CN113004149A - Preparation method of double quaternary ammonium salt compound - Google Patents
Preparation method of double quaternary ammonium salt compound Download PDFInfo
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- CN113004149A CN113004149A CN202110216552.6A CN202110216552A CN113004149A CN 113004149 A CN113004149 A CN 113004149A CN 202110216552 A CN202110216552 A CN 202110216552A CN 113004149 A CN113004149 A CN 113004149A
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- trimethylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The invention belongs to the field of chemistry and provides a preparation method of a bis-quaternary ammonium salt compound. The preparation method comprises the steps of taking dibromoalkane and trimethylamine aqueous solution as raw materials, taking ethanol as a solvent, reacting in a homogeneous system for 4-48 hours at 25-80 ℃, and distilling and washing after the reaction is finished to obtain a pure product. The method has the advantages of simple reaction, high efficiency and low cost, and can avoid using raw materials with high safety risk such as trimethylamine gas and the like and raw materials with high economic cost such as trimethylamine methanol solution and the like in the preparation process; the defects of heterogeneous reaction and low conversion rate caused by independently using a trimethylamine aqueous solution and dibromoalkane as reaction raw materials are overcome; the post-treatment process does not use high-risk organic solvents such as diethyl ether and the like, and all the used organic solvents can be recovered.
Description
Technical Field
The invention belongs to the field of chemistry, and relates to a preparation method of a double quaternary ammonium salt compound, in particular to a preparation method of a double quaternary ammonium salt compound.
Background
The compound of double quaternary ammonium salts such as hexamethonium bromide and the like is a commonly used structure directing agent in the manufacture of molecular sieves and is an important raw material for preparing molecular sieves such as ITQ-13, EU-1 and the like. The preparation method of the double quaternary ammonium salt compound which is simple and economical and can be industrially produced can promote the rapid development of the related molecular sieve manufacturing industry. Two general methods for synthesizing bis-quaternary ammonium salts such as hexamethonium bromide are 1) reaction of aliphatic diamine and methylating agent, and 2) reaction of dibromoalkane and trimethylamine. The two reactions in the prior art have the problems of raw material waste, overlong reaction time, more organic solvents, and/or complex post-treatment, and are not beneficial to large-scale industrial production.
2011, Dai et al disclose a method for synthesizing bis-quaternary ammonium salt compounds such as hexamethonium bromide from aliphatic diamine, dimethyl carbonate, aqueous hydrogen bromide and the like, which requires multi-step reaction, and has expensive raw materials, harsh reaction temperature and low yield (CN 101973887A). In 2014, Xu et al reported a method of obtaining hexamethonium bromide by reacting 1, 6-dibromohexane with trimethylamine gas in ethanol solution overnight at room temperature (RSC adv.,2014,4(91), 49846-49849.). The reaction uses excessive trimethylamine, and the post-treatment needs to use ether to wash out unreacted substances, so the operation is complex, and the yield is not reported. In 2015, Bai et al disclosed a process for synthesizing bis-quaternary ammonium compounds such as hexamethonium bromide and the like from dibromoalkane and trimethylamine aqueous solution, the reaction solution was two-phase, the conversion rate was low, the post-treatment was complicated, operations such as liquid separation extraction and reduced pressure distillation were required, and organic solvents such as diethyl ether were used, and the specific yield was not disclosed (CN 105017032A). Chen and Zeng et al reacted at room temperature or 60 ℃ using 1, 6-dibromohexane and trimethylamine methanol solution as starting materials and DMF as solvent to give a yield of 90%. The method uses expensive methanol trimethylamine solution and DMF solvent, and the post-treatment process also needs to use methanol and ether (Poly. chem.,2016,7(7), 1397-581404; Langmuir,2017,33(23), 5829-5834).
