CN103922968B - Preparation method of hydroxamic acid or hydroxamic acid salt - Google Patents
Preparation method of hydroxamic acid or hydroxamic acid salt Download PDFInfo
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Abstract
The invention discloses a preparation method of hydroxamic acid or hydroxamic acid salt. The method comprises the steps of adding alkaline into a methanol solution of a hydroxylamine salt under a stirring condition, then, adding organic carboxylic acid methyl ester to react, distilling to recover methanol after the reaction is ended to obtain a product hydroxamic acid salt; or cooling a reaction system after the reaction is ended, adding concentrated sulfuric acid into the reaction system, and distilling to recover methanol to obtain hydroxamic acid. The method can be used for greatly increasing the yield of hydroxamic acid or hydroxamic acid salt; methanol as a solvent can be recycled, so that wastewater is prevented from being generated; in addition, the preparation method is wild in reaction condition and beneficial to industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of hydroxamic acid or hydroxamate, belong to flotation collector synthesis field.
Background technology
Hydroximic acid and salt thereof are the known flotation collectors for oxide mineral froth-flotation method.USSR (Union of Soviet Socialist Republics) researchist has been found that the multiple use of this kind of hydroximic acid, such as be described in Pradip and Fuerstenau " using the mineral floating of hydroxamic acid (ester) flotation collector ", reagent (Reagents in theMinerals Industry) in Mineral Industry, Ed.M.J.Jones and R.Oblatt, Inst.Min.Met., London, 1984, page 161-168, the document review and summarization flotation applications of hydroximic acid.Hydroximic acid is used to the flotation of metal or mineral, as fluorite, huebnerite, wolframite, cassiterite, white mica, phosphorite, rhombohedral iron ore, pyrolusite, rhodonite, chrysocolla, malachite, barite, calcite and rare earth.Hydroximic acid is usually more powerful and more selective than conventional lipid acid, fatty amine, sulfonated petro-leum and alkyl-sulphate.
Method for the preparation of alkylhydroxamic acid potassium is disclosed in organic synthesis, volume II, page 67 (OrganicSynthesis, Vol.II, page67).In disclosed method, the solution of mixing KOH in methyl alcohol and NH
2the solution of OHHC1 in methyl alcohol.After excessively filtering KCI by product, the liquid mixture of filtrate with methyl caprylate and methyl caprate is mixed, leave standstill 24 hours afterwards, filter out crystalline product.The main drawback of the method is that hydroxamic acid productive rate is low, long reaction time, and employs the potassium hydroxide of cost higher than sodium hydroxide.
The U.S. Patent No. 3922872 of authorizing Hartlage proposes the claim of improving one's methods of preparation aliphatics hydroxamate.The method makes the methyl esters of hydroxylamine sulfate and lipid acid react under the existence at dimethylamine in anhydrous lower alcohol slurries.Neutralize with the free hydroxamic acid formed with dimethylamine or basic metal alkali, obtain ammonium or an alkali metal salt, gained material precipitates, and filters and drying to it.The main drawback of the method is the dimethylamine employing highly volatile in reaction process is acid binding agent, the high and easy contaminate environment of cost.And speed of reaction is low, such as in methyl alcohol, the reaction times is 15 hours, and in Virahol, the reaction times is 5 days, and productive rate is also lower, is about 75%.
Many Russian researchers report the method for preparing alkylhydroxamic acid and salt thereof in alkaline aqueous medium.Gorlovski etc., Vses.Soveshcn.po Sintetich.Zhirozamenitelyam, Poverkhnostnoaktivn, Veschestvam i Moyushchim Sredstvam, the third edition, Sb.Shebekino, 1965,297-9 chemical abstracts 66,4983h, 1967 report the methyl esters of C7-9 carboxylic acid and the hydroxylamine sulfate aqueous solution and NaOH are reacted with the mol ratio of 1:1.22:2.2 under 55 DEG C or lower temperature, obtained alkylhydroxamic acid sodium.
