CN100374403C - Process for preparing compound of cyclohexdiol - Google Patents
Process for preparing compound of cyclohexdiol Download PDFInfo
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- CN100374403C CN100374403C CNB2005101121945A CN200510112194A CN100374403C CN 100374403 C CN100374403 C CN 100374403C CN B2005101121945 A CNB2005101121945 A CN B2005101121945A CN 200510112194 A CN200510112194 A CN 200510112194A CN 100374403 C CN100374403 C CN 100374403C
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- cyclohexanediol
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- cyclohexdiol
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Abstract
The present invention relates to a method for preparing cyclohexdiol compounds, which belongs to the field of organic compound preparation techniques. Under the conditions of stir and heating, aqueous alkali is directly dropped into a dihydroxybenzene compound, an Ni-Al alloy and a water solution for reaction. The Ni-Al alloy reacts with the aqueous alkali so as to generate hydrogen gas. The dihydroxybenzene is reduced by the hydrogen gas generated in the system so as to generate the cyclohexdiol compound. The cyclohexdiol compound is an important chemical raw material, and the present invention provides a simple and practical method for the deep-processing of petroleum product phenols and has high industrial application value. The method has the advantages of simple process, convenient operation and easy scaled commercial production. The reduction reaction of the present invention is carried out in the water system and does not use any poisonous harmful organic solvents, and the present invention is a green chemistry method.
Description
Technical field
The invention belongs to organic compound manufacturing technology field, be specially the manufacture method of cyclohexanediol compounds.
Background of invention
The cyclohexanediol compounds is very important chemical intermediate, at medicine, and agricultural chemicals, family's industry such as apply some make up has purposes very widely.China's phenol petroleum products amount is big, low price.Make the cyclohexanediol of high added value from the cheap phenol of raw material by hydrogenation reaction, very important economic worth is arranged.The hydrogenation reaction of dihydroxy-benzene class generally need be dissolved into the dihydroxy-benzene compounds in the suitable organic solvent, adds Raney Ni or noble metal then and makes catalyzer, Pt for example, Rh.Reaction conditions needs high temperature (100-200 ℃) high pressure (100-200atm), so dihydroxy-benzene class catalytic hydrogenation reaction generally need be carrying out in the device especially, as autoclave.So far, main synthetic method is:
(1) L.Covert people such as (J.Am.Chem.Soc., 1932,54, page 1651-63) has reported the high-temperature and high-pressure hydrogenation reaction with Resorcinol under the Raney Ni catalysis, and temperature of reaction is 120 degree, pressure 175 normal atmosphere.
(2) J.English people such as (J.Am.Chem.Soc., 1941,71, page 3310-3313) has reported the high-temperature and high-pressure hydrogenation reaction with pyrocatechol under the RaneyNi catalysis, and temperature of reaction is the 140-160 degree, pressure 137 normal atmosphere.
(3) Y.Komachi (Tetrahedron Lett., 1994,35, page 4169-4172) is a reductive agent with Dianization Can, and Resorcinol is reduced to 1, the 4-cyclohexanediol.
Because aforesaid method mostly is the high-temperature and high-pressure hydrogenation reaction greatly, has both needed Raney Ni to make catalyzer, need in special device, carry out again, carry out as autoclave.In view of general factory does not possess autoclave, therefore, general factory is difficult to implement the high-temperature and high-pressure hydrogenation reaction of dihydroxy-benzene class.The method of Komachi uses expensive Dianization Can to be reductive agent in addition, and cost is too high, does not have any use value.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, is easy to form the manufacture method of the cyclohexanediol compounds of mass-producing.
The manufacture method of the cyclohexanediol compounds that the present invention proposes.Its step is as follows: under normal pressure, stirring and heating, alkali aqueous solution directly is added drop-wise to the dihydroxy-benzene compounds, in the mixing solutions of Ni-Al alloy and water; Ni-Al alloy usage quantity is 1-40 a times of dihydroxy-benzene compounds weight, and control reaction temperature is 20 ℃ ~ 100 ℃; After dripping end, continued stirring reaction 5-7 hour.
