阅读说明：本技术 一种有机化合物及其制备方法和应用 (Organic compound and preparation method and application thereof ) 是由 钟宏 孙青� 王帅 于 2020-12-23 设计创作，主要内容包括：本发明公开了一种有机化合物及其制备方法和应用,该有机化合物具有式Ⅰ所示的结构：其中,R为C-1～C-(12)烃基；由烷基硫醚基乙酸和6-氨基乙酸甲酯盐酸盐进行胺酸缩合,再采用羟胺和碱进行羟肟化得到,本发明通过将硫醚、酰氨基和羟肟酸基团结合,开发高效的羟肟酸有机化合物,根据本发明的结构设计使各官能团之间具有较强的协同作用,可用作为金属离子的分析试剂和矿物浮选的捕收剂。另外,本发明的制备方法简单,反应条件温和,易于操作。(The invention discloses an organic compound, a preparation method and application thereof, wherein the organic compound has a structure shown in a formula I: wherein R is C 1 ～C 12 A hydrocarbyl group; the invention relates to a method for preparing a hydroximic acid organic compound by combining thioether, amido and hydroximic acid groups, which is obtained by amino acid condensation of alkyl thioether acetic acid and 6-amino methyl acetate hydrochloride and hydroximization by using hydroxylamine and alkali, and the invention relates to a method for preparing a hydroximic acid organic compound by combining thioether, amido and hydroximic acid groupsThe structural design enables the functional groups to have stronger synergistic effect, and the functional groups can be used as analytical reagents of metal ions and collecting agents of mineral flotation. In addition, the preparation method is simple, mild in reaction condition and easy to operate.)

1. An organic compound having the structure of formula i:

wherein R is C₁～C₁₂A hydrocarbyl group.

2. An organic compound according to claim 1, wherein R is one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, cyclohexyl, heptyl, cycloheptyl, n-octyl, isooctyl, sec-octyl, cyclooctyl, benzyl, phenyl, phenethyl, p-tert-butylbenzyl and dodecyl.

3. A method for producing an organic compound according to claim 1 or 2, comprising the steps of:

s1, condensation reaction of amino acid: taking alkyl thioether-based acetic acid with a structure shown in a formula II and 6-amino methyl caproate hydrochloride as raw materials, 1,1' -carbonyldiimidazole as a condensing agent and triethylamine as a catalyst, and carrying out an amine acid condensation reaction to obtain 6-thioether amido methyl caproate with a structure shown in a formula III;

s2, hydroximization reaction: carrying out hydroximation reaction on 6-thioether amido methyl caproate with a structure shown in a formula III, hydroxylamine and alkali in an aqueous solution to prepare 6-thioether amido hexyl hydroximic acid;

wherein R is C₁～C₁₂A hydrocarbyl group.

4. The method according to claim 3, wherein in step S1, the molar ratio of the alkyl thioether acetic acid, methyl 6-aminocaproate hydrochloride, 1' -carbonyldiimidazole and triethylamine is 1: 1.5-2: 1-2; the temperature of the amine acid condensation reaction is 20-60 ℃, and the reaction time is 6-12 h; in step S2, the molar ratio of methyl 6-thioether-amidohexanoate, hydroxylamine and base is 1: 1.5-2.

5. Use of the organic compound according to claim 1 or 2 or the organic compound produced by the production method according to claim 3 or 4 as a reagent for analyzing metal ions.

6. The use of claim 5, wherein the metal ions comprise at least one of iron ions, manganese ions, copper ions, and aluminum ions.

7. Use according to claim 5 or 6, characterized in that the application method comprises the following steps:

in the process of analyzing the metal ions, adding the organic compound into a metal ion solution, and analyzing the concentration of the metal ions in the metal ion solution by an ultraviolet spectrophotometer; the dosage of the organic compound is 0-5 g/L.

8. Use of the organic compound according to claim 1 or 2 or the organic compound produced by the method of preparation according to claim 3 or 4 as a collector in mineral flotation.

9. The use of claim 8, wherein the mineral is a metal ore comprising at least one of bauxite, tungsten ore, manganese ore, iron ore, tin ore, copper ore, and rare earth.

