CS211412B1 - Method of preparation of the carbonyle and/or aleconols compounds with eight atoms of carbon in a molecule - Google Patents

Abstract

The invention is within the field of organic synthesis. It solves the method of preparing alkylated derivatives 1,3-dioxolane by reaction of octanoxides formula wherein R 1 is η-hexyl, neo-pentyl, n-butyl-, R * 2 is ethyl, methyl, hydrogen and R 2 and R 6 are hydrogen with water in the presence of an acid sulfuric acid at a concentration of 0.1 to 12% % by weight, preferably 1 to 3.0% by weight in such an amount that the water molar ratio contained in the acid solution to the octanoxide was 75-100, 10-10 ° C 90 ° C, preferably 80 to 90 ° C, with vigorous stirring stirring. The reaction product is further separated from an aqueous sulfuric acid solution and distil the prepared substances under pressure less than 15 kPa. Formula of alkylated derivatives prepared 1,3-dioxolane is CH 1 ------------ C ------- R wherein R is n-heptyl-, 4- / 2,2-d imetylpentyl 3-heptyl, R 6 is η-butyl, neo-pentyl, n-hexyl, R 8 is hydrogen, methyl, ethyl.

Description

The invention relates to a process for the preparation of carbonyl compounds and / or alkenols with eight atomic carbon in a molecule by isomerization of octanoxides in the presence of an aqueous solution of sulfuric acid.

Passing propylene oxide vapor through the lithium phosphate catalyst at elevated temperature results in its isomerization to propionaldehyde, acetone and allyl alcohol. Similar products give higher alkene oxides when treated with sulfuric acid solutions. Thus, 2,4,4-trimethylpentane-1,2-oxide in cyclohexane or benzene with 60% sulfuric acid in water at 30 ° C gives up to 90% yield.

2,4,4-trimethylpentane-1-al; less concentrated sulfuric acid promotes conversion to the corresponding diol, with which 2 > 4,4-trimethylpentan-1-al., gives the alkylated 1,3-dioxalane derivative.

Yields up to 90% are obtained using phosphoric acid. Further, 2,4,4-trimethylpentan-1,2-oxide can be isomerized to 2,4,4-trimethylpent-2-en-1-ol in an ethanolic environment at 220 ° C for 5 hours in an autoclave. Similar 2,4,4-trimethylpentane-2,3-dioxide of 10% sulfuric acid for 1 hour, giving 2,4,4-trimety1pent-1-en-3-o1 ^_ a.2,4,4-trimethylpentane-3 and their content has not been quantified. [Gasson EJ et al., J. Org. Chem. 2170-2179, 1954]. The products of isomerization of 2-ethylhexane-1,2-diol in sulfuric acid are not described. The concomitant preparation of carbonyl compounds and alkenyls is also not described.

The drawbacks of the foregoing processes have been eliminated in the invention describing a process for the preparation of carbonyl compounds having an ultra-carbon atom in a molecule of formula (I) wherein R R is η-butyl, neo-pentyl.

R 4 is methyl, ethyl, and 2,4,4-trimethylpentan-3-one and / or alkenols with eight carbon atoms in the molecule of formula II

I

R 1 -CH = C-CH ₂ -OH (11) wherein R 1 'is hydrogen, methyl, η-propyl, tert-butyl, is methyl, ethyl, η-butyl-, neo-pentyl-, and 2, 4,4-trimethylpent-1-en-3-ol by reaction of octanoxides of formula III

Ro (111) wherein R * is η-butyl-, tert-butyl-, neo-pentyl-,

R 2 is hydrogen, methyl, ethyl,

3 ^e hydrogen, methyl, with an aqueous solution of sulfuric acid at a concentration of 0.1 to 10.0% in an amount such that the molar ratio of water contained in the aqueous sulfuric acid solution to the octane oxides of the general formula III is 100: 1, temperature 10 to 90 ° C> preferably 90 ° C with vigorous stirring to guarantee the course in the kinetic region, further separating the reaction product from the aqueous sulfuric acid solution and distilling off the carbonyl compounds having 8 carbon atoms per molecule and / or alkenols having 8 carbon atoms per molecule under pressure less than 15 kPa. The octane oxides of the formula III can also be further treated in the pre-reaction with a separate aqueous phase of the sulfuric acid solution after the loss of its components has been completed.

The course of the reaction can be characterized as the conversion of octanoxides by isomerization due to elevated temperature and the presence of sulfuric acid to carbonyl compounds and alkenols directly.