Shchukina etc., Khim.Prom, Moscow, 197049 (3) 220, report by methyl esters, hydroxylamine sulfate and sodium hydroxide in 20-25 DEG C of reaction 2 hours, and in 55-60 DEG C of reaction 1 hour, then pH4-5 is acidified in the temperature lower than 40 DEG C, obtained free C
7-9hydroxamic acid, productive rate is 72-78%.Shchukina etc., at Sin.Primen.Novykh Proverkh.Veshchestv, in 1973,123-31, and at C.A.80, all report in 1974,95199K and use cause C
7-9ester preparation is by the simple experiment room method named as IM-50 reagent.
After this, the method preparing hydroxamic acid and salt thereof in alkaline aqueous medium is widely adopted.Wherein mainly contain fatty hydroximic acid collecting agent (see structural formula a:A.S. Rothenberg, L.G. horse Leo section. aliphatic hydroxamic acid and the mineral floating collecting agent composition and method of making the same that mixes of oil, CN1303444A, 2001-07-11; Te Lunsi. charles. Hughes. hydroxamate composition and foam flotation method, CN1533305A, 2004-09-29), Using Salicyl Hydroximic Acid is (see structural formula b: Zhou Yulin, Yuan Hao. a kind of improvement production method of Using Salicyl Hydroximic Acid, CN101519365A, 2009-09-02), propylene hydroximic acid (Zhang Hongsong, Li Yuejun, Liu Hao, Xu Kun, king says roc, Cao Weiguang. a kind of preparation method of propylene hydroximic acid, CN102584629A, 2012-07-18), quaternary ammonium salt hydroximic acid is (see structural formula c: Pan Zhiquan, Feng Cheng, Chen Yunfeng.Quaternary ammonium salt hydroximic acid phosphorite flotation collector and preparation method, CN102302983A, 2012-01-04), benzene formhydroxamic acid ammonium (see structural formula d: Lin Xiao, Ye Zhiping, Zhang Zhonghan, Zhang Guanghua, Zhou Xiaotong. a kind of collecting agent compound for floatation of tungsten mineral and preparation method and use thereof).
At present, in alkaline aqueous medium, prepare hydroxamic acid and salt thereof there is a large amount of waste water and need process, and existing organic solvent medium prepares hydroxamic acid and salt thereof, and to there is reaction efficiency low, long reaction time, is unfavorable for the suitability for industrialized production of hydroxamic acid and salt thereof.
Summary of the invention
The invention provides a kind of by mild conditions, fast, the method for high yield synthesis hydroxamic acid or hydroxamate, the method is simple to operate, and cost is low, environmental protection, can suitability for industrialized production.
The invention provides the preparation method of a kind of hydroxamic acid or hydroxamate, the method is under agitation, alkali being joined temperature is not more than in the methanol solution of the hydroxylammonium salt of 45 DEG C, add the organic carboxyl acid methyl esters with formula 1 or formula 2 structure again, react 2 ~ 6 hours at 30 ~ 70 DEG C, after having reacted, Distillation recovery methyl alcohol, obtains the hydroxamate product of formula 3 or formula 4 structure; Or after question response completes, reaction system is cooled to less than 30 DEG C, adds sulfuric acid in reaction system, methyl alcohol is reclaimed in redistillation, obtains the hydroxamic acid of formula 5 or formula 6 structure;
Wherein,
M is alkali metal atom;
R is C
5-C
21alkyl;
X is hydrogen atom or hydroxyl.
The preparation method of hydroxamic acid of the present invention or hydroxamate also comprises following preferred version:
Hydroxylammonium salt in preferred preparation method: alkali: organic carboxyl acid methyl esters: the mol ratio of methyl alcohol is 0.9 ~ 1.2:1.6 ~ 2.5:1:16 ~ 24.
