DE2035558A1 - Process for the oxidation of vicinal diol groups - Google Patents

Description

GERMAN GOLD AND SILBBR SCIIEIDEANSTALT VORIvRLS ROJiSSLER Frankfurt (Main), Weissfrau & nstrasse 9

Process for the oxidation of vicinal pin groups

The subject of the application is a process that is being used for the first time allows vicinal diol groups in organic compounds to be oxidized in a technically useful manner and in high yields with cleavage to carboxyl groups.

Although it is known to convert vicinal diols au means stöchiometx'ischer amounts of silver oxide to the corresponding carboxylic acids, but this method is industrially not applicable (j _t Kubias, Collection Czechoslov. Chem "Conimun., VoI 31 (i960), page 1666 to I676 ).

Another method of cleavage of 1,2-diols has also become known, which is carried out with oxygen in the presence of aprotic polar solvents and in the presence of a cobalt compound. However, this method is only applicable to some specific diols and cannot be applied to other diols. In addition, it is not always reproducible and leads to yields which reach a maximum of only $ 70 (G. de Vries, A. Schors: Tetrahedron Letters, No. 54, pages 5689 to 5690, 1968 ).

It has now been found that vicinalc Diolgx'uppen organic compounds to carboxyl groups in the presence of a heavy metal can oxidize if the vicinal en

109884/1962

203555

Diol groups in the presence of an organic solvent and in the presence of ions or ion mixtures of iron, Nickel, palladium or preferably cobalt or manganese are oxidized with a percarboxylic acid, preferably peracetic acid »

The success of this oxidation was quite surprising, since no reaction occurs when the vicinal diols are heated in aqueous or anhydrous percarboxylic acid.

The oxidation according to the invention can be open-chain on all or cyclic vicinal diols are used which the

structure

H H

R ^ -CCR ¹ II OH OH

1 2

exhibit. R and R herein can be the same or different and can represent a hydrogen atom or any Saturated or unsaturated organic radical are »Examples are substituted or unsubstituted, alipLatisehe, aromatic, araliphatic ^, alicyclic and

■ j heterocyclic radicals. R and R

to be closed in a ring.

1 2

heterocyclic residues. R and R can also be with each other

Examples of such diols, which can be adjusted according to methods known per se, are 1,2-octanediol, 1,2-decanediol, 1,2-dotieeandiol, 1,2-octadecanediol, 1,2-cyclooctanediol, 2-cyclododecanediol, and 1-cyclodecanediol , 2 * Tetradecanediol-7 »8, isomer mixtures of internal and terminal diols, e ^ -Monoalkyiglycerinäther, 1,2-dioxytetralin, hydrindediol, camphor glycol, 9,10-Dih.ydroxystearic acid, 9» 10-Dihydroxystearinsäureester, 9 _t 1Q- Dihydroxyoctadecanol, etc.

109884/1962

The Ox3 are dation ^r mixtures of these vicinal Biole one another and mixtures with other, non-reacting with percarboxylic components available such as mixtures with carboxylic acids. Mixtures obtained by hydroxylation of various acids, for example oleic acid and stearic acid or their esters, can also be used. Accordingly, the oxidation of the vicinal diols according to the invention can be used to obtain a large number of compounds which contain at least one COOH group. These include the carboxylic acids, dicarboxylic acids, polycarboxylic acids or partially esterified "carboxylic acids, for example half-esters.

The oxidation is carried out against an organic solvent. As such, preferred are those who are inert to percarboxylic acids, such as acetic acid, esters, in particular ethyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, t-butyl acetate and benzene.

Both anhydrous and hydrous percarboxylic acids can be used use. When using the anhydrous percarboxylic acids, the above-mentioned esters are preferred as solvents used. According to an advantageous variant of the J Process according to the invention can be derived from water-free * <(-> Peracetic acid, and add this to the reaction vessel in anhydrous form by adding the aqueous peracid through a column equipped with a dephlegmator and a water separator is. The solvent rising from the reaction vessel into the column drags off the water to the same extent as the percarbonic acid so that anhydrous peracid flows into the reaction vessel at the foot of the column. <Percarboxylic acid, preferably ^

■■ '■ .- h 10 9884/196 2

Usually, the percarboxylic acids are used in such amounts that there are about 3 moles of the peracid for every mole of the vicinal diol. You can use a 10 to kO $ strength, preferably 20 to 30 sequence peracid. In addition to the preferred peracetic acid, for example perpropionic, perbutyric and perbenzoic acid can be used »

The oxidation is carried out in the presence of ions or ion mixtures of iron, nickel, palladium or, preferably, cobalt and / or manganese. For these purposes, compounds, in particular salts of these elements, which can have any valency, are added to the reaction solution individually or in a mixture. The use of the acetates is advantageous. They are used in catalytic amounts. These are intended to about 1 mole .- $, based on the diol used not exceed _s, otherwise the uncontrolled collapse of the Percarbansäure increases. Amounts of about 0.01 to 0.1 # are advantageous

The oxidation can be carried out in a temperature range between about 10 and about 110.degree. C., advantageously between about kO and about 60.degree. Since it is exothermic, it may be necessary to ensure rapid heat dissipation.

