CN111777608B - Novel plant modified quinoline quaternary ammonium salt compound, preparation method and application - Google Patents
Novel plant modified quinoline quaternary ammonium salt compound, preparation method and application Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention relates to the technical field of organic synthesis, and discloses a novel plant modified quinoline quaternary ammonium salt compound, and a preparation method and application thereof. The corrosion inhibitor is carboxylate modified by quaternization of camptothecin, and the preparation method comprises the following steps: mixing and dissolving camptothecin and a solvent, adding benzyl halide and a catalyst, heating to 150-160 ℃, stirring and refluxing for reaction for 4-6 hours, removing the solvent, then extracting, and removing an extracting agent; adding alkaline aqueous solution, stirring and reacting for 1-2 hours at 60 ℃, cooling to 0-3 ℃, standing for 12-24 hours, recrystallizing the solid for three times, and removing water to obtain the modified compound. The compound is camptothecin quinoline quaternary ammonium salt, is green and environment-friendly, has low cost, is a cationic surfactant, has good matching property with other functional medicaments when being used as a corrosion inhibitor, has good solubility, achieves the national level 1 standard in corrosion inhibition performance, and has high industrial popularization value.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of chemical synthesis, in particular to a novel plant modified quinoline quaternary ammonium salt compound, a preparation method and application thereof.
[ background of the invention ]
The oil production method is provided at the present stage in order to increase the oil yield and improve the oil production efficiency. Acidification is a measure for strengthening oil recovery, and is an effective technical measure for increasing the yield of an oil and gas well and increasing the injection of a water injection well. The principle is that the permeability of stratum pores and cracks is recovered or improved through the dissolving and corrosion effects of acid liquor on rock cement or stratum pores, plugs in cracks and the like. Acidification can be divided into acid washing, matrix acidification and fracture acidification (also called acid fracturing) according to different processes. The acid cleaning is to inject a small amount of acid liquor into the shaft to remove dirt such as acid-soluble particles, drill cuttings and the like in the perforation of the shaft and dredge the perforation. Matrix acidizing is the injection of an acid into the formation at a pressure below the fracture pressure of the rock, and the solvency of the acid solution is used to modify and increase the permeability of the formation in the near-wellbore region. Acid fracturing is that when the pressure is higher than the rock fracture pressure, acid liquor is injected into a stratum to form cracks on the stratum, and the acid liquor can corrode substances on the wall surfaces of the cracks to enlarge the cracks and enhance the flow conductivity.
In the production of oil and gas wells, it is often necessary to enhance recovery by acidizing. However, in the process of acidizing construction, corrosion of acid liquor to metals can not only damage surface equipment and underground pipe strings, but also a large amount of corroded iron ions can form ferric hydroxide precipitates under certain conditions, so that the acidizing effect is influenced, and sudden breakage accidents of underground pipes can be caused sometimes to cause serious economic loss, and then, an acidizing corrosion inhibitor needs to be added to solve the problems. The modern society develops rapidly, has higher and higher requirements on environmental protection, and has important significance in developing green and pollution-free corrosion inhibitors.
However, the existing common corrosion inhibitors at present comprise toxic inorganic corrosion inhibitors and some organic phosphorus corrosion inhibitors, and the discharge of the corrosion inhibitors can cause eutrophication of water bodies. Most of the existing corrosion inhibitors in the same field have toxic and side effects, or have higher synthesis cost and no market competitiveness.
Therefore, the development of new environment-friendly, cheap and widely available pollution-free corrosion inhibitors is a new direction for the development of the current corrosion inhibitors.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a biodegradable compound which is green and pollution-free and has very good corrosion inhibition performance.
In order to achieve the purpose, the invention provides a novel plant modified quinoline quaternary ammonium salt compound which has good corrosion inhibition performance, wherein the camptothecin is modified by nucleophilic substitution of alkyl halide and then hydrolyzed, and the structure of the obtained camptothecin modified quinoline quaternary ammonium salt compound is as follows:
wherein M is a metal element and represents Na or K; x is halogen and represents one of F, Cl, Br and I, preferably Cl.
The invention also aims to provide a preparation method of the novel plant modified quinoline quaternary ammonium salt compound, which comprises the following steps:
mixing camptothecin and a solvent in proportion, adding benzyl halide and a catalyst, heating to 150 ℃ and 160 ℃, and stirring and refluxing for reaction for 4-6 hours; after the reaction is finished, removing the solvent, extracting, removing the extractant of the extraction phase, slowly adding alkali liquor, stirring and reacting for 1-2 hours at the temperature of 60 ℃, cooling to 0-3 ℃, standing for 12-24 hours, crystallizing and separating out, adding 60 ℃ hot water again to the crystal for dissolving, recrystallizing for three times, removing water, and obtaining the finished product.