Described alkali, for being mainly alkali metal base, is preferably solid sodium hydroxide or potassium hydroxide; Most preferably be sodium hydroxide.
Preferred hydroxylammonium salt is hydroxylamine hydrochloride or hydroxylamine sulfate; Most preferably be oxammonium hydrochloride.
Preferred organic carboxyl acid methyl esters is the methyl esters of caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, Palmiticacid, margaric acid, stearic acid, oleic acid, phenylformic acid, ethyl benzoate, Whitfield's ointment, α-naphthoicacid, β-naphthoic acid, cyclohexane carboxylic acid or cyclopentyl carboxylic acid.
The mol ratio of the sulphur bronsted lowry acids and bases bronsted lowry added in preferred preparation method is 0.9 ~ 2:2.
In preferred preparation method, alkali adds by the methanol solution temperature of hydroxylammonium salt 10 ~ 30 DEG C time.
Preferred reaction is reacted 3 ~ 5 hours at temperature is 45 ~ 55 DEG C.
When adding the vitriol oil in preferred preparation method, system temperature is 0 ~ 15 DEG C.
Preferred preparation method is under agitation, sodium hydroxide is slowly joined in the methanol solution of the hydroxylammonium salt of 10 ~ 30 DEG C, add the organic carboxyl acid methyl esters with formula 1 or formula 2 structure again, react 3 ~ 5 hours at 45 ~ 55 DEG C, after having reacted, Distillation recovery methyl alcohol, obtains the hydroxamate product of formula 3 or formula 4 structure; Or after question response completes, reaction system is cooled to 0 ~ 15 DEG C, adds sulfuric acid in reaction system, methyl alcohol is reclaimed in redistillation, obtains the hydroxamic acid of formula 5 or formula 6 structure; Wherein, hydroxylammonium salt: alkali: organic carboxyl acid methyl esters: the mol ratio of methyl alcohol is 0.9 ~ 1.2:1.6 ~ 2.5:1:16 ~ 24.
Described alkali adds in batches or slowly adds continuously.
Beneficial effect of the present invention: the method that alcohol medium of the prior art produces hydroxamic acid or hydroxamate exists the low problem of yield, generally about 50%; And be although that the method yield that medium prepares hydroxamic acid or hydroxamate improves with water, reach about 80%, can produce a large amount of waste water, the process of waste water can increase the production cost of product.The reaction conditions that alcohol medium in prior art produces hydroxamic acid or hydroxamate by repetition test, is optimized by the present invention, on the one hand by the yield of hydroxamic acid or hydroxamate by of the prior art about 50%, bring up to more than 95%; On the other hand, alcohol dielectric film filter is reused, avoids the generation of waste liquid; In addition, the reaction times of the inventive method shortens greatly, and reaction conditions is gentle, is conducive to suitability for industrialized production.In sum, the inventive method energy is quick, high yield synthesizes hydroxamic acid or hydroxamate, and method is simple to operate, and cost is low, environmental protection, can suitability for industrialized production.
Embodiment
Content of the present invention is further illustrated by the following example, but protection scope of the present invention is not by the restriction of these embodiments.
In embodiment, unless otherwise specified all numbers and percentage ratio all refer to quality.
Comparative example 1
The traditional solvent synthesis of octanohydroxamic acid sodium:
According to organic synthesis, volume II, the method in page 67 (Organic Synthesis, Vol.II, page67) prepares octanohydroxamic acid potassium.By 21g sodium hydroxide (4g in batches, 4g, 4g, 4g, 5g) join in the reaction flask that oxammonium hydrochloride (19.2g) and 150mL methyl alcohol are housed, after sodium hydroxide all adds, 50mL methyl alcohol is poured in reaction flask, make sodium hydroxide and oxammonium hydrochloride reaction 10min, cross and filter NaCl by product, then filtrate and methyl caprylate (40g) are mixed, at room temperature leave standstill 24 hours, filter out product, detect based on ferric ion, the yield of octanohydroxamic acid sodium is 48%.