In many cases it is advantageous, apart from the ones mentioned Metal ions to the reaction mixture in addition to add lead ions, which in the form of lead-2 salts or lead

4 -salts can be done. Here, too, it is advantageous to use lead acetate. That is intermediate in the reaction Forming 4-lead salt acts as an oxygen carrier. Appropriately, the lead salt should only be used in amounts up to

5 UoX. ~ ^>, based on the vic.inale ■ diol used, can be used.

109884/1962

- 5 - λ- ■■■; ■■■

The work-up of the reaction mixture can according to per se known methods take place, for example, the carboxylic acid by distillation or by. Crystallization isolated will. The carboxylic acid derived from the percarboxylic acid can be used here recovered quantitatively and converted back into the peracid. The recovery of the catalyst, for example by cementation, is also possible.

109884/1962

example 1

202 g of 1,2-dodecanediol are dissolved in 1 liter of benzene and added 0.38 g of cobalt acetate (Co (OCOCH) „+ 4 H θ) added» Under good

j ti d.

Stirring, 1 kg of a 25% peracetic acid, dissolved in n-propyl acetate, is added dropwise over the course of 90 minutes. The reaction is exothermic. The temperature is first allowed to rise to 50 to 55 C and then cooled with water. The mixture is then left to stir for a further 30 minutes, then diluted with 2 liters of water, shaken and then the water-acetic acid layer is separated off. The n-propyl acetate layer is washed 2 with water, dried and then evaporated in a rotary evaporator at 30 C / 12 mm. What remains are 200 g of an almost colorless oil, which is subjected to vacuum distillation «After a small forerun (up to b.p. ₁₂ 117 ° C), _{167.4 g of undecanoic acid are distilled at b.p. 12} 157 - 160 ° C, corresponding to 89.7% of the theory»

Example 2

202 g of 1,2-dodecanediol are reacted with peracetic acid in the presence of 0.38 g of 2-manganese acetate, as described in Example 1. The reaction temperature is increased to 60.degree. Work-up yields 161 "4 g of undecanoic acid, corresponding to 86" 7 $ d.Th "at a boiling point of 158 to 16 ° C.

Example 3

The oxidation of 1 mole of Docecandiol-1 _S 2 with peracetic acid is carried out one after the other in the presence of the following Schwerin et al! Ions, as described in Example 1:

The following yields are obtained;

Ni-2 acetate: (0 , 076 -B) 57, 2 * And e c an acid Fe-3 acetate: (0 , 076 B) 54, 8th SI It Pd-2 acetate: (0 , 05 "β) 74, 1 η it

- 7 109884/1982

Example 4

202 g of 1,2-dodecanediol are dissolved in 1 liter of benzene, 3.8 g of 2-lead acetate and 0.38 g of 2-cobalt acetate are added, and 1 kg of a 25% is then left at a temperature between 50 to 55 ° C. igen peracetic acid, dissolved in t-butyl acetate, run in. The catalyst is only partially dissolved. After 2 hours, it is worked up. The catalyst is first filtered off (3.4 g) and the mother liquor is evaporated on a rotary evaporator. The remainder is distilled in vacuo. At bp ₁ P 158 to 160 C 164 g of undecanoic acid are obtained, corresponding to 88.2 %> of theory.

Example 5

230 g of tetradecanediol-7j 8 are dissolved in 600 ml of benzene + 60O ml. Propyl acetate, add 0.38 g of cobalt-2-acetate and oxidize with 1 kg of 25 % peracetic acid, dissolved in propyl acetate, at a temperature of 5 ^l to 55 C. After stirring for two hours, it is filtered and evaporated. The remainder is distilled in vacuo. Obtained when Kp _ 110 to 113 ⁰ C. 220.4 g of enanthic acid, corresponding to 84.7 # theory

Example 6

116 g of 1,2-cyclohexanediol are dissolved in 300 ml of n-propyl acetate and 300 ml of benzene, 3.8 g of 2-lead acetate and 0.4 g of cobalt acetate are added and oxidized at 50 to 6 ° C. with 1 kg of a 25 - $ igen peracetic acid, dissolved in n-propyl acetate. After 2 hours _; .. if you evaporate everything to dryness, add 2 ml of cone. Add HCl and enough boiling water until everything is dissolved. After cooling, adipic acid crystallizes out. Quantity: 105. 1 g = 72 i> d.Th. , Veisse crystals, F 152 ° C.

