CN115197097A - Preparation method of safe bacteriostatic octanoyl hydroximic acid - Google Patents
Preparation method of safe bacteriostatic octanoyl hydroximic acid Download PDFInfo
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- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract
The application relates to the technical field of chemical synthesis, in particular to a preparation method of safe bacteriostatic caprylyl hydroximic acid, which comprises the following steps: s1, preparing n-caprylate: heating and refluxing n-caprylic acid and low-carbon alcohol under the action of a solid acid catalyst to obtain n-caprylic acid ester; s2, preparing caprylyl hydroximic acid: dissolving n-caprylic acid ester and hydroxylamine by using a solvent, reacting under the action of a solid base catalyst, and acidifying, purifying and drying to obtain caprylyl hydroximic acid; the molar ratio of the n-caprylate to the hydroxylamine is 1: (1.01-1.02). The method adopts the solid acid catalyst to replace concentrated sulfuric acid, thereby realizing cyclic utilization, avoiding corrosion to equipment and improving environmental friendliness; the method adopts the solid base catalyst, has good recycling property, keeps higher yield and purity of the caprylyl hydroximic acid after recycling, and reduces the production cost; controlling the molar ratio of the n-caprylate to the hydroxylamine to be 1: (1.01-1.02) can further improve the yield and purity of the caprylhydroxamic acid.
Description
Technical Field
The application relates to the technical field of chemical synthesis, in particular to a preparation method of safe bacteriostatic caprylyl hydroximic acid.
Background
Octanoyl hydroxamic acid, also called octanoyl hydroxamic acid, is one of organic acids, white or off-white powder, has CAS number of 7377-03-9, and chemical structure shown in formula 1:
the caprylyl hydroximic acid has strong chelating ability and can be used as a tyrosinase inhibitor and a preservative bacteriostatic agent. The caprylyl hydroximic acid still has strong bacteriostatic effect when being neutral, and the bacteriostatic ability of the caprylyl hydroximic acid is not influenced by additives such as surfactants, proteins and traditional Chinese medicines. Meanwhile, the caprylyl hydroximic acid is used as a bacteriostatic agent, has better bacteriostatic property in astringent, O/W emulsion, O/W cream and W/O cream, is mild and non-irritant, avoids the safety risk of the traditional bacteriostatic agent, and leads the caprylyl hydroximic acid to be more and more widely applied in cosmetics and medicines.
As the caprylyl hydroximic acid is an ideal bacteriostatic agent, the improvement of the yield and the purity of the caprylyl hydroximic acid is a research and development focus. In the preparation process of caprylyl hydroximic acid, ethyl caprylate is generally obtained by esterification reaction of caprylic acid and ethanol, then hydroximization reaction of the ethyl caprylate and hydroxylamine is carried out, and the caprylyl hydroximic acid is obtained by steps of purification, drying and the like. The patent with publication number CN110845367A discloses a preparation method of safe bacteriostatic caprylyl hydroximic acid, and the yield and the purity of caprylyl hydroximic acid are improved. However, the catalyst for the esterification reaction of n-octanoic acid and ethanol adopts sulfuric acid, the post-treatment method needs to be neutralized by sodium hydroxide, the sulfuric acid is also used in the purification step of octanoyl hydroximic acid, and the use of strong acid and strong alkali is easy to corrode equipment. In addition, in patent CN110845367A, homogeneous catalysts are adopted for both esterification and hydroximization, which cannot be recycled, and the production cost is high, thus being not suitable for industrial production.
Disclosure of Invention
In order to improve the environmental friendliness of the preparation process of the caprylyl hydroxamic acid and reduce the production cost, the application provides a safe bacteriostatic preparation method of the caprylyl hydroxamic acid.
In a first aspect, the application provides a preparation method of safe bacteriostatic octanoyl hydroximic acid, which is realized by adopting the following technical scheme:
a preparation method of safe bacteriostatic octanoyl hydroximic acid comprises the following steps:
s1, preparing n-caprylate: heating and refluxing n-caprylic acid and low-carbon alcohol under the action of a solid acid catalyst to obtain n-caprylic acid ester;
s2, preparing caprylyl hydroximic acid: dissolving n-caprylic acid ester and hydroxylamine by using a solvent, reacting under the action of a solid base catalyst, and acidifying, purifying and drying to obtain caprylyl hydroximic acid; the molar ratio of the n-caprylate to the hydroxylamine is 1: (1.01-1.02).