Comparative example 2
The alkaline aqueous medium method synthesis of benzene formhydroxamic acid:
19.2g oxammonium hydrochloride is dissolved in 40mL water, under agitation toward the solution wherein adding 21g sodium hydroxide and 50mL water and be made into, in 30 minutes, drip 40g methyl caprylate after adding sodium hydroxide solution, be then warming up to 45 DEG C, react after 4 hours, about adjusting solution ph to 4 with concentrated hydrochloric acid, be cooled to 5 DEG C, filter, required benzene formhydroxamic acid is in filter cake, detect based on ferric ion, the yield of phenylformic acid hydroxamic acid is 83%.
Embodiment 1
The synthesis of benzene formhydroxamic acid:
By 21g sodium hydroxide (4g in batches, 4g, 4g, 4g, 5g) join in the reaction flask that 19.2g oxammonium hydrochloride and 150mL methyl alcohol are housed, keep charge temperature to be no more than 30 DEG C, after sodium hydroxide all adds, then 50mL methyl alcohol is poured in reaction flask, sodium hydroxide and oxammonium hydrochloride is made to react 10min again, then 34g methyl benzoate was added drop-wise in reaction flask in 30 minutes, is then warming up to 50 DEG C, react 4 hours.After reaction terminates, reaction mixture temperature is down to less than 5 DEG C, then slow the 7mL vitriol oil is added in reaction flask, keep charge temperature to be less than 5 DEG C simultaneously.After the vitriol oil dropwises, filtrate decompression is distilled methanol removal solvent, obtain benzene formhydroxamic acid product, detect based on ferric ion, the yield of phenylformic acid hydroxamic acid is 97%.
Embodiment 2
The synthesis of bigcatkin willow hydroxamic acid:
Replace 34g methyl benzoate with 38g wintergreen oil, carry out hydroxyl oximation reaction prepare bigcatkin willow hydroxamic acid by the technique that embodiment 1 is similar at 55 DEG C, detect based on ferric ion, the yield of bigcatkin willow hydroxamic acid is 96%.
Embodiment 3
The synthesis of octanohydroxamic acid:
Replace 34g methyl benzoate with 40g methyl caprylate, the technique similar by embodiment 1 prepares octanohydroxamic acid, and detect based on ferric ion, the yield of octanohydroxamic acid is 97%.
Embodiment 4
The synthesis of hexyl hydroxamic acid:
Replace 34g methyl benzoate with 32.5g methyl caproate, prepare hexyl hydroxamic acid by the technique that embodiment 1 is similar, detect based on ferric ion, the yield of hexyl hydroxamic acid is 95%.
Embodiment 5
The synthesis of bay hydroxamic acid:
Replace 34g methyl benzoate with 54g Laurate methyl, prepare hexyl hydroxamic acid by the technique that embodiment 1 is similar, detect based on ferric ion, the yield of bay hydroxamic acid is 97%.
Embodiment 6
The synthesis of 9-octadecylene hydroxamic acid:
Replace 34g methyl benzoate with 74g Witconol 2301, carry out hydroxyl oximation reaction prepare 9-octadecylene hydroxamic acid by the technique that embodiment 1 is similar at 55 DEG C, detect based on ferric ion, the yield of 9-octadecylene hydroxamic acid is 98%.
Embodiment 7
The synthesis of octanohydroxamic acid and hexyl hydroxamic acid mixture:
Replace 34g methyl benzoate with the mixture ester containing 16g methyl caproate and 20g methyl caprylate, prepare hexyl hydroxamic acid by the technique that embodiment 1 is similar, detect based on ferric ion, the total recovery of hexyl hydroxamic acid and octanohydroxamic acid is 96%.
