dibutyldecanoic acid, 5.25 mol 2-octyldodecanol, 0.15% by weight Isopropyl titanate (IPT) and 150 ml of xylene were refluxed for 28 hours on a water separator heated. The temperature rises from 120 ° C to 210 ° C. After cooling was the alcohol excess at 0.68 mbar and a jacket temperature of 175 ° C. separated on the short path evaporator.

Example 22 Oxethylation of 2,4-dibutyldecanol

396 g (1.47 mol) of 2,4-dibutyldecanol were in a 51-oxyethylation reactor 2.0 g of sodium methoxide are added and in portions at 157 ° C. within 60 min 1104 g (25.1 mol) of ethylene oxide were added. After stirring for a further 30 min 157 ° C. was allowed to cool to 80 ° C., a stream of nitrogen was passed through for a further 4 h the product and neutralized with acetic acid. A colorless product was obtained.

Example 23 Sulfation of 2,4-dibutyldecanol with chlorosulfonic acid

268 g (0.99 mol) of 2,4-dibutyldecanol were placed in the sulfating flask and 119.5 g (1.02 mol) of chlorosulfonic acid were added slowly at 30 ° C. in the course of 30 minutes. The drip rate was chosen so that the reaction temperature could be kept constant with ice water cooling. After the addition had ended, the mixture was left to react for a further 30 minutes and neutralized by stirring in 1000 g of a 4.4% strength sodium hydroxide solution. The 2,4-dibutyldecyl sulfate had the following analytical values: WAS 27.7%, NaCl 0.16%, Na ₂ SO ₄ 3.5%, UV 2.9%.

Example 24 Continuous selective hydrogenation of 2,4-dibutyldecenal to 2,4- Dibutyldecanal

89.0% 2,4-dibutyldecenal, 4.1% iso-2,4-dibutyldecenal, 3.3% 2,4-dibutyldecenol were in a fixed bed reactor with a flow rate of 3 ml / min at 130 ° C and 55 bar hydrogenated over a base-doped palladium catalyst. The raw product contained 77.3% 2,4-dibutyldecenal, 7.6% 2,4-dibutyldecenol and 3.5% 2,4- Dibutyldecenol and 2.4% 2,4-dibutyldecanoic acid.

Claims (13)

1. 2,4-dialkyl branched compound of the general formula


wherein
X -CHO, -COOH or their soaps, alkoxylates and esters and -CH ₂ O (C _x H _2x O) _n H or their esters, sulfates, ether carboxylic acids and phosphates with, possibly different for each n, x = 2 to 4 and n = 0 to 100, and
R ¹ and R ^{2 are} independently hydrocarbon groups with 4 to 14 carbon atoms and
R ^{3 is} a linear hydrocarbon group of 5 to 15 carbon atoms. 2. A compound according to claim 1, wherein R ¹ is R ² . 3. A compound according to claim 1, wherein R ¹ is R ² and R ^{3 is} not R ¹ and R ² . 4. A compound according to claim 3, wherein R ^{3 contains} exactly one CH ₂ group more than R ² . 5. A compound according to any one of the preceding claims, wherein R ¹ and R ^{2 are} saturated, linear hydrocarbon chains of the general formula
-C _a H _{2a + 1}
with a = 4 to 14, preferably 4 to 8. 6. A compound according to any one of the preceding claims, wherein X is a carboxyl group -COOH, R ¹ and R ^{2 are} C ₄ H ₉ and R ^{3 is} C ₅ H ₁₁ . 7. Process for the preparation of 2,4-dialkyl branched aldehydes of the general formula


wherein R ¹ , R ² and R ³ have the meaning given in one of the preceding claims,
the method comprising the following steps a) mixed aldol condensation of an unbranched aldehyde in the 2-position and an aldehyde branched in the 2-position and b) optionally selective hydrogenation of the CC double bond, the aldehyde which is not branched in the 2-position has 6 to 14 carbon atoms, the mixed aldol condensation in the presence of a base, - One or more solvents selected from the group consisting of: methanol, ethanol, a C2 to C6 polyol, an ether compound having 2 to 12, preferably 2 to 6 carbon atoms, 1 to 3 ether groups (-O-) and at least 1 hydroxy group , and less than 20% by weight of water, based on the weight of the solvent used and apart from the water which forms during the condensation, is carried out. 8. The method according to claim 7, characterized in that the method further comprises the steps - Selective catalytic hydrogenation of the olefinic double bond of the 2,4-dialkyl branched aldehyde, and - Oxidation of the aldehyde to 2,4-dialkyl branched carboxylic acids of the general formula


wherein R ¹ , R ² and R ³ have the meaning given in one of the preceding claims. 9. The method according to claim 7, characterized in that the method further comprises the step instead of step (b) - Simultaneous hydrogenation of the double bond and the aldehyde function to give the 2,4-dialkyl-branched alcohol of the general formula


wherein R ¹ , R ² and R ³ have the meaning given in one of the preceding claims. 10. The method according to any one of claims 7 to 9, characterized in that step (a) is carried out essentially exclusively in methanol. 11. The method according to any one of claims 7 to 10, characterized in that reaction step (b) is carried out at 60 to 80 ° C. 12. The method according to any one of claims 7 to 11, characterized in that the catalytic hydrogenation (b) with hydrogen and a base-doped palladium Catalyst is carried out. 13. Use of the compounds according to one of claims 1 to 6 for Manufacture of metal or plastic processing and coating agents, Plastic additives, lubricants or lubricant additives, anti-corrosion agents, for Manufacture of detergents, detergents and cleaning agents or for the manufacture of cosmetic and / or pharmaceutical preparations.