By adopting the technical scheme, the solid acid catalyst is adopted to replace concentrated sulfuric acid, so that not only is cyclic utilization realized, but also higher catalytic activity is kept after cyclic utilization, and the corrosion to equipment is also greatly avoided; the application adopts the solid base catalyst, can realize cyclic utilization, and keeps higher caprylyl hydroximic acid's yield and purity after cyclic utilization. Controlling the molar ratio of the n-caprylate to the hydroxylamine to be 1: (1.01-1.02) can improve the yield and purity of the octanoyl hydroximic acid.
Preferably, the mass ratio of the solid acid catalyst to the n-octanoic acid is (1-1.5): 100; further, the mass ratio of the solid acid catalyst to the n-octanoic acid is 1.2:100.
by adopting the technical scheme, the mass ratio of the solid acid catalyst to the n-octanoic acid is controlled to be (1-1.5): 100, the yield of the ethyl n-caprylate is not less than 95.8%, the purity of the ethyl n-caprylate is not less than 99.7%, and when the mass ratio of the solid acid to the n-caprylic acid is 1.2: when the yield is 100, the yield and the purity of the octanoyl hydroximic acid respectively reach 95.1 percent and 99.9 percent, the production cost is lower, and the method is more suitable for industrial production. When the mass ratio of the solid acid to the n-octanoic acid is greater than 1.5: when the reaction time is 100 hours, the production cost is high, and the yield and the purity of the ethyl n-octanoate can be reduced; and when the mass ratio of the solid acid to the n-octanoic acid is less than 1: the yield and purity of the ethyl n-octanoate are lower when the reaction time is 100 hours.
Preferably, the solid acid catalyst is a selenononeoic acid solid phase catalyst loaded with sulfonic acid groups or phosphoric acid groups; more preferably, the solid acid catalyst is a selenononeoic acid solid phase catalyst loaded with sulfonic acid groups.
By adopting the technical scheme, the selenonoxineoic acid solid phase catalyst loaded with sulfonic acid groups or phosphoric acid groups is adopted, can be recycled, keeps higher catalytic activity, can improve the yield and purity of the ethyl n-octanoate, can change the structure of the solid catalyst by adjusting the functional group loading rate on the solid acid catalyst, changes the acid strength of the acid catalyst, improves the yield and reduces byproducts; the acidity of the selenononeoic acid solid-phase catalyst loaded with the sulfonic acid group is stronger than that of the selenononeoic acid solid-phase catalyst loaded with the phosphoric acid group, and the yield of the selenononeoic acid solid-phase catalyst loaded with the sulfonic acid group to the ethyl n-octoate is higher than that of the selenononeoic acid solid-phase catalyst loaded with the phosphoric acid group to the ethyl n-octoate.
Preferably, the sulfonic acid group-supported selenononeoic acid solid phase catalyst is selected from any one of SC18143, SC18141 and SC 18140; more preferably, the selenononeoic acid solid-phase catalyst loaded with sulfonic acid groups is SC18143.
By adopting the technical scheme, the kind of the selenononeonic acid solid phase catalyst loaded with the sulfonic group also has great influence on the yield of the ethyl n-caprylate, wherein SC18143 is superior to SC18140 and is more superior to SC18141.
Preferably, the mass ratio of the solid base catalyst to the n-caprylate is (1.2-1.8): 100, respectively; more preferably, the mass ratio of the solid base catalyst to the n-caprylate is (1.4-1.6): 100, respectively; most preferably, the mass ratio of the solid base catalyst to the n-caprylate is 1.6:100.
by adopting the technical scheme, the mass ratio of the solid base catalyst to the n-caprylate is controlled to be (1.2-1.6): 100, the yield and the purity of the octanoyl hydroximic acid can be improved while the production cost is reduced; when the mass ratio of the solid base catalyst to the n-caprylate is (1.4-1.6): 100, especially when the mass ratio of the solid base catalyst to the ethyl n-octanoate is less than 1.2: at 100 deg.c, the activity of the solid base catalyst is low, and the n-ethyl octanoate can not be completely converted into octanoyl hydroximic acid, so that the yield and purity of the octanoyl hydroximic acid are reduced.
Preferably, the solid base catalyst is a two-dimensional layered double metal hydroxide or a two-dimensional layered trimetallic hydroxide.
