CN103435541B - Synthesis method of 1-benzylpyridinium-3-carboxylate - Google Patents
Synthesis method of 1-benzylpyridinium-3-carboxylate Download PDFInfo
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- CN103435541B CN103435541B CN201310406993.8A CN201310406993A CN103435541B CN 103435541 B CN103435541 B CN 103435541B CN 201310406993 A CN201310406993 A CN 201310406993A CN 103435541 B CN103435541 B CN 103435541B
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Abstract
The invention discloses a synthesis method of 1-benzylpyridinium-3-carboxylate. The 1-benzylpyridinium-3-carboxylate is obtained by performing a chemical reaction on benzyl chloride, nicotinic acid and sodium hydroxide serving as raw materials; fully dissolving the sodium hydroxide in water; adding the nicotinic acid; stirring to fully dissolve; adding a composite catalyst and a buffer; dropwise adding the benzyl chloride and continuously reacting for 1-2 hours after the dropwise adding is finished so as to obtain the 1-benzylpyridinium-3-carboxylate, wherein the composite catalyst is a mixture of K2CO3 or Na2CO3 and quaternary ammonium salt; the quaternary ammonium salt is one or more of tetrabutylammonium bromide, benzyltriethylammonium chloride, dodecyl trimethyl ammonium chloride, methyl trioctyl ammonium chloride, hexadecyl trimethyl ammonium bromide and bromogeramine; the buffer is one of sodium bicarbonate, sodium carbonate, sodium acetate and boric acid. The synthesis method has the advantages of high yield, short reaction time, low cost, high product purity, no environment pollution during production and environmental friendliness.
Description
Technical field
The present invention relates to the synthetic method of alkaline non-cyanide zincate galvanizing additive, refer to a kind of synthetic method of benzyl nicotinate salt particularly.
Background technology
At present, the most frequently used zincincation is cyanide zinc plating wastewater, acid non-cyanogen galvanization and alkaline non-cyanogen galvanization.In view of the toxicity of prussiate and increasingly strict to environmental requirement, cyanide zinc plating wastewater is put into superseded row gradually.
And acid non-cyanogen galvanization and alkaline non-cyanogen galvanization respectively have quality.The advantage of acid non-cyanogen galvanization has: zinc-plated efficiency is high, and luminance brightness is high, non-stimulated smell, and its technique also can be used for ironcasting, high carbon steel.Simultaneously it also have all plate, covering power is poor, the shortcomings such as coating is passivation not easily, coating fragility height, therefore generally should not be used for higher to Functional Requirement or that profile is more complicated workpiece.Alkaline non-cyanogen galvanization then has good covering power and covering power, and there is preferably hiding power at the dark shrinkage pool hole place or coarse iron material of complex part, and equipment itself is not perishable yet simultaneously, and service life of equipment extends relatively.
At present in the zinc-plated scope in the world, the share shared by alkaline non-cyanogen galvanization reaches 50%, and still has the trend of rising.In Japan, U.S.'s electro-galvanizing industry, being widely used with the alkaline non-cyanogen galvanization technique that JASCO company, PAVCO company are representative, especially in automobile, household electrical appliances and haberdashery and hardware industry, is based on alkaline non-cyanide zincate galvanizing substantially.
Current, alkaline non-cyanide zincate galvanizing also has that electroplating efficiency is low, sedimentation velocity slowly, easily occurs oozing the shortcomings such as hydrogen phenomenon, is not suitable for plating high carbon steel or cast iron materials.Benzyl nicotinate salt (BPC-48) is the main leveling agent of alkaline non-cyanogen galvanization, brightening agent.Molecular formula: C13H11NO2, No. CAS: 15990-43-9, product is the yellow transparent liquid product of content 48% or 36%, for cyanideless electro-plating zinc/zinc alloy technique, what fall behind in replacement has the zinc-plated electroplating technology of the prussiate of pollution, promotes there is the effect do not replaced in the process of cleaner production.
At present, the synthesis of benzyl nicotinate salt generally reacts gained according to the following formula:
If simply synthesized according to above-mentioned technique, do not add other catalyzer and buffer reagent, long reaction time, the product colour of gained is dark red even to turn black, and has a large amount of dark thick material, and product water dissolubility is bad, has opalescence after dilution.And through HPLC content detection, product yield, about 70%, contains a large amount of unreacted nicotinic acid, Benzyl Chloride hydrolyzate and other by products in product.Doing in zinc-plated application testing, find that mist sent out by coating, there is embrittlement skin effect phenomenon at edge.