Disclosure of Invention
Aiming at the problems of higher cost of synthetic raw materials, complex post-treatment and the like in the prior art, the invention provides a preparation method of a double quaternary ammonium salt compound, which is characterized in that dibromoalkane and trimethylamine aqueous solution are used as reactants, ethanol is used as a solvent to carry out homogeneous reaction under the heating condition, and the preparation method has the characteristics of fast conversion, high yield, convenient post-treatment and low cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a bis-quaternary ammonium salt compound comprises the following steps: dibromoalkane and trimethylamine aqueous solution are used as reactants, ethanol is used as a solvent, the reaction is carried out for 4 to 48 hours at the temperature of 25 to 80 ℃, and post-treatment is carried out after the reaction is finished, so that the bis-quaternary ammonium salt compound is obtained. The chemical reaction formula is as follows:
wherein the dibromoalkane is
n＝0-4。
The mol ratio of the dibromoalkane to the trimethylamine is 1: 2-3, preferably in a molar ratio of 1: 2.2.
the post-treatment process after the reaction is finished comprises the following steps: and (3) carrying out reduced pressure distillation to recover ethanol to obtain a crude product of the biquaternary ammonium salt compound, and washing, filtering and drying the crude product by using an organic solvent to obtain a refined product. Wherein, the mother liquor obtained by washing and filtering is distilled to recover the organic solvent and the unreacted dibromoalkane.
Further, the reaction time is preferably 60 ℃ and the reaction time is preferably 6 hours.
Further, in the post-treatment process, the organic solvent is petroleum ether, ethyl acetate, dichloromethane or ethanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes trimethylamine aqueous solution as raw material and ethanol as solvent. The raw materials with high safety risk such as trimethylamine gas and the like and the raw materials with high economic cost such as trimethylamine methanol solution and the like are avoided; overcomes the defects of heterogeneous reaction and low conversion rate caused by independently using trimethylamine aqueous solution and dibromoalkane as reaction raw materials.
(2) The post-treatment of the invention does not use high-risk organic solvents such as ether and the like, and all the used organic solvents can be recovered.
(3) The method has the advantages of high reaction efficiency, simplicity, economy, convenience in post-treatment and the like.
Drawings
FIG. 1 is a compound of hexamethonium bromide1H-NMR。
FIG. 2 is a diagram of the compound pentamethylammonium bromide1H-NMR。
FIG. 3 shows the preparation of octamethylammonium bromide1H-NMR。
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1: reaction at different temperatures
1, 6-dibromohexane (24.4g,100mmol) is put into a reaction kettle, 50mL ethanol is added, and the mixture is mixed evenly. Aqueous trimethylamine (30% wt,39.3g,200mmol) was then added and the reaction stirred at different temperatures for several hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. And adding a small amount of ethyl acetate into the crude product, washing and filtering to obtain a product. The yields at different temperatures are shown in table 1.
TABLE 1
As is clear from Table 1, the reaction yield at 25 ℃ was low within 6 hours, and the yield of 91.4% was obtained by extending the reaction time to 12 hours. The reaction yield can be obviously improved by heating the reaction solution to more than 60 ℃. The reaction yield can not be greatly improved when the reaction temperature is increased from 60 ℃ to 80 ℃.
Example 2: reaction at different molar ratios
1, 6-dibromohexane (24.4g,100mmol) is put into a reaction kettle, ethanol is added, and the mixture is mixed evenly. Then, trimethylamine aqueous solution (30% wt) was added in different molar ratios, and the reaction was stirred at 60 ℃ for 6 hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. And adding a small amount of ethyl acetate into the crude product, washing and filtering to obtain a product. The results of the reactions at different molar ratios are shown in table 2.
TABLE 2
| Serial number | n (1, 6-dibromohexane): n (trimethylamine) | Yield (%) |
| 1 | 1:2 | 95.5 |
| 2 | 1:2.2 | 96.9 |
| 3 | 1:2.4 | 96.5 |
As can be seen from Table 2, under otherwise identical reaction conditions, increasing the amount of trimethylamine to 2.2 equivalents increased the reaction yield to a small extent, but continued increase in the amount of trimethylamine did not result in any further increase in the yield.