Embodiment 8
The synthesis of benzene formhydroxamic acid sodium:
By 21g sodium hydroxide (4g in batches, 4g, 4g, 4g, 5g) join in the reaction flask that 19.2g oxammonium hydrochloride and 150mL methyl alcohol are housed, keep charge temperature to be no more than 30 DEG C, after sodium hydroxide all adds, then 50mL methyl alcohol is poured in reaction flask, sodium hydroxide and oxammonium hydrochloride is made to react 10min again, then 34g methyl benzoate was added drop-wise in reaction flask in 30 minutes, is then warming up to 50 DEG C, react 4 hours.After reaction terminates, by reaction mixture underpressure distillation methanol removal solvent, obtain benzene formhydroxamic acid sodium product, detect based on ferric ion, the yield of phenylformic acid hydroxamic acid sodium is 98%.
Embodiment 9
The synthesis (methanol solvate circulation) of benzene formhydroxamic acid sodium:
By the methyl alcohol 1.8m measured
3disposable suction synthesis reactor, opens and stirs, then adds synthesis reactor by disposable for 157 kilograms of oxammonium hydrochlorides; Open synthesis reactor salt solution and oxammonium hydrochloride methanol solution is cooled to less than 30 DEG C, portion-wise addition 180 kilograms of sodium hydroxide, temperature controls below 30 DEG C of degree; Then disposablely add 280kg methyl benzoate, add ester complete after be warming up to 48-52 DEG C of degree, insulation reaction 4 hours; Reaction mixture atmospheric and vacuum distillation is steamed methyl alcohol, and the methanol solvate steamed is collected for synthesis next time, and remaining solid is as product, and test-results is in table 1.
The synthesis result of benzene formhydroxamic acid sodium when table 1 methanol solvate recycles
Claims (7)
1. the preparation method of a hydroxamic acid or hydroxamate, it is characterized in that, under agitation, solid sodium hydroxide or potassium hydroxide being joined temperature is not more than in the methanol solution of the hydroxylammonium salt of 45 DEG C, add the organic carboxyl acid methyl esters with formula 1 or formula 2 structure again, react 2 ~ 6 hours at 30 ~ 70 DEG C, after having reacted, Distillation recovery methyl alcohol, obtains the hydroxamate product of formula 3 or formula 4 structure; Or after question response completes, reaction system is cooled to less than 30 DEG C, adds the vitriol oil in reaction system, when adding the vitriol oil, maintaining temperature of reaction system is 0 ~ 15 DEG C, and methyl alcohol is reclaimed in redistillation, obtains the hydroxamic acid of formula 5 or formula 6 structure;
Wherein,
M is potassium or sodium atom;
R is C
5~ C
21alkyl;
X is hydrogen atom or hydroxyl.
2. preparation method as claimed in claim 1, is characterized in that, hydroxylammonium salt: solid sodium hydroxide or potassium hydroxide: organic carboxyl acid methyl esters: the mol ratio of methyl alcohol is 0.9 ~ 1.2:1.6 ~ 2.5:1:16 ~ 24.
3. preparation method as claimed in claim 1 or 2, it is characterized in that, described hydroxylammonium salt is hydroxylamine hydrochloride.
4. preparation method as claimed in claim 1 or 2, it is characterized in that, described organic carboxyl acid methyl esters is caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, Palmiticacid, margaric acid, stearic acid, phenylformic acid, salicylic methyl esters.
5. preparation method as claimed in claim 1, it is characterized in that, the mol ratio of the sulfuric acid added and solid sodium hydroxide or potassium hydroxide is 0.9 ~ 2:2.
6. preparation method as claimed in claim 1, it is characterized in that, solid sodium hydroxide or potassium hydroxide add by the methanol solution temperature of hydroxylammonium salt 10 ~ 30 DEG C time.
7. preparation method as claimed in claim 1, is characterized in that, described reaction is reacted 3 ~ 5 hours at temperature is 45 ~ 55 DEG C.
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