Summary of the invention
Object of the present invention is exactly to overcome the deficiency existing for prior art, provides a kind of synthetic method of benzyl nicotinate salt.
For achieving the above object, the synthetic method of benzyl nicotinate salt of the present invention, be obtained by reacting for raw material theory of evolution with Benzyl Chloride, nicotinic acid, sodium hydroxide, it is characterized in that: first sodium hydroxide is dissolved completely in water, then add nicotinic acid at 40 ~ 60 DEG C, stir and fully dissolve, add composite catalyst, buffer reagent, at 70 DEG C ~ 100 DEG C, drip Benzyl Chloride, drip off and continue reaction 1 ~ 2 hour, benzyl nicotinate salt can be obtained; Described composite catalyst is K
2cO
3or Na
2cO
3with the mixture of quaternary ammonium salt, described quaternary ammonium salt is one or more in Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, cetyl trimethylammonium bromide, bromogeramine; Described buffer reagent is the one in sodium bicarbonate, sodium carbonate, sodium-acetate, boric acid.
In the present invention, the consumption of described composite catalyst accounts for 1 ~ 5% of the weight of sodium hydroxide, wherein, and K
2cO
3or Na
2cO
3be 1 ~ 3:1 with the weight ratio of quaternary ammonium salt.
In the present invention, the add-on of buffer reagent is to make reaction soln for neutrality is to weakly alkaline.
In order to overcome the deficiency of existing technique, invention has been following 2 improvement: 1) building-up process adds composite catalyst, fast reaction speed, and the reaction times reduces to 2h by 10h, and ensure that raw material Benzyl Chloride does not decompose, product yield is greater than 90%; 2) building-up process adds buffer reagent control reaction soln for neutral to weakly alkaline, and reduce the impurity of Benzyl Chloride hydrolysis generation, product purity is high.
Beneficial effect of the present invention is: the inventive method yield is high, and the reaction times is short, and cost is low, and product purity is high, production process environmentally safe, environmental protection.The alkaline non-cyanide zincate galvanizing additive benzyl nicotinate salt that the present invention obtains, has good all platings and covering power, can be used for cast iron and high carbon steel product.
Accompanying drawing explanation
The chromatograms of the benzyl nicotinate salt that Fig. 1 obtains for the present invention.
The detected result of the benzyl nicotinate salt that Fig. 2 obtains for the present invention.
The chromatograms of the benzyl nicotinate salt that Fig. 3 obtains for existing method.
The detected result of the benzyl nicotinate salt that Fig. 4 obtains for existing method.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
In 5L four-hole boiling flask, add 2.2kg deionized water, after adding the dissolving of 0.4kg sodium hydroxide, more slowly add 1.23kg nicotinic acid at 40 DEG C, continue stirring and dissolving, progressively add 5gK
2cO
3, 5g tri-n-octyl methyl ammonium chloride, 10g boric acid, solution is in neutral, be warmed up to 80 DEG C, start to drip Benzyl Chloride 1.26kg, dropping temperature 80 ~ 90 DEG C, dropwises, this temperature 1 hour, reaction completed, and obtains benzyl nicotinate salt, and outward appearance is light yellow clear liquid.
Benzyl nicotinate salt embodiment 2 obtained detects through HPLC, and as shown in Figure 1, by Fig. 2 as calculated, concentration is 92.953% to the chromatograms obtained.
Embodiment 2
In 1L four-hole boiling flask, add 480g deionized water, after adding the dissolving of 80g sodium hydroxide, more slowly add 240g nicotinic acid at 50 DEG C, continue stirring and dissolving, progressively add 1gNa
2cO
3, 0.5g Tetrabutyl amonium bromide, 5g sodium bicarbonate, solution is weakly alkaline, be warmed up to 70 DEG C, start to drip Benzyl Chloride 200g, dropping temperature 70 ~ 80 DEG C, dropwises, this temperature 2 hours, reaction completed, and obtains benzyl nicotinate salt, and outward appearance is yellow transparent liquid.Concentration is 90.17%.