By adopting the technical scheme, the two-dimensional layered double metal hydroxide or the two-dimensional layered trimetal hydroxide is adopted, so that the catalyst can be recycled, the higher catalytic activity is kept, and the yield of the caprylyl hydroximic acid can be improved; meanwhile, the production cost of the two-dimensional layered trimetal hydroxide is higher than that of the two-dimensional layered bimetal hydroxide.
Preferably, the two-dimensional layered double hydroxide is selected from any one of MgAl-LDH, znAl-LDH and NiAl-LDH; more preferably, the two-dimensional layered double hydroxide is MgAl-LDH.
By adopting the technical scheme, the alkalinity of the two-dimensional layered double hydroxide MgAl-LDH is stronger than that of ZnAl-LDH and NiAl-LDH, and the yield of the octanoyl hydroximic acid corresponding to the MgAl-LDH is higher than that of the octanoyl hydroximic acid corresponding to the ZnAl-LDH and the NiAl-LDH.
Preferably, the lower alcohol in the step S1 is methanol or ethanol; the solvent in the step S2 is a mixture of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is (10-15): 1.
by adopting the technical scheme, when the low-carbon alcohol is methanol, the yield of the methyl n-caprylate is 95.5 percent, the purity is 99.6 percent, and the yield of the caprylyl hydroximic acid is 94.4 percent, and the purity is 99.7 percent; when the lower alcohol is ethanol, the yield of the ethyl n-octanoate is 95.8 percent, the purity is 99.7 percent, and the yield of the octanoyl hydroximic acid is 94.9 percent, and the purity is 99.8 percent. In the reaction of the step S2, the solvent is prepared from (10-15) by mass: 1, the ethanol and the deionized water are mixed, so that the purification at the later stage is facilitated, the purity of the caprylyl hydroximic acid can be improved, and the ethyl n-caprylate and the hydroxylamine can be better dissolved in a system, so that the conversion of the ethyl n-caprylate is promoted, and the yield of the caprylyl hydroximic acid is improved.
Preferably, the acidification in the step S2 is performed by: and adjusting the pH of the system to 3-4 by using a citric acid aqueous solution.
Through adopting above-mentioned technical scheme, this application adopts the acidizing of citric acid aqueous solution to replace concentrated sulfuric acid acidizing, and the operation is safe, and environment friendly nature is high, and concentrated sulfuric acid acidizing easily makes caprylyl hydroximic acid have certain irritability.
Preferably, the purification operation in the step S2 is: filtering, collecting filtrate, distilling the filtrate under reduced pressure to remove ethanol, placing in ice water, separating out white solid, filtering to obtain precipitate, and washing with water.
By adopting the technical scheme, the purity of the caprylyl hydroximic acid can be improved by firstly acidifying and then purifying.
In summary, the present application has the following beneficial effects:
1. the method adopts the solid acid catalyst to replace concentrated sulfuric acid, thereby realizing cyclic utilization, avoiding corrosion to equipment and improving environmental friendliness; the method adopts the solid base catalyst, has good recycling property, keeps higher yield and purity of the caprylyl hydroximic acid after recycling, and reduces the production cost; controlling the molar ratio of the n-caprylate to the hydroxylamine to be 1: (1.01-1.02) can further improve the yield and purity of the caprylhydroxamic acid.
2. The selenononeonic acid solid-phase catalyst loaded with sulfonic acid groups or phosphoric acid groups can be recycled, keeps higher catalytic activity and can improve the yield and purity of the ethyl n-caprylate.
3. This application adopts two-dimensional stratiform bimetal hydroxide or two-dimensional stratiform trimetal hydroxide, can recycle and keep higher catalytic activity, can improve octanoyl hydroximic acid's yield.
4. This application adopts the acidizing of citric acid aqueous solution to replace concentrated sulfuric acid acidizing, and the operation is safe, and can avoid the irritability that concentrated sulfuric acid acidizing leads to, and the octanoyl hydroximic acid of this application preparation is more mild.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the present application are commercially available, and those not mentioned in the present application are purchased from national chemical group, chemical reagents, ltd.
Examples
Examples 1-21 provide a method for preparing safe bacteriostatic octanoyl hydroxamic acid, and are described below in example 1.
