阅读说明：本技术 由包含2-乙基己醛和甲酸3-庚酯的混合物制备3-庚醇的方法 (Process for the preparation of 3-heptanol from a mixture comprising 2-ethylhexanol and 3-heptanoate formate ) 是由 J·H·特莱斯 J·希蒙 M·德恩 M·丹兹 R·德恩 于 2014-06-25 设计创作，主要内容包括：本发明涉及制备3-庚醇或包含3-庚醇的混合物的方法,所述方法包括以下步骤：(i)将包含一种或多种碱金属氢氧化物的水溶液(A)加入至少包含2-乙基己醛和甲酸3-庚酯的混合物(B)中,其特征在于水溶液(A)中碱金属氢氧化物的浓度为至少40重量％。(The present invention relates to a process for the preparation of 3-heptanol or a mixture comprising 3-heptanol, said process comprising the steps of: (i) adding an aqueous solution (A) comprising one or more alkali metal hydroxides to a mixture (B) comprising at least 2-ethylhexanal and 3-heptanoformate, characterized in that the concentration of alkali metal hydroxide in the aqueous solution (A) is at least 40% by weight.)

1. A process for preparing 3-heptanol or a mixture comprising 3-heptanol comprising the steps of:

(i) adding an aqueous solution (A) comprising one or more alkali metal hydroxides to a mixture (B) comprising at least 2-ethylhexanol and 3-heptanoformate at a pressure of at most 3 bar,

wherein the concentration of the alkali metal hydroxide or hydroxides in the aqueous solution (A) is at least 40% by weight, and wherein the mixture (B) consists of:

2-ethylhexanal: 10-20% by weight

Formic acid 3-heptyl ester: 50-60% by weight

3-heptanol: 5-10% by weight

3/4-heptanone: 8-15% by weight

2-ethylhexanoic acid: 2-5% by weight

Water: < 1% by weight.

2. The process according to claim 1, wherein the one or more alkali metal hydroxides are selected from potassium hydroxide and sodium hydroxide and combinations thereof.

3. The process according to claim 1, wherein the concentration of the alkali metal hydroxide or hydroxides in the aqueous solution (A) is at least 45% by weight.

4. The process according to claim 1, wherein the molar amount of the one or more alkali metal hydroxides is at least 1.5 times the sum of the molar amounts of 3-heptyl formate, 2-ethylhexanal and 2-ethylhexanoic acid in mixture (B).

5. The process according to claim 4, wherein the molar amount of the one or more alkali metal hydroxides is at least 2 times the sum of the molar amounts of 3-heptyl formate, 2-ethylhexanal and 2-ethylhexanoic acid in mixture (B).

6. The process according to claim 1, wherein the addition of the aqueous solution (A) to the mixture (B) is carried out over a period of at least 3 hours.

7. The process according to claim 1, wherein after the addition of the aqueous solution (A) to the mixture (B) has been carried out, the resulting mixture (C) is stirred for a period of at least 6 hours.

8. The process according to claim 7, wherein after the addition of the aqueous solution (A) to the mixture (B) has been carried out, the resulting mixture (C) is stirred for a period of at least 9 hours.

9. The process according to claim 7, wherein after the addition of the aqueous solution (A) to the mixture (B) has been carried out, the resulting mixture (C) is stirred for a period of at least 12 hours.

10. The process according to claim 1, wherein the addition of the aqueous solution (A) to the mixture (B) is carried out at a temperature of at least 50 ℃.

11. The process according to claim 10, wherein the addition of the aqueous solution (a) to the mixture (B) is carried out at a temperature of at least 100 ℃.

12. The process according to claim 10, wherein the addition of the aqueous solution (a) to the mixture (B) is carried out at a temperature of at least 120 ℃.

13. The process according to claim 1, wherein the addition of the aqueous solution (A) to the mixture (B) is carried out at a pressure of at most 1 bar.

14. The process according to claim 1, wherein, after the addition of the aqueous solution (A) to the mixture (B) has taken place, the resulting mixture (C) is mixed with water in a further reaction step (ii) and the phases formed are separated.

15. The process according to claim 14, wherein in a further reaction step (iii), the organic phase obtained is washed with water and then optionally dried.

16. The process according to claim 15, wherein in a further reaction step (iv) the washed and optionally dried organic phase is distilled to separate into its components.

17. A mixture comprising 3-heptanol, wherein the mixture is prepared by the process according to any one of claims 1 to 16, and wherein the mixture comprises 2-ethylhexanol and 3-heptanoate in a total concentration of < 5% by weight based on the mixture.

18. The mixture according to claim 17, wherein the mixture comprises 2-ethylhexanol and 3-heptylic formate in a total concentration of <2 weight percent, based on the mixture.

Examples 1 to 12:

the feed used was an untreated low boiler stream from the production of ethyl hexanoic acid. The composition of the stream can here vary within the following limits:

formic acid 3-heptyl ester: 50 to 60 percent by weight of the composition,

3-heptanol: 5 to 10 percent by weight of a solvent,

2-ethylhexanal: 10 to 20 percent by weight of a solvent,

3-/4-heptanone: 8 to 15 percent by weight of the total weight of the composition,

2-ethylhexanoic acid: 2 to 5 percent by weight of a catalyst,

water: 0.6-0.9 wt%.

The acid ester was 43 and the ester number was 249.

The amount of base (equivalents) described in Table 1 is based in each case on the sum of the molar amounts of 3-heptyl formate, 2-ethylhexanol and 2-ethylhexanoic acid in the feed and the base concentration is based on the aqueous solution used.

Conversion and yield were determined by means of quantitative GC analysis of the starting material.

The yield of 3-heptanol relates to the sum of 3-heptanoate and 3-heptanol in the feed.

General procedure for the experiments at atmospheric pressure (examples 1 to 10):

the low boiler first fraction was placed in a 1L jacketed vessel and heated to the respective temperature. Then, the base was added dropwise as an aqueous solution over 3 hours. When the dropwise addition was complete, the poststirring was carried out at the temperature for the time indicated in the table ("reaction time").

The mixture was then mixed with water to dissolve the precipitated salts and the phases were separated at 50 ℃. The conversion and yield were determined by means of quantitative GC analysis of the organic phase.

General procedure for pressure experiments (examples 11 and 12):

the low boiler initial fraction and the aqueous alkali metal hydroxide solution were placed in a 300ml steel autoclave and heated to the respective temperatures. Then, post-stirring was carried out at the temperature for the time indicated in the table ("reaction time").

The mixture was then mixed with water to dissolve the precipitated salts and the phases were separated at 50 ℃. The conversion and yield were determined by means of quantitative GC analysis of the organic phase.

Table 1: summary of the experiments