At the same time, the alkane oxide is hydrolyzed to the corresponding diol, which in turn reacts with the present alkane211122 oxide to diglycol; starting with a carbonyl compound to a cyclic acetal or ketal-alkylated derivative of 1,3-dioxalane, both reactions being equilibrium. However, the formation of diglycols under conditions within the scope of the invention is significantly suppressed. By varying the reaction parameters, it is possible to achieve the preferred formation of the desired product over a relatively wide range, the reaction conditions being feasible without particular demands on the apparatus in a simple manner. According to the invention, it is possible to process 2-ethylhexane-1,2-oxide, 2,4,4-trimethylpentane-1,2-oxide and 2,4,4-trimethylpentane-2,3-oxide into the corresponding carbonyl compounds and / or or alkenols described in more detail in the examples. Octane-1,2-oxide does not give these products.

Example 1

In a 250 ml conical flask with a reflux condenser, thermometer and stirrer, heat the aqueous sulfuric acid solution to the desired temperature with stirring. Then 0.1 mole of 2-ethylhexane-1,2-oxide is added, tempered and stirred for a specified time. After this time, the organic phase is separated and analyzed by gas ehromatography. The products are separated by distillation at a pressure of less than 15 kPa. The conditions of the individual experiments as well as the yields of the reaction products of 2-ethylhexane-1,2-oxide are given in Table 2. First

Table no. Γ

Experimental conditions and conversion products of 2-ethyl-hexane-1,2-oxide.

number of test temperature / ° C /

Concentration conditions % sulfuric acid in water / 7 wt. (mole ratio of water: 2-ethylhexane-1,2-oxide time / min)

1 50 0, 1 100 50 2 70 0.1 100 7.5 3 80 0.1 100 7.5 4 90 0.1 100 7.5 5 90 0, 1 100 60 6 50 1.0 100 90 7 90 1.0 100 7.5 8 20 3.0 100 90 9 90 3.0 1 000 7.5 10 90 3.0 100 7, 5

Table no. 1 Composition /% weight basis number 2-etylhe- 2-ethyl- alkenols 2-etylhe- diglycols ⁺⁺ 2/1-ethylpentyl / - experiment xanthine 1,2-dioxide hexane ^c ; xanthine 1,2- 4-ethyl-4-Butyl 1-al diol -1,3-dioxolane 1 0.9 19.5 19.5 67.9 0 2.2 2 0.7 8.2 16.5 74.0 0 0.8 3 0.7 9.9 17.9 69.6 0 about 4 0.3 9.0 16.5 71.7 0 1.3 5 0 9.4 24.7 56.2 0 6.2 6 0.2 5.8 13.0 77.2 0.3 4.5 7 0.8 10.4 16.4 63.3 0 5.9 8 0 8.1 13.5 74.0 0 2.4 9 0.8 9.8 16.7 50.8 0.4 17.9 0 1.0 9.2 16.1 23, 9 5.1 40.0

+ alkenols Cg ⁼ · collective designation for 2-butyl-trans-but-2-en-1-ol, 2-butyl-cis-but-2-en-t-ol, 2-ethyl-trans-hex-2- en-1-ol and 2-ethyl-cis-hex-2-en-1-ol.

++ diglycols = collective designation for three isomeric diglycols, formed by the reaction of 2-ethylhexane-1,2-oxide with 2-ethylhexane-1,2-diol.

Example 1 and d 2

The procedure is as in Example 1, except that 2,4,4-trimethylpentane-1,2-oxide is added instead of 2-ethylhexane-1,2-oxide. The conditions of the individual experiments as well as the yield of the reaction products of 2,4,4-trimethylpentan-1,2-oxide are shown in Table 2. Second

Table 2

Experimental Conditions and Products Sources of 2,4,4-trimethylpentane-1,2-oxide.

Conditions number experiment temperature / ° C / conc. sulfuric acid in water /% w / mole ratio of water: 2,4,4-trimethylpentane-1,2-dioxide time / Min / .1 30 of 1 100 90 2 90 0.1 100 3 _ 3 40 3.0 100 15 4 40 1.0 100 5 5 90 1.0 100 120 6 10 10.0 100 8 7 90 10.0 * 100 2 8 90 10.0 100 15 continue of table no. 2

Number experiment ¹ Composition /% w / 2,4,4-trimethylpentane-1,2-oxide 2,4,4-tri- methylpentan 1-al ^C 8 alkenols 2,4,4-Trimethylpentane-1,2-diol 2 / 1,3., -Trimethylbutyl / -4-methyl-4- (2,2'-dimethylpropyl) -1,1-dioxolane 1 y. 0 18.8 15.9 57.0 0 2 0.3 24.8 12.3 54.3 2.8 3 0.9 18.0 10.1 66.0 0 4 1.9 25.1 10.6 62.7 3.7 5 0 35, 0 7.8 1, 2 47.9 6 0.7 24.0 9.8 50.8 8.7 . 7 0.6 50.8 . 10.7 13.3 19.4 8 1.2 55,2 ' 4.9 4.9 30.0

alkenols C « ⁼ collective designation for 2,4,4-trimethylpent-1-en-3-ol and 2,4,4-trimethylpent-2-eno

3-ol.