10. Use according to claim 8 or 9, characterized in that the application method comprises the following steps:

in the mineral flotation process, adding the organic compound, mixing the slurry, and then floating out the minerals by a froth flotation method; wherein the dosage of the organic compound is 10-200 mg/L, and the pH value of the ore pulp is 7-9.

Technical Field

The invention relates to the field of organic compounds, in particular to an organic compound, a preparation method and application thereof, and more particularly relates to a 6-thioether amido hexyl hydroximic acid organic compound, a preparation method thereof and application thereof as an analytical reagent of metal ions and a collector of mineral flotation.

Background

The chelating agent has strong capability of chelating metal ions, can react with the metal ions to generate chelates with completely different properties, reduces and controls the concentration of the metal ions, and is widely applied to mineral flotation, hydrometallurgy, extraction and separation of metal elements and other processes. Hydroximic acid is a relatively common chelating agent because of its unique structure and chemical reactivity, it can combine with metal cation through two O atoms in carbonyl and hydroxyl to form five-membered ring structure. Chinese patents (applications) CN 108503563B, CN 110523541A, CN 103301952A and CN 103301953 a disclose the preparation of hydroxamate (structural formula a), thioether ethyl hydroxamic acid (structural formula b), 6-aliphatic amido hexyl hydroxamic acid (structural formula c) and 6-aryl amido hexyl hydroxamic acid (structural formula d), respectively.

Hydroxamic acids can be readily chelated with metal ions to form stable complexes. Cao et al reported that modification of conventional oleic acid with hydroxamic acid can effectively remove iron from potassium feldspar at a lower cost (formula e, Cao Z F, Qiu P, Wang S, et al. Benzohydroxamic acid to improve iron removal from reactive iron feldspars [ J ]. Journal of Central South University 2018,25(9): 2190-.

Hydroximic acids are widely used as collectors because of their high flotation selectivity for oxidized ores such as rare earths, ilmenites, tints and tungstates. Sun et al reported the flotation performance studies of benzylthioethylhydroxamic acid on cassiterite, calcite and quartz (formula f, Sun Q, Lu Y X, Wang S, et al. A novel surfactant 2- (benzylthio) -acetic hydroxamic acid: Synthesis, flotation performance and adsorption mechanism to casting, calcite and quartz [ J ]. Applied Surface Science,2020,522: 146509). Deng et al reported a study of the flotation performance of scheelite and calcite with N-benzoylaminohexyl hydroxamic acid (formula G, Deng L Q, ZHao G, Zhong H, et al. investment on the selection of N- ((hydroxyamino) -alkyl) alkyl amides surfactants for scheelite/calcium flotation separation [ J ]. Journal of Industrial and Engineering Chemistry,2016,33: 131-.

(Structure a, R is aryl, cycloalkyl or alkyl, Y is Na or K)

(Structure b)

(Structure C, R is C₂～C₁₈Aliphatic hydrocarbon radical)

(structure d, R is H or C₁～C₈Alkyl radical)

(Structure e)

(Structure f)

(Structure g)

However, thioether hydroxamic acids have the problems of poor solubility in aqueous solutions and poor hydrophobicity of the short carbon chains in amido hydroxamic acids.

Disclosure of Invention

In order to solve the above technical problems in the prior art, an object of the present invention is to provide an organic compound, which is prepared by combining thioether, amido and hydroximic acid groups to develop a highly efficient organic compound of hydroximic acid, and the structural design according to the present invention provides a strong synergistic effect between the functional groups, thereby effectively solving the problems of poor solubility of thioether-based hydroximic acid in aqueous solution and poor hydrophobicity of short chain of amido hydroximic acid.

In order to achieve the purpose, the technical scheme of the invention is as follows:

an organic compound having the structure shown in formula i:

wherein R is C₁～C₁₂A hydrocarbyl group.

In some embodiments, R is one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, cyclohexyl, heptyl, cycloheptyl, n-octyl, isooctyl, sec-octyl, cyclooctyl, benzyl, phenyl, phenethyl, p-tert-butylbenzyl, and dodecyl.