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Example 7

316. ^ 5 S 9 · 10-dihydroxystearic acid is suspended in 1,000 ml of t-butyl acetate, 0.5 is added. g cobalt-2-acetate is added and oxidized at 50 to 55 ° C. with 1 kg peracetic acid (25 dissolved in t-butyl acetate. It is then filtered and the solution is evaporated in vacuo. The residue is treated with benzene. The remaining crystals are recrystallized from water 153 S of azelaic acid with a melting point of 106 ° C. is obtained, corresponding to a yield of 81.3% of the theoretical value. The benzene solution is evaporated in vacuo and fractionated at 1 k mm Hg. 135.4 g of pelargona acid distill at 139 ° to 141 ° C. Yield $ 85.7 of the amount

Example 8

202 g of 1,2-dodecanediol are dissolved in 1.5 liters of n-butyl acetate in a 31 flask and a mixture of 0.2 g each of cobalt and 2-manganese acetate is added. A 1 m column with a dephlegmator, coil cooler and water separator is then placed on the flask. The column has a nozzle at a height of 40 cm for the inlet of the aqueous peracetic acid. A vacuum of 100 torr is applied and the solution is heated with stirring until n-butyl acetate flows back through the water separator. 700 g of a 38% aqueous peracetic acid are then slowly added dropwise into the column. The water is drawn off as the peracetic acid flows in. At the foot of the column, anhydrous peracetic acid flows into the flask, where the oxidation takes place (reaction temperature 45 ° C). Customary work-up gives 151.3 S undecanoic acid, _{boiling point 12} 159 to 160 ° C. Yield: 80.8 # of theory

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Example 9

567 g of a mixture of 282.5 g of oleic acid and 284.5 g of stearic acid are dissolved in 1.2,198% formic acid. At 40 to 50 ° C., 100 g of 70% hydrogen peroxide are allowed to slowly flow in while stirring. The reaction is exothermic. The mixture is stirred for a further 4 hours at 50 ° C. and then diluted with 1,000 ml of 5% sulfuric acid. The suspension Av 'is further boiled under reflux for 6 hours with vigorous stirring, then cooled and then taken up in 1.25 liters of n-butyl acetate. The aqueous layer is separated off, the ester layer is washed twice with water, the water is separated off well and 0.5 g of cobalt acetate (Co (OCOCH) + 4 H _? 0), dissolved in 20 ml of glacial acetic acid, is then added.

At 40 to 50 ° C., 1 kg of a 25% peracetic acid, dissolved in n-butyl acetate, is now added dropwise over the course of 60 minutes. It is then diluted with 1 liter of water, stirred well and the ester layer is separated off. This is dried and evaporated in vacuo at 40 C / 1.2 mm Hg. Then it is diluted with 1 liter of petroleum ether and left to stand in the refrigerator overnight. The azelaic acid ( ^{mp 106 o} C) crystallizes out and is suction filtered (141 · 3 g) · The mother liquor is freed from petroleum ether in a vacuum and then fractionally distilled. 129.4 g of pelargonic acid distill at a bp _{i2f 139 to 142 ° C.} Stearic acid remained in the distillation residue (279.3 s)

- 10 <-

ORIGINAL INSPECTED

1098 84/1962

Claims (4)

Claims Process for the oxidation of vicinal diol groups of organic Connections to carboxyl groups in the presence of a heavy metal, characterized by the fact that the vicinal diol groups in the presence of an organic solvent and in the presence of ions or mixtures of ions of iron, nickel, palladium or, preferably, cobalt or manganese with a percarboxylic acid, before- ™ preferably peracetic acid, oxidized. 2.) The method according to claim 1, characterized in that at a temperature between about 10 C and about 110 ° C., preferably between about 40 and about 6 ° C., is oxidized. 3.) Process according to claims 1 or 2, characterized in that that a 10 to 40, preferably 20 to 30, peracetic acid is used. 4.) Process according to claims 1 to 3 »thereby gekennfe draws that one oxidizes in the presence of lead ions. Dr.No/Wa
July 14, 1970 109884/1962