Further, the solvent is one or more of methanol, ethanol, isopropanol and Dimethylformamide (DMF); the mass ratio of the camptothecin to the solvent is 10: (20-50);
further, the catalyst is one or more of benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride;
further, the alkali liquor is one or two of sodium hydroxide and potassium hydroxide, and the content of the alkali liquor is 10 wt%;
further, the molar ratio of the camptothecin to the catalyst to the benzyl halide to the base is 10: (0.1-0.5): (10-12): (10-12);
further, the halogen atom of the benzyl halide is one of F, Cl, Br and I, preferably Cl;
further, the solvent removal is carried out by a reduced pressure distillation method;
further, the extraction step is to add an extracting agent, extract three times, combine extract phases and evaporate the extracting agent; the extractant is one of benzene, toluene, ether and chloroform.
The principle of the preparation method of the invention is as follows: camptothecin is a nitrogen-containing heterocycle, contains tertiary amine in a molecule, has strong biological activity, can perform nucleophilic substitution reaction with alkyl halide, and has enhanced solubility after quaternary ammonium salt is generated.
The invention also aims to provide the application of the novel plant modified quinoline quaternary ammonium salt compound as the corrosion inhibitor in the acidification construction, the compound is added into the acid liquor according to the mass fraction of 0.1-2%, and according to the specific corrosion inhibition performance requirement, the compound can be added into the acid liquor according to the mass fraction of 0.1-0.5%, so that the corrosion inhibition effect can be achieved.
Further, the acid solution can be hydrochloric acid or earth acid, and the acid concentration of the acid solution can be in the range of 15-20 wt%;
furthermore, in the acidification construction application, the water treatment agent can be compatible with other corrosion inhibitors, bactericides, scale inhibitors and other medicaments according to specific working conditions.
The invention has the beneficial effects that:
1) the compound raw material is extracted from plants, is a renewable resource, and is green and environment-friendly;
2) the compound has simple synthesis process, the purification process mainly adopts water as a recrystallization solvent, the cost is low, and the industrial production is convenient;
3) the compound is a cationic surfactant, has good matching property with other functional medicaments when used on site, has good solubility in an alcohol-water solution and good corrosion inhibition effect, and can reach the national level 1 standard in an acidification experiment at 90 ℃.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention is further described in detail with reference to the following detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Respectively taking 1mol of camptothecin and 700g of methanol, mixing and dissolving, adding 1.1mol of benzyl chloride and 0.01mol of benzyltriethylammonium chloride, heating to 150 ℃, and stirring for reflux reaction for 6 hours; distilling under reduced pressure to remove solvent, extracting with diethyl ether for three times, mixing extractive phases, and evaporating diethyl ether; slowly adding 1.1mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 2 hours, cooling to 3 ℃, standing for 24 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
In the experiment, benzyl chloride is used for carrying out nucleophilic substitution reaction on camptothecin under the action of a catalyst, and then carboxylate with high solubility is generated through hydrolysis reaction, so that the camptothecin derivative has the characteristic of a cationic surfactant and has good solubility in an alcohol-water solution.