Among the present invention, described alkali aqueous solution is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, cesium hydroxide or baryta water etc.Described dihydroxy-benzene compounds is pyrocatechol, Resorcinol or Resorcinol.
In the aforesaid method, the alkali aqueous solution concentration of dropping generally can be 0.2-10wt%, and dripping quantity is the 40-150% of aforementioned mixed liquor volume, and the dropping time is 30-90 minute.
Among the present invention, stirring reaction is cooled to room temperature after finishing, and filters, and removes insolubles, aqueous solution ethyl acetate extraction, organic layer anhydrous magnesium sulfate drying, concentrating under reduced pressure.Product after concentrating with gas chromatographic analysis, it consists of cyclohexanediol, and dihydroxy-benzene is reduced fully.
Among the present invention, by Al in the Ni-Al alloy and water reaction, generate hydrogen, the hydrogen reducing that the dihydroxy-benzene compounds is generated generates the cyclohexanediol compound.Characteristics of the present invention are: in water, utilize the Ni-Al alloy as reductive agent, under the normal pressure, realized the hydrogenation reaction of benzene Polyphenols.The advantage of present method is: (1) does not use any poisonous and hazardous organic solvent; (2) water itself is as hydrogen source; (3) do not use any special device.Therefore, present method has been avoided the step of Recovery of Organic Solvent, reduces three industrial wastes eliminating amount, alleviates the destruction to physical environment, is a kind of environmentally friendly chemical reaction (Eco-friendly reaction), promptly is a kind of Green Chemistry method.Because present method makes water as solvent and hydrogen source, does not use any special device, has reduced production cost, and has had practicality and Yi Hangxing, is easy to form industrially scalable.In addition,, utilize present method, be very easy to obtain the high added value cyclohexanol kind,, have higher industrial application value for the deep processing of the petroleum products phenol of abundant raw material provides a kind of simple method from the cheap phenol of raw material.The physical environment of both having protected us to depend on for existence has been realized the deep processing and utilization of natural resources again.
Concrete experiment method
In the three-necked bottle of embodiment 1:500 milliliter, thermometer is installed, agitator adds Resorcinol (10 mmoles, 1.11 grams), Ni-Al alloy (10g), and water (100 milliliters) begins to be heated with stirring to 90 ℃ then.With 1 hour dropping 1% aqueous sodium hydroxide solution (100 milliliters).Control reaction temperature is 90 ℃-100 ℃.After 1% aqueous sodium hydroxide solution dripped and finishes, restir was 5 hours under this temperature.Be cooled to room temperature then, filter, elimination insolubles, aqueous solution ethyl acetate extraction, organic layer with anhydrous magnesium sulfate drying after, concentrating under reduced pressure.Product after concentrating with the gas chromatography analysis then, the transformation efficiency of Resorcinol is 100%, 1, the productive rate of 4-cyclohexanediol is 84%.
In the three-necked bottle of embodiment 2:500 milliliter, thermometer is installed, agitator adds Resorcinol (10 mmoles, 1.11 grams), Ni-Al alloy (7g), and water (100 milliliters) begins to be heated with stirring to 80 ℃ then.With 1 hour dropping 3% aqueous sodium hydroxide solution (100 milliliters).Control reaction temperature is 80 ℃-100 ℃.After 3% aqueous sodium hydroxide solution dripped and finishes, restir was 7 hours under this temperature.Be cooled to room temperature then, filter, elimination insolubles, aqueous solution ethyl acetate extraction, organic layer with anhydrous magnesium sulfate drying after, concentrating under reduced pressure.Product after concentrating with the gas chromatography analysis then, the transformation efficiency of Resorcinol is 100%, 1, the productive rate of 4-cyclohexanediol is 83%.
