CN1544406A - Ethylene glycol diarylether preparation method - Google Patents
Ethylene glycol diarylether preparation method Download PDFInfo
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- CN1544406A CN1544406A CNA2003101166881A CN200310116688A CN1544406A CN 1544406 A CN1544406 A CN 1544406A CN A2003101166881 A CNA2003101166881 A CN A2003101166881A CN 200310116688 A CN200310116688 A CN 200310116688A CN 1544406 A CN1544406 A CN 1544406A
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- dichloroethane
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Abstract
The invention discloses an easy-to-operate, high yield preparation process for ethylene glycol di-aromatic ether suitable for industrialized production which comprises the steps of, charging substituted phenol and queous alkali into reactor for stirring reaction, filling excess dichloroethane and phase transition catalyst, carrying out inverse flow reaction at 70-100 deg. C, the reacting time being 15-35 hours, concentrating water at 95-130 deg. C, thus completing the reaction, watering so as to dissolve inorganic salt completely, abandoning the water layer, recrystallizing the residue.
Description
One, the technical field
The invention relates to a preparation method of an organic ether compound, and in particular belongs to a preparation method of ethylene glycol diaryl ether.
Second, background Art
The ethylene glycol diaryl ether can be used as a sensitizer of a thermal recording material, a synthetic polymer material and a raw material of various flame retardants, and has large international market demand. The ethylene glycol diaryl ether has the structural formula (I), wherein R1-R5Hydrogen, alkyl, alkoxy, halogen, and the like may be mentioned.
The synthesis of such compounds generally employs the theoretical process described in equation (II), which is generally believed to be a nucleophilic substitution reaction of a phenoxide anion with dichloroethane. Since the chlorine atom has a weak ability as a leaving group and dichloroethane causes side reactions (III) such as elimination and hydroxyl group substitution under alkaline conditions, the reaction is carried out at a constant temperature according to a general synthetic procedure using 2 equivalents of phenol, 1 equivalent of dichloroethane and 2 equivalents of liquid alkali as raw materials, and the yield is not very desirable, and is generally about 50%.
(III)
The methods published to date for the synthesis of such compounds have focused essentially on how to avoid side reactions of dichloroethane under basic conditions and thus to increase the yield of the reaction. Generally, controlling the concentration of the free base is a basic idea employed in the respective invention. Therefore, the initial invention mainly used the excess phenol method (Kokukusan , vol 66, 979-. The basic idea is that the large excess of phenol is adopted, so that the equilibrium of the reaction can be moved to the right, and on the other hand, the existence of the large excess of phenol can inhibit the concentration of free hydroxyl, thereby inhibiting the side reaction to a certain extent and improving the reaction yield (72%). Since this method uses a large excess of expensive phenol, it not only increases the equipment and labor requirements in phenol recovery, but also causes difficulties in separation and purification of the product, thus it is not suitable for industrial mass production. Another method for preparing such compounds, the stepwise alkali addition method, is reported in Japanese patent publication (Japanese examined patent publication No. 6-21083). In this process, the ratio of phenol to dichloroethane is substantially 2 to 1, however, the authors employ gradual alkali addition to gradually increase the alkali concentration in the system, so that side reactions due to free alkali can be suppressed to some extent, however, since the phenol oxyanion concentration in the system is low, the reaction progress is partially affected, so that the yield does not change much (72.8%) compared with the former, and in addition, the alkali concentration in the system needs to be finely controlled for a long time, and the operation is complicated and difficult to control.
The invention aims to provide a preparation method of ethylene glycol diaryl ether, which has high yield and simple operation.
Third, the invention
In the synthesis of such compounds, generally, at least two equivalents of phenol should be added to ensure that the two chlorine atoms in the dichloroethane are reacted as far as possible. However, since such a reaction is an equilibrium reaction, it is difficult to carry out the reaction completely, and the reaction yield is generally low due to the influence of side reactions.
In order to further improve the yield of such reactions and reduce the cost of industrial production, we have conducted detailed studies on such reactions. We note that the previous inventive idea has focused on how to avoid side reactions of dichloroethane due to hydroxyl substitution and elimination. In addition, since there is a fear of the formation of a mono-substituted by-product, the molar ratio of the phenol to dichloroethane to be used is generally 2: 1 or more. Through experimental exploration, we found the strange phenomenon that no monosubstitution can be detected in the reaction process. According to the usual thinking, a substituent should be an indispensable intermediate for the reaction, and this phenomenon suggests that the intermediate for the reaction should be more active and that the next reaction takes place as soon as it is formed, and thus it is consumed quickly. Through the examination of the molecular structure of the primary substituent, the substitution of the second chlorine atom in the reaction process is considered to be an "ortho group participation mechanism" (IV) rather than a general nucleophilic substitution mechanism. The ortho group participation mechanism means that a group on a carbon atom (sometimes further away) adjacent to a carbon chain on which a leaving group is located has a lone pair of electrons or contains a pi bond, and the lone pair of electrons or the pi bond has nucleophilicity, so that the compound participates in nucleophilic substitution.