It is a second object of the present invention to provide a method for producing an organic compound according to any one of the above embodiments, the method comprising the steps of:

s1, condensation reaction of amino acid: taking alkyl thioether-based acetic acid with a structure shown in a formula II and 6-amino methyl caproate hydrochloride as raw materials, 1,1' -carbonyldiimidazole as a condensing agent and triethylamine as a catalyst, and carrying out an amine acid condensation reaction to obtain 6-thioether amido methyl caproate with a structure shown in a formula III;

s2, hydroximization reaction: carrying out hydroximation reaction on 6-thioether amido methyl caproate with a structure shown in a formula III, hydroxylamine and alkali in an aqueous solution to prepare 6-thioether amido hexyl hydroximic acid;

wherein R is C₁～C₁₂A hydrocarbyl group.

In some embodiments, R is one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, sec-hexyl, cyclohexyl, heptyl, cycloheptyl, n-octyl, isooctyl, sec-octyl, cyclooctyl, benzyl, phenyl, phenethyl, p-tert-butylbenzyl, and dodecyl.

In some embodiments, in step S1, the molar ratio of alkyl thioether acetic acid, methyl 6-aminocaproate hydrochloride, 1' -carbonyldiimidazole and triethylamine is 1: 1.5-2: 1-2; the temperature of the amine acid condensation reaction is 20-60 ℃, and the reaction time is 6-12 h; in step S2, the molar ratio of methyl 6-thioether-amidohexanoate, hydroxylamine and base is 1: 1.5-2.

In some embodiments, the base is a water-soluble metal hydroxide, including but not limited to sodium hydroxide, potassium hydroxide, and the like.

It is a further object of the present invention to provide use of the organic compound according to any one of the above embodiments or the organic compound obtained by the method for producing an organic compound according to any one of the above embodiments as a reagent for analyzing a metal ion.

In some embodiments, the metal ions include at least one of iron ions, manganese ions, copper ions, and aluminum ions.

In some embodiments, the method of applying the organic compound as an analytical reagent for metal ions comprises the steps of:

in the process of analyzing the metal ions, adding the organic compound into a metal ion solution, and analyzing the concentration of the metal ions in the metal ion solution by an ultraviolet spectrophotometer; the dosage of the organic compound is 0-5 g/L, and the dosage is more than 0.

The fourth object of the present invention is to provide the use of the organic compound according to any of the above embodiments or the organic compound produced by the method for producing an organic compound according to any of the above embodiments as a collector for mineral flotation.

In some embodiments, the mineral is a metal ore including at least one of bauxite, tungsten ore, manganese ore, iron ore, tin ore, copper ore, and rare earth.

In some embodiments, the method of using an organic compound as a mineral flotation collector comprises the steps of:

in the mineral flotation process, adding the organic compound, mixing the slurry, and then floating out the minerals by a froth flotation method; wherein the dosage of the organic compound is 10-200 mg/L, and the pH value of the ore pulp is 7-9; preferably, the dosage of the organic compound is 25-200 mg/L.

Compared with the prior art, the invention has the following beneficial effects:

the organic compound provided by the invention is 6-thioether amido hexyl hydroximic acid, the structure of which comprises a thioether group, an amido group and a hydroximic acid group, wherein the thioether group can increase the hydrophobic property of a hydrophobic chain, the amido group can promote the directional arrangement of the molecular structure of the compound to improve the dispersibility of the compound in a solution (shown in a formula IV), and the synergistic effect of the thioether group, the amido group and the hydroximic acid group can remarkably promote the performance of the compound. Based on the strong synergistic effect of the functional groups of the compound, the compound can be used as an analytical reagent of metal ions and a collector for mineral flotation, and particularly has good flotation effect when being used for flotation of nonferrous metal ores. The compound can improve the recovery rate of minerals such as bauxite, tin ore, wolframite and the like in flotation, and the organic compound of the invention is used as a collecting agent, so that the flotation recovery rate can be improved by about 40 percent compared with benzohydroxamic acid; compared with benzylthioethyl hydroximic acid, the flotation recovery rate can be improved by about 10 percent.

The preparation method of the organic compound provided by the invention is simple to operate, mild in reaction condition and easy to operate.