Example 2
Respectively taking 1mol of camptothecin, 435g of methanol and 435g of DMF, mixing and dissolving, adding 1.2mol of benzyl bromide and 0.03mol of tetrabutylammonium bromide, heating to 160 ℃, and stirring and refluxing for reaction for 4 hours; distilling under reduced pressure to remove solvent, extracting with toluene for three times, mixing the extract phases, and evaporating to dryness; slowly adding 1mol of potassium hydroxide 10% wt aqueous solution, stirring and reacting for 1 hour at 60 ℃, cooling to 0 ℃, standing for 12 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolving, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Example 3
Respectively taking 1mol of camptothecin, 400g of isopropanol, 500g of methanol and 500g of ethanol, mixing and dissolving, adding 1.0mol of benzyl chloride, 0.017mol of tetrabutylammonium hydrogen sulfate, 0.017mol of trioctylmethylammonium chloride and 0.017mol of dodecyltrimethylammonium chloride as catalysts, heating to 155 ℃, and carrying out stirring reflux reaction for 5 hours; distilling under reduced pressure to remove solvent, extracting with chloroform for three times, mixing extractive phases, and evaporating chloroform; slowly adding 0.6mol of 10wt% aqueous solution of sodium hydroxide and 0.6mol of 10wt% aqueous solution of potassium hydroxide, stirring and reacting for 1.5 hours at the temperature of 60 ℃, cooling to 2 ℃, standing for 20 hours, pouring out the upper aqueous solution after crystallization is completed, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Example 4
Respectively taking 1mol of camptothecin, mixing with 1000g of ethanol and 740g of methanol for dissolving, adding 1.2mol of benzyl bromide, 0.013mol of dodecyl trimethyl ammonium chloride and 0.007mol of tetradecyl trimethyl ammonium chloride, heating to 160 ℃, and stirring for reflux reaction for 6 hours; distilling under reduced pressure to remove the solvent, repeatedly washing with benzene for three times, and evaporating to remove benzene; slowly adding 0.6mol of 10wt% aqueous solution of sodium hydroxide and 0.6mol of 10wt% aqueous solution of potassium hydroxide, stirring and reacting for 1.5 hours at the temperature of 60 ℃, cooling to 0 ℃, standing for 14 hours, pouring out the upper aqueous solution after crystallization is completed, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Example 5
Respectively taking 1mol of camptothecin, mixing and dissolving the camptothecin with 400g of ethanol, 540g of methanol, 400g of isopropanol and 400g of DMF, adding 1.2mol of benzyl chloride, then respectively adding 0.07mol of benzyltriethylammonium chloride, 0.07mol of tetrabutylammonium bromide, 0.07mol of tetrabutylammonium chloride, 0.07mol of tetrabutylammonium hydrogen sulfate, 0.07mol of trioctylmethylammonium chloride, 0.07mol of dodecyltrimethylammonium chloride and 0.08mol of tetradecyltrimethylammonium chloride, heating to 150 ℃, and stirring and refluxing for reaction for 6 hours; distilling under reduced pressure to remove the solvent, repeatedly washing with benzene for three times, and evaporating to remove benzene; slowly adding 1.2mol of aqueous solution with 10 percent by weight of potassium hydroxide, stirring and reacting for 1.5 hours at the temperature of 60 ℃, cooling to 0 ℃, standing for 14 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolving, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 1
Respectively taking 1mol of camptothecin and 400g of methanol, mixing and dissolving, adding 1.1mol of benzyl chloride and 0.01mol of benzyltriethylammonium chloride, heating to 150 ℃, and stirring for reflux reaction for 6 hours; distilling under reduced pressure to remove solvent, extracting with diethyl ether for three times, mixing extractive phases, and evaporating diethyl ether; slowly adding 1.1mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 2 hours, cooling to 3 ℃, standing for 24 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 2
Respectively taking 1mol of camptothecin and 700g of methanol, mixing and dissolving, adding 0.9mol of benzyl chloride and 0.01mol of benzyltriethylammonium chloride, heating to 150 ℃, and stirring for reflux reaction for 6 hours; distilling under reduced pressure to remove solvent, extracting with diethyl ether for three times, mixing extractive phases, and evaporating diethyl ether; slowly adding 1.1mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 2 hours, cooling to 3 ℃, standing for 24 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 3
Respectively taking 1mol of camptothecin and 700g of methanol, mixing and dissolving, adding 1.1mol of benzyl chloride and 0.01mol of benzyltriethylammonium chloride, heating to 150 ℃, and stirring for reflux reaction for 6 hours; distilling under reduced pressure to remove solvent, extracting with diethyl ether for three times, mixing extractive phases, and evaporating diethyl ether; slowly adding 0.9mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 2 hours, cooling to 3 ℃, standing for 24 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 4
Respectively taking 1mol of camptothecin and 700g of methanol, mixing and dissolving, adding 1.1mol of benzyl chloride and 0.01mol of benzyltriethylammonium chloride, heating to 150 ℃, and stirring for reflux reaction for 3 hours; distilling under reduced pressure to remove solvent, extracting with diethyl ether for three times, mixing extractive phases, and evaporating diethyl ether; slowly adding 1.1mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 2 hours, cooling to 3 ℃, standing for 24 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 5