Example 1
The reaction principle of the lower alcohol described in example 1 being ethanol and caprylhydroxamic acid is as follows:
the preparation process of caprylyl hydroxamic acid provided in example 1 comprises the following steps:
s1, preparing ethyl n-caprylate: adding 14.42g (0.1 mol) of n-octanoic acid and 0.144g of solid acid catalyst into 200mL of absolute ethyl alcohol, starting stirring, reacting at 80 ℃ for 8h, cooling to room temperature, filtering to obtain precipitate and filtrate, recovering the precipitate, and distilling the filtrate under reduced pressure to remove the absolute ethyl alcohol to obtain 16.48g of ethyl n-octanoate, wherein the yield is 95.8%, and the purity is 99.7%;
s2, preparing caprylyl hydroximic acid: uniformly mixing 100mL of ethanol and 10mL of deionized water, adding 8.61g (0.05 mol) of ethyl n-octanoate, 1.67g of 50wt% hydroxylamine aqueous solution and 0.103g of solid base catalyst, starting stirring, reacting at 35 ℃ for 1h, dropwise adding 0.1mol/L citric acid aqueous solution after reaction to adjust the pH of the system to 3, filtering to obtain a precipitate and a filtrate, recovering the precipitate, distilling the filtrate under reduced pressure to remove the ethanol, adding 100mL of deionized water at 0 ℃ and standing to separate out a white solid, filtering to obtain the precipitate, washing with water, and drying to obtain white octanoyl hydroximic acid, wherein the yield is 94.9%, and the purity is 99.8%;
wherein the purity of the n-octanoic acid is 99 percent, and the n-octanoic acid is purchased from Nanjing Baimuda Biotech limited;
the solid acid catalyst is a sulfonic group-loaded selenononeoic acid solid phase catalyst with the model of SC18141 and is purchased from Suzhou selenononeoic new material science and technology company, inc.;
the 50wt% aqueous solution was purchased from Nanjing Primordial chemical Co., ltd;
the solid base catalyst is a two-dimensional layered double hydroxide ZnAl-LDH with the product number of BK2021020609-02, which is purchased from Beijing Ke New materials science and technology Limited.
Example 2 on the basis of example 1, the reaction principle of replacing the lower alcohol from ethanol to methanol and octanoyl hydroxamic acid is as follows:
the preparation process of caprylyl hydroxamic acid provided in example 2 comprises the following steps:
s1, preparing n-methyl caprylate: adding 14.42g (0.1 mol) of n-octanoic acid and 0.144g of solid acid catalyst into 200mL of anhydrous methanol, starting stirring, reacting at 80 ℃ for 8h, cooling to room temperature, filtering to obtain precipitate and filtrate, recovering the precipitate, and distilling the filtrate under reduced pressure to remove the anhydrous methanol to obtain 16.48g of methyl n-octanoate, wherein the yield is 95.5% and the purity is 99.6%;
s2, preparing caprylyl hydroximic acid: uniformly mixing 100mL of ethanol and 10mL of deionized water, adding 7.91g (0.05 mol) of methyl n-octanoate, 1.67g of 50wt% of hydroxylamine aqueous solution and 0.095g of solid base catalyst, starting stirring, reacting at 35 ℃ for 1h, dropwise adding 0.1mol/L of citric acid aqueous solution after reaction to adjust the pH of the system to 3, filtering to obtain a precipitate and a filtrate, recovering the precipitate, distilling the filtrate under reduced pressure to remove the ethanol, adding 100mL of deionized water at 0 ℃ and standing to separate out a white solid, filtering to obtain the precipitate, washing with water, and drying to obtain white octanoyl hydroximic acid, wherein the yield is 94.4%, and the purity is 99.7%.
Examples 3-8, like example 1, differ only in that: the synthesis conditions, yields and yields of the octanoyl hydroxamic acid are different, and are shown in table 1.
TABLE 1 Synthesis conditions of octanohydroxamic acids
With reference to the data in table 1, from examples 1 and 3-4, it can be seen that in the preparation method of safe bacteriostatic octanoyl hydroximic acid, the yield of octanoyl hydroximic acid is not less than 94.8%, the purity is not less than 99.8%, the yield of ethyl n-octanoate is not less than 95.8%, the purity is not less than 99.7%, and the yield and purity of octanoyl hydroximic acid in examples 3 and 4 respectively reach 95.1% and 99.9%, and from the viewpoint of production cost, example 4 has lower production cost and is more suitable for industrial production.