Firstly, under the action of alkali, phenol is converted into phenoxide anion, and then nucleophilic substitution reaction is carried out on the phenoxide anion and dichloroethane to generate a monosubstituted substance. In the molecular structure of dichloroethane, since the leaving ability of chlorine atom is weak and another chlorine atom will cause large steric hindrance (V) to the nucleophilic substitution reaction of the first step, it is not difficult to imagine that the first step substitution reaction of the reaction proceeds slowly and is a rate control step. However, once a monosubstituted compound is produced, nucleophilic substitution within the molecule occurs due to the "ortho group participation effect" of the lone pair of electrons on the oxygen atom, and a cyclic oxonium ion is produced. The cyclic oxonium ion has high reactivity and, once formed, undergoes a substitution reaction with another molecule of a phenoxide anion to form a product. Based on this theory, even if an excess of dichloroethane is used, there is no fear of an excess of a substitution by-product, but rather, it is advantageous to replenish the dichloroethane lost by substitution or elimination of side reactions.
The invention discloses a preparation method of ethylene glycol diaryl ether, which is characterized in that substituted phenol and alkali solution are added into a reactor and stirred for reaction; adding excessive dichloroethane and a phase transfer catalyst, and carrying out reflux reaction at 70-100 ℃; then concentrating and dividing water at 90-130 ℃to ensure that the reaction is complete; adding water to dissolve inorganic salt, discarding water layer, and recrystallizing residue to obtain the final product.
According to the mechanism of the present invention, once a monosubstituted compound is formed, it is converted into a highly reactive cyclic oxonium ion, which is immediately reacted with another phenoxide counter-ion to form a product, so that there is no fear that an excess of dichloroethane causes an excess of monosubstituted by-product, but rather, it is advantageous to replenish the dichloroethane consumed by the side reaction. In general, the amount of dichloroethane used is from 0.6 to 1.5 equivalents, preferably from 0.8 to 1.2 equivalents, based on the substituted phenol.
In the molecular structure of dichloroethane, the first-step substitution reaction proceeds slowly due to the weak leaving ability of chlorine atom and the larger steric hindrance of the nucleophilic substitution reaction of the first-step reaction caused by the other chlorine atom, which is a rate control step. We have found that the addition of a catalytic amount of a phase transfer catalyst is effective in increasing the rate of reaction and thus facilitates the reaction. The phase transfer catalyst used in the present invention includes various quaternary ammonium salts and polyethylene glycol, of which polyethylene glycol is the most effective. The polyethylene glycol used may be a single component or a mixture of polyethylene glycols of different molecular weights, and is generally used in an amount of 5 to 30%, preferably 10%, by weight of the phenol.
The excessive dichloroethane is used independently without adding a phase transfer catalyst, the reaction is not good, mainly because the activation energy of the nucleophilic substitution reaction in the first step is high, the reaction rate is slow, a large part of dichloroethane is consumed due to the side reaction shown in the reaction formula (III), and the reaction yield is not ideal. In addition, if the molar ratio of phenol to dichloroethane is kept at 2 to 1, the reaction yield cannot be effectively improved even if catalysis is carried out using a phase transfer catalyst. In the conditions adopted by the invention, the phase transfer catalyst is adopted for catalysis, and excessive dichloroethane is added, so that the reaction can achieve the best effect.
The base used in the present invention is sodium hydroxide or potassium hydroxide. The activity of sodium hydroxide is less than that of potassium hydroxide, so that the reaction yield is slightly reduced, the solubility of sodium chloride generated after the reaction in water is not as good as that of potassium chloride, the sodium chloride is not easy to be washed away by a certain amount of water, and the ash content in the product is increased. The potassium hydroxide can avoid the defects, and the generated potassium chloride can be used as a raw material of a fertilizer after purification. The alkali used in the present invention is preferably potassium hydroxide, and the amount thereof is preferably 1 to 3 equivalents, more preferably 2 equivalents, based on the phenol.
