DE1238914B - Process for the preparation of carboxylic acid hydroxy esters and hydroxycarboxylic acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

C07d
German class: 12 ο - 27

Number: 1238 914

File number: E28116IVb / 12o

Filing date: November 12, 1964

Open date: April 20, 1967

The invention relates to a method of manufacture of carboxylic acid hydroxy esters and hydroxycarboxylic acid esters of the general formulas

OR ₂

R ₁ -CO-CH ₂ -C-CH ₂ -OH (A)

R ₃

OR ₂
R ₁ -CH ₂ OCC-CH ₂ -OH (B)

in which R _{1 is} a hydrogen atom, an alkyl group with 1 to 17 carbon atoms, an alkenyl group with 2 to 8 carbon atoms, a cyclopentyl, ao cyclohexyl, cyclohexenyl, phenyl, tolyl, naphthyl, benzyl or furyl group and R ₂ and R ₃ denote alkyl groups with 1 to 4 carbon atoms.

The presence is characteristic of the esters which can be prepared by the process of the invention a neopentyl group.

The production of esters by condensation of aldehydes has already been described by L. C1 a i s e η in Ber., 20, p. 646 (1887). The condensation reaction was later described by V. E. T i s c h e η k ο examined in detail. The research results of V. E. Tischenko were published in J. Russ. Phys. Chem. Soc, 38, p. 355 (1906). Based on this research, the reaction is named Tisehenko reaction. The condensation of aldehydes has recently been continued by V i 11 i a η i and Nord, J. Amer. Chem. Soc, 68, p. 1674 (1946), investigated which different catalyst systems for the reaction developed. Suitable catalysts are in processes for the preparation of carboxylic acid hydroxyesters and Hydroxycarboxylic acid esters

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff, H. Bartels
and Dipl.-Chem. Dr. J. Brandes, Patent Attorneys, Stuttgart 1, Langestr. 51

Named as inventor:
Roy B. Duke, Jr., Smyrna, Ga .; Milton Armor Perry,
Longview, Tex. (V. St. A.)

Claimed priority:
V. St. ν. America November 14, 1963 (323 602)

for example the alkoxides of aluminum or the alkali metals. It has been shown that when using of alkali metal alkoxides besides the simple esters, which are the main reaction products by condensation of 2 moles of aldehyde accumulate, glycol monoesters are formed, which by trimolecular condensation in lower yield can be obtained.

US Pat. No. 3,091,632 describes a process for the preparation of glycol monoesters, which proceeds according to the following reaction equation:

CH ₃

3CH, - CH - CHO

NaOR

CH ₃ CH ₃ O CH ₃

CH ₃ -CH-CH-C-CH ₂ -OC-CH-Ch ₃ OH CH ₃

So far it has been assumed that the Tischenko wrote that the reaction only takes place as an anomalous Tischenko reaction when catalysts 50 have been drawn, after which a self-condensation of have been added. In the journal J. Org. Chem., 25, hydroxypivaldehyde by simple heating of the S. 2219 (1960), a method sawn aldol about 8O ⁰ C, namely 8 to 48 hours, more recently long,

709 550/378

can be achieved. This so-called anomalous Tischenko reaction takes place without the addition of a catalyst away.

It has now been found, surprisingly, that an anomalous, non-catalytic Tischenko reaction also occur between an aldol and a simple aldehyde with the formation of mixed esters can.

The process of the invention is characterized in that a tertiary formaldol of the general formula

R ₂
HO-CH ₂ -C-CHO

R,

in which R ₂ and R _{3 have} the meaning given, with an aldehyde of the general formula

R ₁ - CHO

in which R _{1 has} the meaning given, is reacted at a temperature of 100 to 30O ⁰ C in the absence of a catalyst.

If R _{1 has} the meaning of an alkyl group, this can be straight-chain or branched and, for example, consist of a methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, hexyl, 2-ethylhexyl group , Heptyl, decyl, dodecyl, pentadecyl or heptadecyl group.

R ₂ and R ₃ can likewise be straight-chain or branched-chain alkyl groups, it being possible for the alkyl groups to be identical to or different from one another.

The method of the invention can thus be represented by the following reaction equation:

I. R ₁ -CHO + HO-CH ₂ -C-CHO

R ₃
O

R ₂ OR ₂

R ₁ -CO-CH ₂ -C-CH ₂ -OH + R ₁ -CH ₂ -OCC-CH ₂ -OH

(A)

where R ₁ , R ₂ and R _{3 have} the meaning given.

It has proven to be particularly advantageous if 3 to 5 moles of aldehyde are mixed with 1 mole of tertiary formaldol implements.