From examples 4 to 6, it can be seen from the data in Table 1 that the amount of the solid acid catalyst used affects the yield and purity of ethyl n-octanoate, and the mass ratio of the solid acid to n-octanoic acid is 1.2:100 is preferred, and when the mass ratio of the solid acid catalyst to the n-octanoic acid is greater than 1.5: when the reaction time is 100 hours, the production cost is high, and the yield and the purity of the ethyl n-caprylate can be reduced, which is probably because the solid acid catalyst is too much in use and is easy to agglomerate, and the dispersibility of the catalyst in a system can be influenced; and when the mass ratio of the solid acid to the n-octanoic acid is less than 1: at 100 hours, the catalytic activity is low, and the n-caprylic acid cannot be completely converted into the ethyl n-caprylate, so that the yield and the purity of the ethyl n-caprylate are reduced.
From the data in Table 1, it can be seen from examples 4, 7-8 that the amount of solid base used affects the yield and purity of octanoyl hydroxamic acid, wherein the mass ratio of the solid base catalyst to ethyl n-octanoate is 1.6: the yield and purity of 100 corresponding caprylhydroxamic acid are high, and when the mass ratio of the solid base catalyst to the ethyl n-caprylate is 1.4: the yield of the corresponding octanoyl hydroximic acid is 95.0 percent and the purity is 99.90 percent when the mass ratio of the solid base catalyst to the n-octanoic acid ethyl ester is less than 1.2: the activity of the solid base catalyst is lower at 100 ℃, and the ethyl n-caprylate can not be completely converted into the caprylyl hydroximic acid, so that the yield and the purity of the caprylyl hydroximic acid are reduced.
Example 9, like example 4, differs only in that: the model of the selenonovir neo acid solid phase catalyst loaded with sulfonic acid groups is SC18140, and is purchased from Suzhou selenonovir new material science and technology Co.
Example 10, like example 4, differs only in that: the selenononeoic acid solid-phase catalyst loaded with sulfonic acid groups is SC18143 and is purchased from Suzhou selenononeoic new material science and technology Co.
Example 11, like example 4, differs only in that: the solid acid catalyst is a phosphoric acid-supported selenononovanoic acid solid phase catalyst with the model of SC18161 and is purchased from Suzhou selenononov new material science and technology company Limited.
In this application, the yield and purity data for examples 4, 9-11 are shown in Table 2
TABLE 2 yield and purity of examples 4, 9-11
| Yield/purity | Example 4 | Example 9 | Example 10 | Example 11 |
| Yield of ethyl n-octanoate | 95.9％ | 96.2％ | 96.6％ | 95.7％ |
| Purity of ethyl n-octanoate | 99.8％ | 99.9％ | 99.9％ | 99.7％ |
| Yield of octanoyl hydroximic acid | 95.1％ | 95.4％ | 95.8％ | 94.8％ |
| Purity of octanoyl hydroximic acid | 99.9％ | 99.9％ | 99.9％ | 99.8％ |
With reference to the data in table 2, it can be seen from examples 4 and 9 to 11 that the solid acid catalyst of the present application has a greater effect on the yield of ethyl n-octanoate, wherein the yield of ethyl n-octanoate in the sulfonic acid group-supported selenononeoic acid solid phase catalyst is higher than the yield of ethyl n-octanoate in the phosphoric acid group-supported selenononeoic acid solid phase catalyst, which is probably due to the fact that the acidity of the sulfonic acid group-supported selenononeoic acid solid phase catalyst is stronger than the acidity of the phosphoric acid group-supported selenononeoic acid solid phase catalyst; and the type of the selenononeonic acid solid-phase catalyst loaded with the sulfonic group also has a great influence on the yield of the ethyl caprylate, wherein the SC18143 is superior to the SC18140 and is more superior to the SC18141.
Example 12, like example 10, differs only in that: the solid base catalyst is a two-dimensional layered double hydroxide MgAl-LDH with the product number of BK102912-01, which is purchased from Beijing Ke New materials science and technology Limited.
Example 13, like example 10, differs only in that: the solid base catalyst is two-dimensional layered double hydroxide NiAl-LDH with the product number of BK2021020608-02, which is purchased from Beijing Ke New materials science and technology Limited.