Embodiment 3
In 1L four-hole boiling flask, add 520g deionized water, after adding the dissolving of 80g sodium hydroxide, more slowly add 246g nicotinic acid at 60 DEG C, continue stirring and dissolving, progressively add 3gK
2cO
3, 1g bromogeramine, 6g sodium-acetate, solution is weakly alkaline, is warmed up to 80 DEG C, starts to drip Benzyl Chloride 240g, and dropping temperature 80 ~ 95 DEG C, dropwises, and this temperature 1 hour, reaction completed, and obtains benzyl nicotinate salt, and outward appearance is yellow transparent liquid.Concentration is 91.26%.
Embodiment 4
In 5L four-hole boiling flask, add 2kg deionized water, after adding the dissolving of 0.4kg sodium hydroxide, more slowly add 1.15kg nicotinic acid at 45 DEG C, continue stirring and dissolving, progressively add 8gK
2cO
3, 3g cetyl trimethylammonium bromide, 6g sodium carbonate, solution is weakly alkaline, be warmed up to 80 DEG C, start to drip Benzyl Chloride 1.2kg, dropping temperature 80 ~ 95 DEG C, dropwises, this temperature 1 hour, reaction completed, and obtains benzyl nicotinate salt, and outward appearance is yellow transparent liquid.Concentration is 90.62%.
Comparative example
In 5L four-hole boiling flask, add 2.2kg deionized water, add 0.4kg sodium hydroxide, after dissolving, add 1.23kg nicotinic acid again, continue stirring and dissolving, be warmed up to 80 DEG C, start to drip Benzyl Chloride 1.26kg, dropping temperature 80 ~ 100 DEG C, dropwise, this temperature 10 hours, reaction completed, and obtains BPC product (benzyl nicotinate salt), outward appearance dark brown red liquid, has dark thick thing.
Benzyl nicotinate salt comparative example obtained detects through HPLC, and as shown in Figure 3, by Fig. 4 as calculated, concentration is 76.50% to the chromatograms obtained as calculated.
Claims (2)
1. the synthetic method of a benzyl nicotinate salt, be obtained by reacting for raw material theory of evolution with Benzyl Chloride, nicotinic acid, sodium hydroxide, it is characterized in that: first sodium hydroxide is dissolved completely in water, nicotinic acid is added again at 40 ~ 60 DEG C, stir and fully dissolve, add composite catalyst, buffer reagent, at 70 DEG C ~ 100 DEG C, drip Benzyl Chloride, drip off and continue reaction 1 ~ 2 hour, benzyl nicotinate salt can be obtained;
Described composite catalyst is K
2cO
3or Na
2cO
3with the mixture of quaternary ammonium salt, described quaternary ammonium salt is one or more in Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, Dodecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, cetyl trimethylammonium bromide, bromogeramine; Described buffer reagent is the one in sodium bicarbonate, sodium carbonate, sodium-acetate, boric acid.
2. the synthetic method of benzyl nicotinate salt according to claim 1, is characterized in that: the consumption of described composite catalyst accounts for 1 ~ 5% of the weight of sodium hydroxide, wherein, and K
2cO
3or Na
2cO
3be 1 ~ 3:1 with the weight ratio of quaternary ammonium salt.
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2013
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| JPH0649685B2 (en) * | 1986-12-29 | 1994-06-29 | 広栄化学工業株式会社 | 1-benzylpyridinium salt derivative and method for producing the same |
| CN1267289A (en) * | 1997-06-17 | 2000-09-20 | 先灵公司 | Carboxy piperidylacetamide tricyclic compounds useful for inhibition of G-protein function and for treatment of proliferative diseases (farnesyl protein transferase inhibitors) |
| RU2141948C1 (en) * | 1998-02-02 | 1999-11-27 | Институт нефтехимии и катализа АН республики Башкортостан и Уфимского научного центра РАН | Alkyl(or aryl)benzylpyridinium chlorides as steel corrosion inhibitor in mineralized media |
| CN102491944A (en) * | 2011-12-13 | 2012-06-13 | 东阳市威达环保助剂有限公司 | Method for preparing brominated 1-benzyl-3-carboxypyridine and preparation method thereof |
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