In addition, particularly advantageous results are obtained if a tertiary aldol of the general formula

R ₆

OH-CH ₂ -C-CHO

R ₇

in which R ₆ and R _{7 represent} alkyl groups having 1 to 4 carbon atoms, with an aliphatic aldehyde of the formula

R ₅ -CR ₄

CHO

(B)

these compounds with dibasic acids such as adipic, pimeline, azelaic and tereph thalic acid excellent plasticizer for a wide variety of synthetic plastics, such as in particular Polyester. Furthermore, higher homologs can be esterified with monobasic acids, making excellent synthetic lubricants. The hydroxy esters (A) are particularly advantageous Properties. They are also particularly suitable as chain-terminating alcohols in production of polyesters of high hydrolytic stability, for example a polyester prepolymer with Acid end groups are reacted with hydroxyneopentyl - 2 - ethyl hexanoate.

Theoretically, a catalyzed Tischenko reaction between an aldol and a simple Aldehyde, other compounds are also formed, for example according to the following reaction equations:

55 II. 2R ₁ -CHO

R ₁ -CH ₂ -OCR ₁

R,

in which R ₃ , R ₄ and R _{5 are} hydrogen atoms or alkyl groups or phenyl groups with 1 to 10 carbons. 2HO - CH ₂ - C - CHO are substances, at a temperature of about 100 to 6o

200 ° C in an inert atmosphere. ^

The hydroxy esters (A) and (B) are bright viscous ³

Liquids are characterized by excellent hydrolytic stability and high resistance

against thermal or oxidative degradation 65

and are particularly useful as solvents, hydraulic fluids and plasticizers. For example, the tetra-esters R ₂

OR ₂

HO-CH ₂ C-CH ₂ -OC C-CH ₂ OH

5 6

where R ₁ , R ₂ and R _{3 have} the meaning already given

because there is no control of product distribution

is possible. 3 moles of isobutyraldehyde and 1 mole of hydroxypiv-

However, it has now been shown that the non-aldehyde were heated for 8 hours in an autoclave catalytic Tischenko reaction of the invention below 5 under a nitrogen pressure of 36 kg / cm ² at 160 ⁰ C complete exclusion of the specified reaction. The implementation took place in the absence of equation II expires. A catalyst was also found. After removal of the Reaktionsdaß by the method of the invention product producible from the autoclave the Reaktionsbaren mixed esters in yields of 60 to 80 was / distilled ° ₀ product, wherein the temperature can be the Destilerhalten when using a three- to io lationsgefäßes was increased up to 200 ° C. A five-fold molar excess of aliphatic, 1.87 moles (93.5%) isobutyraldehyde, alicyclic, aromatic or heterocyclic, was recovered. The distillation product was then operated under vacuum aldehyde. The absence of the fractionally distilled, with 0.77 mol (77%) Hy-catalyst, prevents the expiration of one of the three possible droxyneopentyl isobutyrate with a boiling point of reactions, and of the remaining 15 105 to 110 ° C at a pressure of 20 mm Hg and two reactions that lead to mixed esters 0.17 mol (17%) hydroxyneopentylhydroxypivalate, preferably when the reaction components have a boiling point of 128 to 130 ° C at a pressure of 1 mm applied in the given ratios Hg have been obtained,
will.

The method of the invention thus enables the 20 B is ρ ie 1 2
Manufacture of a new class of hydroxy esters

the given structural formula (A), which compared to 3 moles of 2-ethylhexanal and 1 mole of hydroxypiv-

thermal, hydrolytic and oxidative attacks aldehyde were refluxed in for 24 hours

Resistant and heated as a solvent, absence of a catalyst. The Rea-

hydraulic fluids, plasticizers, marriage product was then distilled, with 1.75 mol

mix intermediates and use blank (87.5 ° / ₀₎ of 2-ethylhexanal was recovered,

The Tischenko reaction product was then used as chain-terminating alcohols in the

Production of polymers can be used vacuum distilled, with 0.80 mol (80 ° / ₀ ) hydroxy

nen. In the same way can be after the neopentyl-2-ethylhexanoate with a boiling point of

drive the invention preparable hydroxyester (B) 30 142 to 146 ⁰ C at a pressure of 2 mm Hg and

use. 0.11 mol (11 ° / ₀₎ ER hydroxyneopentylhydroxypivalate

The method of the invention can be kept in the manner
be carried out that one has a tertiary form

aldol with an aliphatic, alicyclic or example 3
aromatic aldehyde or furfural at a temperature of 35

temperature of about 100 to 300 ⁰ C for 1 to 48 hours 3 moles of isobutyraldehyde and 1 mole of 2-ethyl-2-butyl in the absence of a catalyst. Preferred 3-hydroxypropanal were used in an autoclave with 3 to 5 moles of the ^{aldehyde per mole of the aldol under a nitrogen pressure of 36 kg / cm 2 for} 16 hours. If necessary, the reform can be heated to 175 ⁰ C for. No catalyst action in an inert solvent such as 40 was used. From the reaction product, benzene, toluene or xylene would then be carried out. 1.9 mol (95%) of isobutyr by heating up to 220 ° C. This can be carried out at atmospheric pressure. aldehyde withdrawn. The Tischenko esters were then However, it is also possible distilled at reduced pressure or fractionated to obtain 0.71 mol (71 ° / ₀₎ 2-ethyl-pressure work. If the process is carried out under 2-butyl-3-hydroxypropyl isobutyrate with a boiling pressure, for example at a pressure of 45 points from 133 to 137 ° C. at a pressure of up to about 36 kg / cm ² , an autoclave is used , 2 mm Hg were obtained,
turns into which an inert gas, such as nitrogen, is injected. The reaction products can Example 4
NEN from the reaction mixture according to known