Example 14, like example 10, differs only in that: the solid base catalyst is a two-dimensional layered trimetal hydroxide ZnNiAl-LDH with the product number of BK102956-01, and is purchased from Beijing Ke Xin Material science and technology Co.
For the present application, the yield and purity data for examples 10, 12-14 are shown in Table 3.
TABLE 3 yield and purity of examples 10, 12-14
| Yield/purity | Example 10 | Example 12 | Example 13 | Example 14 |
| Yield of ethyl n-octanoate | 96.6％ | 96.6％ | 96.6％ | 96.6％ |
| Purity of ethyl n-octanoate | 99.9％ | 99.9％ | 99.9％ | 99.9％ |
| Yield of octanoyl hydroximic acid | 95.8％ | 96.2％ | 95.6％ | 96.0％ |
| Purity of octanoyl hydroximic acid | 99.9％ | 100％ | 99.8％ | 100％ |
With reference to the data in table 3, it can be seen from examples 10 and 12-14 that the production cost of the two-dimensional layered trimetallic hydroxide ZnNiAl-LDH used in the present application is higher, the two-dimensional layered trimetallic hydroxide ZnNiAl-LDH has stronger alkalinity than the two-dimensional layered trimetallic hydroxides ZnAl-LDH and two-dimensional layered trimetallic hydroxides NiAl-LDH, and the yield of octanoyl hydroximic acid corresponding to ZnNiAl-LDH is higher than that corresponding to NiAl-LDH and NiAl-LDH. The yield of the caprylyl hydroxamic acid corresponding to MgAl-LDH is higher than that of the caprylyl hydroxamic acid corresponding to ZnAl-LDH and NiAl-LDH, and is also higher than that of the caprylyl hydroxamic acid corresponding to ZnNiAl-LDH.
Example 15, like example 12, differs only in that: the solid base catalyst is a two-dimensional layered double hydroxide MgAl-LDH which is recovered for 1 time;
the treatment method after recovery of the two-dimensional layered double hydroxide MgAl-LDH is as follows: the two-dimensional layered double hydroxide MgAl-LDH is placed in deionized water, ultrasonic washing is carried out for 5min under the power of 200W, and vacuum drying is carried out for 6h at the temperature of 70 ℃.
Example 16, like example 15, differs only in that: 1 recovery was replaced by 5 recoveries.
Example 17, like example 15, differs only in that: 1 recovery was replaced with 50 recoveries.
In this application, the yield and purity data for examples 12, 15-17 are shown in Table 4.
TABLE 4 yield and purity of examples 12, 15-17
| Yield/purity | Example 12 | Example 15 | Example 16 | Example 17 |
| Yield of ethyl n-octanoate | 96.6％ | 96.6％ | 96.6％ | 96.6％ |
| Purity of ethyl n-octanoate | 99.9％ | 99.9％ | 99.9％ | 99.9％ |
| Yield of octanoyl hydroximic acid | 96.2％ | 96.2％ | 96.2％ | 96.1％ |
| Purity of octanoyl hydroximic acid | 100％ | 100％ | 100％ | 99.9％ |
In combination with the data in table 4, from examples 12 and 15-17, it can be seen that the present application uses the two-dimensional layered double hydroxide MgAl-LDH, which can maintain the catalytic activity for the first use after 1 and 5 times of recovery, maintain the yield of caprylhydroxamic acid at 96.2% and the purity of caprylhydroxamic acid at 100%, and reduce both the yield and the purity by only 1% after 50 times of recovery, indicating that the cyclic applicability of the two-dimensional layered double hydroxide MgAl-LDH is very good.
Example 18, like example 12, differs only in that: the solid acid catalyst is a sulfonic group-loaded selenononeoic acid solid phase catalyst (model SC 18143) which is recovered for 1 time;
wherein the treatment mode after the recovery of the sulfonic group-supported selenononeoic acid solid-phase catalyst (model SC 18143) is as follows: placing the selenononeoic acid solid-phase catalyst (model is SC 18143) loaded with sulfonic group in ethanol, ultrasonically washing for 5min under 200W power, and vacuum drying for 6h at 50 ℃.
Example 19, like example 18, differs only in that: 1 recycle was replaced by 5.
Example 20, like example 18, differs only in that: the 1 recovery was replaced with 50 recoveries.
For the present application, the yield and purity data for examples 12, 18-20 are shown in Table 5.