Drawings

FIG. 1 is a schematic structural diagram of N-benzylthioacetamidohexyl hydroxamic acid prepared in example 1 of the present invention;

FIG. 2 is a NMR spectrum of N-benzylthioacetamidohexyl hydroxamic acid of example 1;

FIG. 3 is a NMR carbon spectrum of N-benzylthioacetamidohexyl hydroxamic acid of example 1;

FIG. 4 is a chart of the infrared spectrum of N-benzylthioacetamidohexyl hydroxamic acid of example 1;

FIG. 5 shows the optimal configuration of N-benzylthioacetamidohexyl hydroxamic acid at DFT/B3LYP 6-311G (d) level;

FIG. 6 is a graph of the highest occupied orbital (HOMO) and lowest occupied orbital (LUMO) of N-benzylthioacetylhexylhydroxamic acid at DFT/B32LYP 6-311G (d) level.

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Example 1: preparation of N-benzylsulfanylacetoaminohexyl hydroxamic acid

Weighing 3.64g of 96.15% benzylthio acetic acid, adding the weighed 96.15% benzylthio acetic acid into 50ml of dichloromethane, adding 3.24g of 99% 1,1' -carbonyldiimidazole and 3.63g of 98% methyl 6-aminocaproate hydrochloride, reacting for 6 hours at room temperature, and after the reaction is finished, carrying out reduced pressure distillation, water washing and drying to obtain methyl N-benzylthio-acetyl-aminocaproate; weighing 2.94g of 96 percent sodium hydroxide, slowly dripping the 96 percent sodium hydroxide into 2.68g of 99.5 percent hydroxylamine hydrochloride solution, and stirring for 0.5 h; weighing 10.82g N-benzylthioacetamidohexanoate, adding into mixed solution of hydroxylamine hydrochloride and sodium hydroxide, heating to 40 deg.C under stirring, and reacting for 4 hr to obtain desired product N-benzylthioacetamidohexyl hydroxamic acidThe structure is shown in figure 1; the optimal configuration at the level of DFT/B3LYP 6-311G (d) is shown in FIG. 5; the highest occupied orbital (HOMO) and lowest occupied orbital (LUMO) at the DFT/B32LYP 6-311G (d) level are shown in FIG. 6. The yield based on benzylthioglycolic acid was 68.60%.¹H NMR、¹³The C NMR and infrared spectra are shown in Table 1, Table 2 and FIGS. 2 to 4, respectively.

TABLE 1 NMR Hydrogen and carbon Spectroscopy results

TABLE 2 Infrared Spectroscopy results

The quantum chemical calculation results show that the hydrophobic constant ClogP value of the N-benzylthioacetamidohexyl hydroximic acid is 0.8544, and the energy values of the highest occupied orbital (HOMO) and the lowest occupied orbital (LUMO) of the molecule are-0.2345 and-0.0303 a.u. The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital can be used as an index of stability of an organic substance. The energy gap between the highest occupied molecular orbit and the lowest unoccupied molecular orbit of the N-benzylthioacetamidohexyl hydroximic acid is 0.2042a.u., which is smaller than that of the benzohydroxamic acid and the benzylthioethyl hydroximic acid (see table 3), so that the N-benzylthioacetamidohexyl hydroximic acid has stronger collecting capability and is suitable for the flotation of oxidized minerals.

TABLE 3 Single Point energy, HOMO and LUMO energy values and CLOGP values for hydroximic acid collectors at DFT/B3LYP 6-311G (d) levels

Example 2: preparation of N-benzylsulfanylacetoaminohexyl hydroxamic acid

Weighing 18.20g of 96.15% benzylthio acetic acid, adding the weighed 96.15% benzylthio acetic acid into 50ml of dichloromethane, adding 16.20g of 99% 1,1' -carbonyldiimidazole and 18.15g of 98% methyl 6-aminocaproate hydrochloride, reacting for 10 hours at room temperature, and after the reaction is finished, carrying out reduced pressure distillation, water washing and drying to obtain methyl N-benzylthio-acetyl-aminocaproate; weighing 4.20g of 96 percent sodium hydroxide, slowly dripping the 96 percent sodium hydroxide into 3.82g of 99.5 percent hydroxylamine hydrochloride solution, and stirring for 0.5 h; weighing 15.45g N-benzylthioacetamidohexanoate, adding into the mixed solution of hydroxylamine hydrochloride and sodium hydroxide, heating to 40 ℃ under stirring, and reacting for 4h to obtain the required product of N-benzylthioacetamidohexyl hydroximic acid. The yield based on benzylthioglycolic acid was 76.21%.