In order to avoid side reactions such as elimination and hydroxyl substitution of dichloroethane at high temperature, the reflux reaction temperature is generally controlled to 70-100 ℃, usually 75-95 ℃, and the reaction time is generally 15-35 hours, usually 18-24 hours. In order to complete the reaction in the latter stage, it is necessary to concentrate the reaction system and to increase the concentration of the residual phenoxide anions to participate in the reaction as much as possible. The concentration and water separation temperature is controlled to be between 95 and 130 ℃, the temperature is between 95 and 120 ℃ usually, and the water separation time is 2 to 6 hours usually, 3 to 4 hoursusually.
By using 1 equivalent of phenol, 0.8-1.2 equivalents of dichloroethane, 2 equivalents of potassium hydroxide and 10% of polyethylene glycol, we obtain the ethylene glycol diaryl ether with high yield and high purity, wherein the yield is more than 80%, and the purity is more than 99%. Although the method uses excessive dichloroethane, the unit operation is simple, the dichloroethane is low in price, and the yield of the product is high, so that the method is very favorable for industrial production.
Compared with the prior art, the method has the advantages of simple operation and high yield which reaches 80-85%.
Fourth, the embodiment
The present invention will be further described with reference to examples, wherein examples 1, 4 and 5 are embodiments of a method for preparing an ethylene glycol diaryl ether according to the present invention, and examples 2 and 3 are comparative examples.
Example 1, 2-bis (3-methylphenoxy) ethane
108 g (1 mol) of m-cresol was added to a 1000ml four-necked flask, stirred, added with 50% potassium hydroxide solution (56 g of potassium hydroxide +56 ml of water), and heated to 80 ℃ for half an hour. 99(1 mol) g of dichloroethane and 10 g of PEG1000 were added, refluxed for 7 hours (76-83 ℃), then a 50% potassium hydroxide solution (56 g of potassium hydroxide +56 ml of water) was added, followed by stirring at 87-93 ℃ for 13 hours. Heating and concentrating to make the temperature gradually reach 120 ℃ in about 3 hours, and preserving the heat for one hour at the temperature of 118-. Adding 350ml of water, stirring vigorously at about 100 ℃ for 10 minutes, standing for demixing, and removing a water layer. Adding 270ml of isopropanol into the oil layer, heating and distilling back to dissolve the solid, slowly reducing the temperature to 60 ℃ within two hours, preserving the temperature for one hour, then slowly reducing the temperature to 5 ℃, keeping the temperature for two hours, filtering, washing the product with 30ml of isopropanol multiplied by 3, and drying to obtain 99g of product, wherein the yield is 81 percent, and the purity is more than 99 percent.
Example 2.1, 2-bis (3-methylphenoxy) ethane
The amount of dichloroethane used was 49.5 g (0.5 mol), the other materials used and the procedure of example 1. 68 g of product is obtained, the yield is 56 percent, and the purity is more than 99 percent.
Example 3, 2-bis (3-methylphenoxy) ethane
The PEG1000 was not used, and the other materials were used in the same amounts and procedures as in example 1. 75 g of the product is obtained, the yield is 62 percent, and the purity is more than 99 percent.
Example 4.1, 2-bis (4-methylphenoxy) ethane
108 g (1 mol) of p-cresol was put into a 1000ml four-necked flask, stirred, added with 50% potassium hydroxide solution (56 g potassium hydroxide +56 ml water), and heated to 80 ℃ for half an hour. 99(1 mol) g of dichloroethane and 10 g of PEG1000 were added, refluxed for 7 hours (76-83 ℃), then a 50% potassium hydroxide solution (56 g of potassium hydroxide +56 ml of water) was added, followed by stirring at 87-93 ℃ for 13 hours. Heating and concentrating to make the temperature gradually reach 120 ℃ in about 3 hours, and preserving the heat for one hour at the temperature of 118-. 350ml of water is added, the temperature is raised to 100 ℃, the mixture is stirred vigorously for 0.5 hour, the temperature is lowered to 80 ℃, the mixture is filtered, 100ml of warm water is washed twice, the obtained solid is dried in vacuum and recrystallized to be 104 g, the yieldis 85 percent, and the purity is more than 99 percent.
Example 5, 2-bis (phenoxy) ethane
94 g (1 mol) of p-cresol was added to a 1000ml four-necked flask, stirred, added with 50% potassium hydroxide solution (56 g potassium hydroxide +56 ml water), and heated to 80 ℃ for half an hour. 99(1 mol) g of dichloroethane and 9.4 g of PEG1000 were added, refluxed for 7 hours (76-83 ℃), then a 50% potassium hydroxide solution (56 g of potassium hydroxide +56 ml of water) was added, followed by stirring at 87-93 ℃ for 13 hours. Heating and concentrating to make the temperature gradually reach 120 ℃ in about 3 hours, and preserving the heat for one hour at the temperature of 118-. Adding 350ml of water, heating to 100 ℃, violently stirring for 0.5 hour, standing for 10 minutes, removing a water layer, adding 270ml of isopropanol into an oil layer, heating, stirring and dissolving, slowly cooling to 60 ℃ within two hours, preserving heat for 1 hour at the temperature, then slowly cooling to 5 ℃, keeping the temperature for two hours, filtering, washing a product with 30ml of isopropanol multiplied by 3, and drying to obtain 89g of a product, wherein the yield is 83% and the purity is more than 99%.