Example 3: washing with different washing solvents
1, 6-dibromohexane (24.4g,100mmol) is put into a reaction kettle, 50mL ethanol is added, and the mixture is mixed evenly. Aqueous trimethylamine solution (30% wt,39.3g,200mmol) was then added and the reaction stirred at 60 ℃ for 6 hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. And adding a small amount of organic solvent into the crude product, washing and filtering to obtain a product. The yields after washing with different organic solvents and suction filtration are shown in table 3.
TABLE 3
| Serial number | Solvent(s) | Yield (%) |
| 1 | Ethyl acetate | 95.5 |
| 2 | Petroleum ether | 96.3 |
| 3 | Methylene dichloride | 96.0 |
| 4 | Ethanol | 92.8 |
As can be seen from Table 3, different washing solvents lead to a significant difference in yield, which is mainly related to the difference in solubility of the bis-quaternary ammonium compounds in different organic solvents. Hexamethonium bromide is more soluble in ethanol and relatively less soluble in petroleum ether and methylene chloride.
Example 4: preparation of hexamethonium bromide
1, 6-dibromohexane (48.7g,200mmol) is put into a reaction kettle, 100mL ethanol is added, and the mixture is mixed evenly. Aqueous trimethylamine solution (30% wt,78.6g,400mmol) was then added and the reaction stirred at 60 ℃ for 6 hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. Adding a small amount of petroleum ether into the crude product, washing, and filtering to obtain the product (of hexamethonium bromide)1H-NMR as shown in FIG. 1) was a white solid (70g), and the yield was 97.2%.
Example 5: preparation of pentamethyl ammonium bromide
1, 5-dibromopentane (46.0g,200mmol) is put into a reaction kettle, 50mL ethanol is added, and the mixture is mixed evenly. Aqueous trimethylamine solution (30% wt,86.5g,440mmol) was then added and the reaction stirred at 60 ℃ for 6 hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. Adding a small amount of ethyl acetate into the crude product, washing, and filtering to obtain the product (of pentamethyl ammonium bromide)1H-NMR as shown in FIG. 2) was a white solid (63.5g), and the yield was 91.5%.
Example 6: preparation of ammonium octamethylammonium bromide
1, 8-dibromooctane (27.2g,100mmol) is put into a reaction kettle, 50mL ethanol is added, and the mixture is mixed evenly. Aqueous trimethylamine solution (30% wt,39.3g,200mmol) was then added and the reaction stirred at 60 ℃ for 6 hours. After the reaction is finished, the solvent is distilled off under reduced pressure to obtain a white solid crude product. Adding a small amount of dichloromethane into the crude product, washing and filtering to obtain the product (of octamethyl ammonium bromide)1H-NMR as shown in FIG. 3) was a white solid (38.6g), and the yield was 99.2%.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (5)
1. A preparation method of a double quaternary ammonium salt compound is characterized by comprising the following steps: dibromoalkane and trimethylamine aqueous solution are used as reactants, ethanol is used as a solvent, the reaction is carried out for 4 to 48 hours at the temperature of 25 to 80 ℃, and post-treatment is carried out after the reaction is finished, so as to obtain a biquaternary ammonium salt compound; the chemical reaction formula is as follows:
wherein the dibromoalkane is
The mol ratio of the dibromoalkane to the trimethylamine is 1: 2 to 3.
2. The method for preparing a bis-quaternary ammonium salt compound according to claim 1, wherein the molar ratio of the dibromoalkane to the trimethylamine is preferably 1: 2.2.
3. the method for preparing a bis-quaternary ammonium salt compound according to claim 1, wherein the reaction time is preferably 60 ℃ and the reaction time is preferably 6 hours.
4. The method for preparing a bis-quaternary ammonium salt compound according to claim 1, 2 or 3, wherein the post-treatment process after the reaction is: and (3) carrying out reduced pressure distillation to recover ethanol to obtain a crude product of the biquaternary ammonium salt compound, and washing, filtering and drying the crude product by adopting an organic solvent to obtain a product.
5. The method according to claim 4, wherein the organic solvent is selected from petroleum ether, ethyl acetate, dichloromethane, and ethanol.
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- 2021-02-26 CN CN202110216552.6A patent/CN113004149A/en active Pending
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