Separation process, for example, by fractionated 50 3 moles of benzaldehyde and 1 mole of hydroxypivaldehyde

Distillation can be obtained. were refluxed for 24 hours. It

Particularly suitable tertiary formaldoles that were not used as a catalyst. The reaction

Starting compounds can be used, product was then distilled, leaving 1.75 mol

are for example hydroxypivaldehyde, 2,2-diethyl- (87.5%) of the benzaldehyde recovered.

3 - hydroxypropanal, 2,2 - di - η - propyl - 3 - hydroxy- 55 Furthermore, 0.68 mol (68%) of hydroxyneo-

propanal, 2,2-diisopropyl-3-hydroxypropanal, 2,2-dipentylbenzoate with a boiling point of 129 to

η - butyl - 3 - hydroxypropanal, 2 ~ methyl-2-ethyl- 136 ° C at a pressure of 1 mm Hg.

3-hydroxypropanal or 2-ethyl-2-n-butyl-3-hy-hydroxy-pivalic acid benzyl ester was

droxypropanal. Particularly suitable aldehydes, which are obtained as yield of 22%.
Starting compounds can be used, 60

are for example acetaldehyde, propionaldehyde, Bu-Example5
tyraldehyde, isobutyraldehyde, valeraldehyde, capro-

aldehyde, heptanal, decanal, dodecanal, tetrahydro- 3 moles 2-methylpentanal and 1 mole hydroxypiv-

Benzaldehyde, benzaldehyde, o-toluene aldehyde, p-to-aldehyde were in an autoclave under one

luene aldehyde, <x - toluene aldehyde, 1 - naphtha! dehyde, 65 nitrogen pressure of 36 kg / cm ^{2 for} 12 hours

2-naphthaldehyde or furfural. 160 ⁰ C heated in the absence of a catalyst. the

The following examples are intended to illustrate the process of mixing the mixture was then removed from the autoclave

Illustrate the invention in more detail. and distilled, the temperature of the distillation

vessel up to 220 ⁰ C was increased. 1.8 moles (90%) of 2-methylpentanal were recovered. The Tischenko esters were then distilled to give 0,75MoI (75%) Hydroxyneopentyl-2-methylpentanoate having a boiling point from 135 to 138 ⁰ C at a pressure of 1.2 mm Hg and 0.15 mole (15%) obtained hydroxyneopentylhydroxypivalate became.

A wide variety of other hydroxyesters can be prepared using the methods described in the examples of structural formulas (A) and (B) using a wide variety of tertiary formaldoles and aldehydes are produced.

Claims (4)

Patent claims: 1. Process for the preparation of carboxylic acid hydroxyesters and hydroxycarboxylic acid esters of the general formulas R ₁ -CO-CH ₂ -C-CH ₂ -OH (A) indicates that one is a tertiary formaldol the general formula R ₂ HO-CH ₂ -C-CHO R ₃ ίο in which R ₂ and R _{3 have} the meaning given, with an aldehyde of the general formula R ₁ - CHO in which R _{1 has} the meaning given, is reacted at a temperature of 100 to 300 ^° C. in the absence of a catalyst. 2. The method according to claim 1, characterized in that 3 to 5 moles of aldehyde with 1 mole converts tertiary formaldol. 3. The method according to claim 1 and 2, characterized in that there is a tertiary aldol of general formula R ₆ OH - CH, CHO and OR ₂ R ₁ -CH ₂ -OCC-CH ₂ -OH (B)
R ₃ in which R _{1 is} a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, naphthyl, benzyl or furyl group and R ₂ and R ₃ denote alkyl groups with 1 to 4 carbon atoms, thereby in which R ₆ and R _{7 represent} alkyl groups having 1 to 4 carbon atoms, with an aliphatic aldehyde of the formula R ₃ R ₅ -CR ₄ CHO in which R ₃ , R ₄ and R _{5 are} hydrogen atoms or alkyl groups or phenyl groups with 1 to 10 carbons, is reacted at a temperature of about 100 to 200 ^° C. in an inert atmosphere. 4. The method according to claim 3, characterized in that that one uses 5, preferably 3 to 4 moles of aliphatic aldehyde per mole of aldol. 709 550/378 4.67 © Bundesdruckerei Berlin