Claims (6)
1. A method for preparing ethylene glycol diaryl ether is characterized in that substituted phenol and alkali solution are added into a reactor and stirred for reaction; adding excessive dichloroethane and a phase transfer catalyst, and carrying out reflux reaction at 70-100 ℃ for 15-35 hours; then concentrating and dividing water at 95-130 ℃ to ensure that the reaction is complete; adding water to dissolve inorganic salt, discarding water layer, and recrystallizing residue to obtain the final product.
2. A process forthe preparation of ethylene glycol diaryl ether according to claim 1, wherein dichloroethane is used in an amount of 0.6 to 1.5 equivalents based on the substituted phenol.
3. A process for the preparation of ethylene glycol diaryl ether according to claim 1 or 2, wherein dichloroethane is used in an amount of 0.8 to 1.2 equivalents based on the substituted phenol.
4. The process for the preparation of ethylene glycol diaryl ether according to claim 1, wherein the phase transfer catalyst is quaternary ammonium salt or polyethylene glycol, and the amount of the phase transfer catalyst is 5-30% by weight based on the phenol.
5. A process for the preparation of ethylene glycol diaryl ether according to claim 4, wherein said polyethylene glycol is a single component or a mixture of polyethylene glycols of different molecular weights.
6. The process for preparing ethylene glycol diaryl ether according to claim 1, wherein the aqueous alkali solution is an aqueous solution of potassium hydroxide or sodium hydroxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276432A (en) * | 2011-05-17 | 2011-12-14 | 潍坊大有生物化工有限公司 | Synthetic method of 1,2-bis(3-methyllphenoxy)ethane thermosensitive sensitizer |
| CN103073398A (en) * | 2013-02-20 | 2013-05-01 | 连云港珂玫琳科技有限公司 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
| CN103772159A (en) * | 2014-01-06 | 2014-05-07 | 寿光富康制药有限公司 | Preparation method of thermosensitive sensitizer |
| CN104710287A (en) * | 2013-12-13 | 2015-06-17 | 北京北朋科技有限公司 | Industrial preparation method of 1,2-diphenoxyl ethane and its analog |
| CN109369349A (en) * | 2018-10-26 | 2019-02-22 | 沈阳感光化工研究院有限公司 | The preparation method of bis- (3- methylphenoxy) ethane of 1,2- |
-
2003
- 2003-11-27 CN CN 200310116688 patent/CN1237040C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276432A (en) * | 2011-05-17 | 2011-12-14 | 潍坊大有生物化工有限公司 | Synthetic method of 1,2-bis(3-methyllphenoxy)ethane thermosensitive sensitizer |
| CN102276432B (en) * | 2011-05-17 | 2015-02-04 | 潍坊大有生物化工有限公司 | Synthetic method of 1,2-bis(3-methyllphenoxy)ethane thermosensitive sensitizer |
| CN103073398A (en) * | 2013-02-20 | 2013-05-01 | 连云港珂玫琳科技有限公司 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
| CN103073398B (en) * | 2013-02-20 | 2015-07-29 | 连云港珂玫琳科技有限公司 | The preparation method of two (3-methylphenoxy) ethane of 1,2- |
| CN104710287A (en) * | 2013-12-13 | 2015-06-17 | 北京北朋科技有限公司 | Industrial preparation method of 1,2-diphenoxyl ethane and its analog |
| CN104710287B (en) * | 2013-12-13 | 2017-12-08 | 北京北朋科技有限公司 | The industrialized process for preparing of 1,2 biphenoxyl ethanes and the like |
| CN103772159A (en) * | 2014-01-06 | 2014-05-07 | 寿光富康制药有限公司 | Preparation method of thermosensitive sensitizer |
| CN109369349A (en) * | 2018-10-26 | 2019-02-22 | 沈阳感光化工研究院有限公司 | The preparation method of bis- (3- methylphenoxy) ethane of 1,2- |
| CN109369349B (en) * | 2018-10-26 | 2021-08-03 | 沈阳感光化工研究院有限公司 | Preparation method of 1, 2-bis (3-methylphenoxy) ethane |
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| CN1237040C (en) | 2006-01-18 |
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