Example 3

The procedure was as in Example 1 except that 2,4,4-trimethylpentane-2,3-oxide was added instead of 2-ethylhexane-1,2-oxide. The conditions of the individual experiments as well as the yields of the reaction products of 2,4,4-trimethylpentane-2,3-oxide are shown in Table 2. Third

Table no. 3

Experimental conditions and conversion products of 2,4,4-trimethylpentane-2,3-oxide.

number experiment temperature / ° C / Conditions ended. sulfuric acid in the aqueous phase / 2 wt./ mole ratio of water! 2,4,4-trimethylpentan-2,3-oxide time / Min / 1 40 0.1 100 90 2 70 0.1 100 15 3 90 0.1 100 8 4 90 0.1 100 90 5 90 3.0 100 5 6 90 3.0 100 90 7 10 10.0 100 8 8 10 10.0 100 90 9 90 . 10.0 100 ' 3

and

Table no. 3 number experiment 2,4,4-trimethylpentane-2,3 'oxide Composition 2,4,4-trimethylpentan-3on /% By weight of ^C 8 alkenol ./ 2,4,4-tri- methylpentan 2,3-diol 2- (1'-Dimethylethyl) -4-di-ethyl-5- (1,1-dimethylethyl-1,3-dioxolane) 1 0.3 2.8 30.8 53.0 2.2 2 0.2 2.8 30.3 56.9 2.1 3 0.8 3.5 28.8 57.7 2.1 4 0.6 2.6 30.7 59.0 1.9 5 0 4.9 42.8 38.5 0 6 0 8.7 66.8 1.5 1, 5. 7 0 0 33.0 65.1 0 8 0 2.4 39.3 51.3 2.1 9 0.3 5.5 54.7 23.7 3.1

+ alkenols C 8 = 2,4,4-trimethylpent-1-en-3-ol.

The invention is applicable to the preparation of 2-ethylhexan-1-alu, 2-butyltrans-but-tran-but-2-en-1-ol, 2-butyl-cis-but-2-en-1-ol, 2- ethyl trans-hex-2-en-1-ol, 2,4,4-trimethylpentan-1-alu,

2,4,4-trimethylpentan-1-en-3-ol, 2,4,4-trimethylpent-2-en-3-ol, 2,4,4-trimethylpentan-3-one and 2,4,4- trimethylpent-1-en-3-ol starting from 2-ethylhexane-1,2-oxide, 2,4,4-trimethylpentane-1,2-oxide and 2,4,4-trimethylpentane-2,3 oxide.

Claims (2)

OBJECT OF THE INVENTION 1. Process for the preparation of carbonyl compounds and / or alkenols with eight carbon atoms in a molecule of the formula I CH-CHO (1) wherein R is n-butyl, neo-pentyl, R ₂ is methyl, ethyl, and 2,4,4-trimethylpentane-3-one and / or alkenols with eight carbon atoms in the molecule of ^ formula II R> CH = C-CH _n -OH 1, Z (11) wherein R 4 is hydrogen, methyl, η-propyl, tert-butyl, R ₂ is methyl-, ethyl-, η-butyl-, neo-pentyl-, and 2,4,4-trimethylpenten-1-ene-3-buu from the reaction of the octane oxides of formula III (III) wherein R 4 is η -butyl-, tert-butyl-, neo-pentyl-, is hydrogen, methyl-, ethyl-, R-4 I ^e ° UIK, methyl, characterized in that the oktánoxidy of formula III with an aqueous solution of sulfuric acid at 0.1 to 10.0 by weight in an amount such that the molar ratio of water contained in the aqueous solution of sulfuric acid to the octanoxides of formula III was 100: 1, at a temperature of 10 to 90 ° C, preferably 90 ° C, with vigorous stirring to guarantee the reaction in the kinetic region, further separating the reaction product from the aqueous sulfuric acid solution and distilling off carbonyl compounds having eight carbon atoms in the molecule and / or alkenols having eight carbon atoms in the molecule at a pressure of less than 15 kPa. 2. The process of claim 1 wherein the octanoxides of formula III are treated with a separate aqueous phase of the sulfuric acid solution from the previous reaction after the addition of its components.