TABLE 5 yield and purity of examples 12, 18-20
| Yield/purity | Example 12 | Example 18 | Example 19 | Example 20 |
| Yield of ethyl n-octanoate | 96.6％ | 96.6％ | 96.5％ | 96.4％ |
| Purity of ethyl n-octanoate | 99.9％ | 99.9％ | 99.9％ | 99.8％ |
| Yield of octanoyl hydroximic acid | 96.2％ | 96.2％ | 96.1％ | 95.9％ |
| Purity of octanoyl hydroximic acid | 100％ | 100％ | 100％ | 99.9％ |
From the data in table 5, it is understood from examples 12 and 18 to 20 that the sulfonic acid group selenomonovinoneo acid solid phase catalyst SC18143 used in the present invention can maintain the catalytic activity for the first use even after 1 recovery, maintain the yield of ethyl n-octanoate at 96.6% and the purity of ethyl n-octanoate at 99.9%, reduce the yield by 1% and the purity at 99.9% after 5 recovery, reduce the yield by 2% and the purity by 1% after 50 recovery, and show that the sulfonic acid group selenomonovinoneo acid solid phase catalyst SC18143 has good recycling performance.
Example 21, the same as example 1, only differs: the step S2 is different, and specifically comprises the following steps:
uniformly mixing 100mL of ethanol and 100mL of deionized water, adding 8.61g (0.05 mol) of ethyl n-octanoate, 1.67g of 50wt% of hydroxylamine aqueous solution and 0.103g of solid base catalyst, starting stirring, reacting at 35 ℃ for 1h, dropwise adding 0.1mol/L of citric acid aqueous solution after reaction to adjust the pH of the system to 3, filtering to obtain a precipitate and a filtrate, recovering the precipitate, distilling the filtrate under reduced pressure to remove the ethanol, adding 100mL of deionized water at 0 ℃ and standing to separate out a white solid, filtering to obtain the precipitate, washing with water, and drying to obtain white octanoyl hydroximic acid, wherein the yield is 94.7%, and the purity is 99.7%.
Comparative example
Comparative example 1, the same as example 1, except that: the step S2 is different, and specifically comprises the following steps:
uniformly mixing 100mL of ethanol and 10mL of deionized water, adding 8.61g (0.05 mol) of ethyl n-octanoate, 1.67g of 50wt% hydroxylamine aqueous solution and 0.103g of solid base catalyst, starting stirring, reacting at 35 ℃ for 1h, filtering to obtain a precipitate and a filtrate, recovering the precipitate, distilling the filtrate under reduced pressure to remove the ethanol, adding 100mL of deionized water, standing, cooling to 0 ℃, dropwise adding 0.1mol/L of citric acid aqueous solution to adjust the pH of a system to 3, separating out a white solid, filtering to obtain the precipitate, washing with water, and drying to obtain white octanoyl hydroximic acid, wherein the yield is 94.8% and the purity is 99.6%.
Comparative example 2, like example 1, differs only in that: the step S2 is different, and specifically comprises the following steps:
mixing 1.67g of 50wt% hydroxylamine aqueous solution with 50mL of ethanol, adding 0.0774g of sodium acetate and 0.05g of sodium carbonate into 50mL of deionized water, adding 8.61g (0.05 mol) of ethyl n-octanoate after dissolution, reacting for 1h at 35 ℃, filtering to obtain a filtrate, distilling the filtrate under reduced pressure to remove the ethanol, adding 100mL of deionized water, standing, cooling to 0 ℃, dropwise adding 0.1mol/L of citric acid aqueous solution to adjust the pH of the system to 3, separating out a white solid, filtering to obtain a precipitate, washing with water, and drying to obtain white octanoyl hydroximic acid, wherein the yield is 94.3%, and the purity is 99.6%.
Comparative example 3, like example 1, differs only in that: the molar ratio of the ethyl n-octanoate to the hydroxylamine is 1:1.
comparative example 4, like example 1, differs only in that: the molar ratio of the ethyl n-octanoate to the hydroxylamine is 1:1.05.
in this application, the yield and purity data for example 1 and comparative examples 3-4 are shown in Table 6.