Respectively taking 1mol of camptothecin, 1000g of methanol and 1000g of DMF, mixing and dissolving, adding 1.2mol of benzyl bromide and 0.03mol of tetrabutylammonium bromide, heating to 160 ℃, and stirring and refluxing for reaction for 4 hours; distilling under reduced pressure to remove solvent, extracting with toluene for three times, mixing the extract phases, and evaporating to dryness; slowly adding 1mol of potassium hydroxide 10% wt aqueous solution, stirring and reacting for 1 hour at 60 ℃, cooling to 0 ℃, standing for 12 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolving, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 6
Respectively taking 1mol of camptothecin, 435g of methanol and 435g of DMF, mixing and dissolving, adding 1.4mol of benzyl bromide and 0.03mol of tetrabutylammonium bromide, heating to 160 ℃, and stirring and refluxing for reaction for 4 hours; distilling under reduced pressure to remove solvent, extracting with toluene for three times, mixing the extract phases, and evaporating to dryness; slowly adding 1mol of potassium hydroxide 10% wt aqueous solution, stirring and reacting for 1 hour at 60 ℃, cooling to 0 ℃, standing for 12 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolving, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 7
Respectively taking 1mol of camptothecin, 435g of methanol and 435g of DMF, mixing and dissolving, adding 1.2mol of benzyl bromide and 0.03mol of tetrabutylammonium bromide, heating to 160 ℃, and carrying out stirring reflux reaction for 7 hours; distilling under reduced pressure to remove solvent, extracting with toluene for three times, mixing the extract phases, and evaporating to dryness; slowly adding 1mol of potassium hydroxide 10% wt aqueous solution, stirring and reacting for 1 hour at 60 ℃, cooling to 0 ℃, standing for 12 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolving, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Comparative example 8
Respectively taking 1mol of camptothecin, 435g of methanol and 435g of DMF, mixing and dissolving, adding 1.2mol of benzyl bromide and 0.03mol of tetrabutylammonium bromide, heating to 160 ℃, and stirring and refluxing for reaction for 4 hours; distilling under reduced pressure to remove solvent, extracting with toluene for three times, mixing the extract phases, and evaporating to dryness; slowly adding 1.4mol of 10wt% aqueous solution of potassium hydroxide, stirring at 60 ℃ for reaction for 1 hour, cooling to 0 ℃, standing for 12 hours, pouring out the upper aqueous solution after crystallization is finished, adding 60 ℃ hot water again for dissolution, recrystallizing for three times, removing water by using a rotary evaporator, and finally obtaining the camptothecin modified quinoline quaternary ammonium salt compound.
Experimental example 1
And (3) performing performance test on the corrosion inhibitor samples obtained in the above embodiments and comparative examples by referring to a petroleum industry standard SY/T5405-2019 corrosion inhibitor performance test method and evaluation index for acidification. The experimental conditions were: the corrosion medium is 20% hydrochloric acid solution, the test piece is made of N80 steel, the acidification temperature is 90 ℃, the addition amount of the corrosion inhibitor is 1%, and the acidification time is 4 hours.
The corrosion test results are shown in table 1.
Table 1 acidizing corrosion test data
| Compound sample | Hydrochloric acid concentration (%) | Addition amount (%) | Etching Rate (g/(m)2h) | Rank of |
| Example 1 | 20％ | 1％ | 5.4961 | 1 |
| Example 2 | 20％ | 1％ | 5.3834 | 1 |
| Example 3 | 20％ | 1％ | 5.6972 | 1 |
| Example 4 | 20％ | 1％ | 5.6131 | 1 |
| Example 5 | 20％ | 1％ | 5.7030 | 1 |
| Comparative example 1 | 20％ | 1％ | 6.3110 | 2 |
| Comparative example 2 | 20％ | 1％ | 6.8309 | 2 |
| Comparative example 3 | 20％ | 1％ | 6.2215 | 2 |
| Comparative example 4 | 20％ | 1％ | 6.3685 | 2 |
| Comparative example 5 | 20％ | 1％ | 6.7251 | 2 |
| Comparative example 6 | 20％ | 1％ | 6.2203 | 2 |
| Comparative example 7 | 20％ | 1％ | 7.1127 | / |
| Comparative example 8 | 20％ | 1％ | 7.3611 | / |
As can be seen from the data in Table 1, the compounds prepared in examples 1 to 4 all have good corrosion inhibitor effect in an acidification test at 90 ℃, can well protect N80 steel, slow down acid corrosion and have corrosion rate less than the national standard specified value of 6.00 (g/(m)2h) And the corrosion inhibition performance reaches grade 1 by judging according to the industrial standard. The principle is that the camptothecin modified quaternary ammonium salt quinoline compound blocks acid corrosion on the surface of steel in a physical and chemical adsorption mode and an interface film forming mode, and plays a role in corrosion inhibition.
Comparative examples 1 to 4 are comparative examples of example 1 under changed reaction conditions, respectively, and it can be seen from comparative examples 1 to 4 that when the amount of the solvent is insufficient, the amount of the benzyl halide is insufficient, the alkali solution required for hydrolysis is insufficient, and the affinity substitution reaction time is insufficient, the corrosion rate test performance of the obtained product is remarkably lowered, and does not reach grade 1. The reason is that the reaction system affects the conversion rate of camptothecin, and the quality of the product is reduced.