The N-benzylthioacetamidohexyl hydroxamic acid prepared in example 1 (or example 2) was subjected to metal ion concentration analysis and mineral flotation, see in particular examples 3-6.

Example 3: analysis of iron ions in solution with N-benzylthioacetamidohexyl hydroxamic acid

50ml of a 1% solution of N-benzylthioacetamidohexyl hydroxamic acid and 10ml of Fe of unknown concentration³⁺The solution is mixed and shaken for 10min in a constant temperature oscillator at 30 ℃, and the comparison between the absorbance of the measured water phase and the absorbance of the original N-benzylthioacetamidohexyl hydroximic acid solution shows that Fe³⁺The concentration of (B) was 0.12 g/L. Therefore, the N-benzylthio-acetamidohexyl hydroximic acid can be used as an analysis reagent for iron ions, and is less toxic and more environment-friendly compared with the o-phenanthroline which is a common analysis reagent for iron ions.

Example 4: flotation of bauxite with N-benzylthio-acetamidohexyl hydroximic acid

Compared with the prior benzylthioethyl hydroximic acid and benzohydroxamic acid, the N-benzylthioacetamidoxy hydroximic acid is used for flotation of bauxite, the fixed concentration of the hydroximic acid is 150mg/L, the pH value of ore pulp is 8, and the concentration of a foaming agent methyl isobutyl carbinol (MIBC) is 30mg/L, the bauxite with the grain diameter of 0.038 mm-0.076 mm is respectively subjected to flotation. Wherein, when N-benzylthio-acetamidohexyl hydroximic acid is used as a collecting agent, the flotation recovery rate of bauxite is 90.26%; when benzylthio ethyl hydroximic acid is used as a collecting agent, the flotation recovery rate of bauxite is 89.91%; when benzohydroxamic acid is used as a collecting agent, the flotation recovery rate of bauxite is 19.88%. Therefore, the collecting performance of the N-benzylthioacetamidohexyl hydroximic acid on bauxite is stronger than that of benzylthioethyl hydroximic acid and benzohydroxamic acid.

Example 5: flotation of wolframite with N-benzylthio-acetamidohexyl hydroximic acid

Compared with the prior benzylthioethyl hydroximic acid and benzohydroxamic acid, the N-benzylthioacetamidoxyl hydroximic acid is used for floating wolframite, the concentration of the fixed hydroximic acid is 150mg/L, the pH value of ore pulp is 8, and the concentration of a foaming agent MIBC is 30mg/L, and the wolframite with the grain diameter of 0.038 mm-0.076 mm is respectively floated. Wherein, when the N-benzylthio-acetamidohexyl hydroximic acid is used as a collecting agent, the flotation recovery rate of the wolframite is 80.05%; when benzylthioethyl hydroximic acid is used as a collecting agent, the flotation recovery rate of the wolframite is 69.54 percent; when benzohydroxamic acid is used as a collecting agent, the flotation recovery rate of the wolframite is 59.12%. Therefore, the collecting performance of the N-benzylthioacetamidohexyl hydroximic acid on wolframite is obviously better than that of benzylthioethyl hydroximic acid and benzohydroxamic acid.

Example 6: flotation of cassiterite with N-benzylthioacetamidohexyl hydroximic acid

Compared with the prior benzylthioethyl hydroximic acid and benzohydroxamic acid, the N-benzylthioacetamidoxyl hydroximic acid is used for floating cassiterite, the fixed concentration of the hydroximic acid is 25mg/L, and when the pH value of ore pulp is 8, cassiterite with the particle size of 0.038 mm-0.076 mm is respectively floated. The flotation result shows that when the N-benzylthio-acetamidohexyl hydroximic acid is used as a collecting agent, the flotation recovery rate of the cassiterite can reach 87.24%; when benzylthioethyl hydroximic acid is used as a collecting agent, the flotation recovery rate of the cassiterite is 79.79 percent; when benzohydroxamic acid is used as a collecting agent, the flotation recovery rate of the cassiterite is 44.55 percent. The collecting performance of the N-benzylthioacetamidohexyl hydroximic acid on the cassiterite is obviously stronger than that of benzylthioethyl hydroximic acid and benzohydroxamic acid.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.