TABLE 6 yield and purity of example 1, comparative examples 3-4
| Yield/purity | Example 1 | Comparative example 3 | Comparative example 4 |
| Yield of octanoyl hydroximic acid | 94.8％ | 93.9％ | 94.8％ |
| Purity of octanoyl hydroximic acid | 99.8％ | 99.2％ | 99.5％ |
In combination with the data of table 6, it can be seen from example 1 and comparative examples 3 to 4 that the molar ratio of ethyl n-octanoate to hydroxylamine was controlled to 1: (1.01-1.02) can improve the yield and purity of the octanoyl hydroximic acid; and when the molar ratio of the ethyl n-octanoate to the hydroxylamine is 1:1, its value is less than 1:1.01, the yield of caprylhydroxamic acid is reduced, probably because the ethyl n-octanoate is not completely converted, and the ethyl n-octanoate may also be present in the product, which also reduces the purity of the caprylhydroxamic acid; and when the molar ratio of the ethyl n-octanoate to the hydroxylamine is 1:1.05, its value is greater than 1:1.02, the purity of the octanoyl hydroximic acid is reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of safe bacteriostatic caprylyl hydroximic acid is characterized by comprising the following steps:
s1, preparing n-caprylate: heating and refluxing n-caprylic acid and low-carbon alcohol under the action of a solid acid catalyst to obtain n-caprylate;
s2, preparing caprylyl hydroximic acid: dissolving n-caprylic acid ester and hydroxylamine by using a solvent, reacting under the action of a solid base catalyst, and acidifying, purifying and drying to obtain caprylyl hydroximic acid; the molar ratio of the n-caprylate to the hydroxylamine is 1: (1.01-1.02).
2. The method for preparing a safe bacteriostatic caprylyl hydroximic acid according to claim 1, wherein the mass ratio of the solid acid catalyst to n-caprylic acid is (1-1.5): 100.
3. the preparation method of a safe bacteriostatic octanoyl hydroximic acid according to claim 2, wherein said solid acid catalyst is selenonoxinoic acid solid phase catalyst loaded with sulfonic acid group or phosphoric acid group.
4. The preparation method of safe bacteriostatic octanoyl hydroximic acid according to claim 3, wherein said sulfonic acid group-loaded selenonoxinoic acid solid phase catalyst is selected from any one of SC18143, SC18141, and SC 18140.
5. The preparation method of a safe bacteriostatic octanoyl hydroximic acid according to claim 1, wherein the mass ratio of the solid base catalyst and n-octanoate is (1.2-1.8): 100.
6. the method for preparing safe bacteriostatic octanoyl hydroximic acid according to claim 5, wherein said solid base catalyst is two-dimensional layered double metal hydroxide or two-dimensional layered trimetal hydroxide.
7. The preparation method of safe bacteriostatic octanoyl hydroximic acid according to claim 6, wherein said two-dimensional layered double hydroxide is selected from any one of MgAl-LDH, znAl-LDH, niAl-LDH.
8. The method for preparing safe bacteriostatic caprylyl hydroximic acid according to any one of claims 1 to 7, wherein the lower alcohol in the step S1 is methanol or ethanol; the solvent in the step S2 is a mixture of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is (10-15): 1.
9. the method for preparing safe bacteriostatic octanoyl hydroximic acid according to claim 8, wherein the acidification operation in the step S2 is as follows: adjusting the pH value of the system to 3-4 by using citric acid aqueous solution.
10. The method for preparing safe bacteriostatic octanoyl hydroximic acid according to claim 9, wherein the purification operation in the step S2 is: filtering, collecting filtrate, distilling the filtrate under reduced pressure to remove ethanol, placing in ice water, separating out white solid, filtering to obtain precipitate, and washing with water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010111849A1 (en) * | 2009-04-02 | 2010-10-07 | 北京化工大学 | Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof |
| CN110845367A (en) * | 2019-11-16 | 2020-02-28 | 菏泽新东方日化科技有限公司 | Preparation process of caprylyl hydroximic acid |
| CN112279784A (en) * | 2020-10-23 | 2021-01-29 | 烟台东方化学有限公司 | Preparation process of caprylyl hydroximic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111849A1 (en) * | 2009-04-02 | 2010-10-07 | 北京化工大学 | Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof |
| CN110845367A (en) * | 2019-11-16 | 2020-02-28 | 菏泽新东方日化科技有限公司 | Preparation process of caprylyl hydroximic acid |
| CN112279784A (en) * | 2020-10-23 | 2021-01-29 | 烟台东方化学有限公司 | Preparation process of caprylyl hydroximic acid |
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