Comparative examples 5 to 8 are comparative examples of example 2 with the change of reaction conditions, respectively, and it can be seen from comparative examples 5 to 8 that the product corrosion inhibition performance is affected to less than grade 1 when the solvent is excessive, the benzyl halide is excessive, the alkali solution required for hydrolysis is excessive, and the affinity substitution reaction time is too long. The possible reason is that when the solvent is excessive, the concentration of the reaction substrate is too low, and the reaction conversion rate is influenced; excessive benzyl halide, excessive alkali liquor required for hydrolysis and too long time of affinity substitution reaction, side reaction may occur, which affects the performance of the product.
Further experiments were conducted on the relevant conditions of camptothecin substitution reaction, hydrolysis reaction and purification in combination with comparative examples 1-8, and the reaction conditions and value ranges in examples 1-5 are preferred conditions for implementing the present invention.
Experimental example 2
The performance of the camptothecin modified compound after being compatible with various functional medicaments in table 2 is tested and is as follows.
TABLE 2 compatibility test of drugs
The medicaments with various functions in the table 2 are common medicaments, and the properties show that the camptothecin modified compound has good matching property when used on site, and does not have negative influence on compatible medicaments, because the quaternary ammonium salt structure generated after camptothecin modification and carboxylate formed by hydrolysis have good matching property on the medicaments, and in addition, the quaternary ammonium salt structure also has a sterilization function. In conclusion, the camptothecin modified corrosion inhibitor can be completely used as an ideal choice of the corrosion inhibitor in acidification construction.
The camptothecin modified quinoline quaternary ammonium salt compound and the preparation method thereof are described in detail with reference to the specific embodiments, but the description of the embodiment examples is illustrative and not restrictive, and several examples can be cited according to the limited scope, so that changes and modifications without departing from the spirit and scope of the technology of the present invention shall fall within the protection scope of the present invention.
Claims (11)
1. A plant-modified quaternary quinoline ammonium salt compound having a structural formula of formula (I):
（I）
wherein M represents Na or K; x represents one of F, Cl, Br and I.
2. The compound of claim 1, wherein X in the formula is Cl.
3. A process for the preparation of a compound according to claim 1, comprising the steps of:
mixing camptothecin and a solvent, adding benzyl halide and a catalyst, heating to 150-160 ℃ for reflux reaction, removing the solvent, extracting, hydrolyzing at 60 ℃ under an alkali liquor condition, and then crystallizing, recrystallizing and removing water to obtain a compound shown in the formula (I);
the alkali liquor is sodium hydroxide and/or potassium hydroxide solution;
the benzyl halide is one of benzyl fluoride, benzyl chloride, benzyl bromide and benzyl iodide.
4. The method of claim 3, wherein the benzyl halide is benzyl chloride.
5. The method for preparing the compound according to claim 3, wherein the solvent is one or more of methanol, ethanol, isopropanol and dimethylformamide.
6. The method for preparing the compound according to claim 3, wherein the catalyst is one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.
7. The method for preparing the compound according to claim 3, wherein the mass ratio of the camptothecin to the solvent is 10: (20-50).
8. The process for the preparation of a compound according to claim 3, wherein the molar ratio of camptothecin, catalyst, benzyl halide and base is 10: (0.1-0.5): (10-12): (10-12); the concentration of the alkali liquor is 10 wt%.
9. A process for the preparation of a compound according to claim 3, characterized in that:
the reflux reaction time is 4-6 hours;
the hydrolysis reaction time is 1-2 hours;
the extractant in the extraction step is chloroform;
the crystallization step is to cool the temperature to 0 to 3 ℃ and place the mixture for 12 to 24 hours;
the recrystallization step is dissolving with hot water at 60 ℃, cooling and repeating for three times.
10. The method for preparing the compound according to claim 3, wherein the extractant in the extraction step is one of benzene, toluene and diethyl ether; the catalyst is one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.
11. Use of a compound according to claim 1 or 2 for the preparation of an acidified corrosion inhibitor.
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Denomination of invention: A Novel Plant Modified Quinoline Quaternary Ammonium Salt Compound and Its Preparation Method and Application Effective date of registration: 20230922 Granted publication date: 20210803 Pledgee: Wuhan area branch of Hubei pilot free trade zone of Bank of China Ltd. Pledgor: Hubei Jingyu Materials Co.,Ltd. Registration number: Y2023980058034 |