In the three-necked bottle of embodiment 3:500 milliliter, thermometer is installed, agitator adds Resorcinol (10 mmoles, 1.11 grams), Ni-Al alloy (8g), and water (100 milliliters) begins to be heated with stirring to 90 ℃ then.With the 1.5 hours dropping 8% cesium hydroxide aqueous solution (100 milliliters).Control reaction temperature is 90 ℃-100 ℃.After the 8% cesium hydroxide aqueous solution dripped and finishes, restir was 5 hours under this temperature.Be cooled to room temperature then, filter, elimination insolubles, aqueous solution ethyl acetate extraction, organic layer with anhydrous magnesium sulfate drying after, concentrating under reduced pressure.Product after concentrating with the gas chromatography analysis then, the transformation efficiency of Resorcinol is 100%, 1, the productive rate of 4-cyclohexanediol is 82%.
In the three-necked bottle of embodiment 4:500 milliliter, thermometer is installed, agitator adds Resorcinol (10 mmoles, 1.11 grams), Ni-Al alloy (9g), and water (100 milliliters) begins to be heated with stirring to 90 ℃ then.With 40 minutes dropping 1% potassium hydroxide aqueous solutions (100 milliliters).Control reaction temperature is 90 ℃-100 ℃.After 1% aqueous sodium hydroxide solution dripped and finishes, restir was 5 hours under this temperature.Be cooled to room temperature then, filter, elimination insolubles, aqueous solution ethyl acetate extraction, organic layer with anhydrous magnesium sulfate drying after, concentrating under reduced pressure.Product after concentrating with the gas chromatography analysis then, the transformation efficiency of Resorcinol is 100%, 1, the productive rate of 4-cyclohexanediol is 88%.
Claims (5)
1. the manufacture method of a cyclohexanediol is characterized by: under normal pressure, stirring and heating, alkali aqueous solution directly is added drop-wise in the mixing solutions of dihydroxy-benzene compounds, Ni-Al alloy and water; Ni-Al alloy usage quantity is 1-40 a times of dihydroxy-benzene compounds weight, and control reaction temperature is 20 ℃～100 ℃, after dropping finishes, continues stirring reaction 5-7 hour.
2. the manufacture method of cyclohexanediol according to claim 1 is characterized in that described dihydroxy-benzene compounds is pyrocatechol, Resorcinol or Resorcinol.
3. the manufacture method of cyclohexanediol according to claim 1 is characterized in that employed alkali aqueous solution is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, cesium hydroxide or the baryta water.
4. the manufacture method of cyclohexanediol according to claim 1 is characterized in that the alkali aqueous solution concentration that drips is 0.2-10wt%, and dripping quantity is the 40-150% of described mixed liquor volume, and the dropping time is 30-90 minute.
5. the manufacture method of cyclohexanediol according to claim 1, it is characterized in that stirring reaction finishes after, be cooled to room temperature, filter, remove insolubles, aqueous solution ethyl acetate extraction, organic layer anhydrous magnesium sulfate drying, concentrating under reduced pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101121945A CN100374403C (en) | 2005-12-29 | 2005-12-29 | Process for preparing compound of cyclohexdiol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101121945A CN100374403C (en) | 2005-12-29 | 2005-12-29 | Process for preparing compound of cyclohexdiol |
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| CN1793095A CN1793095A (en) | 2006-06-28 |
| CN100374403C true CN100374403C (en) | 2008-03-12 |
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| CNB2005101121945A Expired - Fee Related CN100374403C (en) | 2005-12-29 | 2005-12-29 | Process for preparing compound of cyclohexdiol |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949033B (en) * | 2016-05-11 | 2019-02-05 | 浙江工业大学 | A kind of method that 1,4-benzoquinone catalytic hydrogenation prepares 1,4- cyclohexanediol |
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2005
- 2005-12-29 CN CNB2005101121945A patent/CN100374403C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 1，2－环己二醇及其衍生物的合成与应用. 孙利民等.河南化工，第22卷第3期. 2005 * |
| 间苯二酚催化加氢制备1，3－环己二醇的研究. 王飞军等.中国矿业大学学报，第32卷第6期. 2003 * |
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Granted publication date: 20080312 Termination date: 20101229 |