CN103193723A - Benzotriazole Schiff base compound and preparation method thereof - Google Patents
Benzotriazole Schiff base compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method for a benzotriazole Schiff base compound. A synthetic method comprises the steps of: (1) adding 5-carboxy benzotriazole, LiAlH4 and THF (tetrahydrofuran) into a flask, dripping TPAP/NMO (tetrapropylammonium perruthenate/N-morpholine oxide), CH2Cl2, THF and DMF (dimethyl formamide) after stirring for 2 hours, and reacting for 12 hours, so as to obtain white 5-aldehyde benzotriazole; (2) sequentially adding the product obtained in the step (1), formaldehyde, acetic acid and water into the flask, and carrying out stirring, standing and suction filtration, so as to obtain white 1-hydroxymethyl-5-aldehyde benzotriazole; (3) adding the product obtained in the step (2), CHCl3 and TBAB (tetrabutylammonium bromide) into the flask, dropwise adding CrO3 and a concentrated H2SO4 water solution after heating and dissolving the mixture, stirring until the solution becomes deep green, skimming, regulating the pH of an inorganic layer to be approximate to 8, and carrying out chloroform extraction, anhydrous sodium sulfate drying and rotary evaporation, so as to obtain orange red 1,5-dialdehyde benzotriazole; and (4) adding the product obtained in the step (3) into the flask, adding 6-aminoquinoline after dissolving the product by the ethanol, and carrying out backflow, filtering and recrystallization, so as to obtain a target compound of benzotriazole Schiff base. According to the target compound, the structure is novel, the corrosion inhibition performance is high, and the problem of acid washing of carbon steel can be effectively solved.
Description
Technical field
The present invention relates to a kind of benzotriazole schiff base compounds and preparation method thereof.
Background technology
Pickling has a wide range of applications in industries such as metallic substance, machinery, metallurgy, electric power and chemical industry.Comprise that in industrial pickling pickling removes the pickling descaling of removing iron scale, metallic substance and equipment.It not only can produce the huge social economic benefit pickling, and safety problem and environment protection also are significant.
Acid commonly used in the acid cleaning process has hydrochloric acid, sulfuric acid and nitric acid etc.In acid cleaning process, acid has corrosive nature to hardware and material, especially mineral acid; In addition, the hydrogen that metal and acid-respons generate can cause the hydrogen embrittlement of hardware, and hydrogen also can be taken certain sour gas out of, forms inner acid mist, causes the deterioration of labor condition.Therefore, in acid cleaning process, generally all need to add inhibiter, suppress the corrosion of metal in acidic medium thereby reach, reduce the consumption of acid, promote the purpose of pickling effect and prolongation service life of equipment.
Phase early 1950s, people just find that benzotriazole has good corrosion mitigating effect to copper and alloy thereof, and in order further to strengthen the corrosion mitigating effect of benzotriazole, the benzotriazole derivatives of synthesizing new has become the emphasis of people's research.With-C=N-functional group is the schiff base compounds of sign, itself is exactly a class has fine function of prevent erosion to copper and iron inhibiter.Both contained the higher N atom of electronegativity that lone-pair electron can be provided in the Schiff's base molecular structure, contained the double bond structure that πDian Zi and unoccupied orbital can be provided again, and it had been easy at metallic surface formation self-assembled film, thereby plays the effect that suppresses corrosion reaction.Schiff's base has also that cost is low, easily synthetic and purification, good water solubility, nontoxicity and characteristics such as of a great variety.Up to now, existing a large amount of relevant Schiff bases compound synthesizes and reports as Research on Corrosion Inhibitor.And Schiff's base functional group is combined with benzotriazole, on structure, can increase its active centre, increase compound molecule and the interactional chance of steel surface, infer in theory to obtain better corrosion mitigating effect.Actually rare about the report of benzotriazole schiff base compounds both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of benzotriazole schiff base compounds.
A kind of structural formula of benzotriazole schiff base compounds is as follows:
The preparation method of this benzotriazole schiff base compounds:
(1) in the 100ml round-bottomed flask, adds 3.26g (20mmol) 5-carboxyl benzotriazole, an amount of LiAlH
4And THF, the control temperature inwardly drips an amount of TPAP/NMO, CH behind induction stirring 10h about 20 ℃
2Cl
2, THF, DMF normal-temperature reaction 12h obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white behind the decompress filter.(productive rate: 89%)
(2) in the 100ml round-bottomed flask, add 2.62g (18mmol) A successively, 0.54g (18mmol) formaldehyde, 20ml acetic acid, 50ml water stirs 1h, places 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole B2.88g.(productive rate: 90%)
(3) in the 100ml two-neck bottle, add 2.83g (16mmol) B, 30ml CHCl successively
3With 1.5g phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving.The aqueous solution that will be dissolved with 1.60g (16mmol) chromium trioxide and the 2.4ml vitriol oil slowly drops in the two-neck bottle, and the control temperature continue to stir 1h about 52 ℃, when solution colour can be stopped when blackish green by orange becoming.Separatory, inorganic layer is regulated pH ≈ 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.92g (11mmol) C, add then an amount of ethanol make it the dissolving, add 3.17g (22mmol) 6-quinolylamine again, reflux 4h, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound D4.04g.(productive rate: 86%)
The building-up reactions equation of this benzotriazole schiff base compounds is:
Benzotriazole schiff base compounds molecular formula of the present invention is C
26H
17N
7, molecular weight is 427.46; This target compound is not seen bibliographical information so far, and synthetic method is simple, the reaction conditions gentleness, and simple to operate, productive rate is higher, and product is easy to separate, purify.
Described benzotriazole schiff base compounds is in the application of carbon steel pickling corrosion inhibitor.The present invention is as the principle of inhibiter: benzotriazole schiff base compounds intramolecularly contains heterocycle, nitrogen-atoms and-C=N-, when metal immerses corrosion inhibitor solution, these heteroatomss are inserted lone-pair electron the unoccupied orbital of metal, make inhibiter molecule and metallic surface form firm and stable chemical bond, form constitutionally stable assembling film at steel surface, thereby reach the purpose of inhibition.
Embodiment
Embodiment 1: preparation benzotriazole schiff base compounds:
(1) in the 100ml round-bottomed flask, adds 3.26g (20mmol) 5-carboxyl benzotriazole, an amount of LiAlH
4And THF, the control temperature inwardly drips an amount of TPAP/NMO, CH behind induction stirring 10h about 20 ℃
2Cl
2, THF, DMF normal-temperature reaction 12h obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white behind the decompress filter.(productive rate: 89%)
(2) in the 100ml round-bottomed flask, add 2.62g (18mmol) A successively, 0.54g (18mmol) formaldehyde, 20ml acetic acid, 50ml water stirs 1h, places 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole B2.88g.(productive rate: 90%)
(3) in the 100ml two-neck bottle, add 2.83g (16mmol) B, 30ml CHCl successively
3With 1.5g phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving.The aqueous solution that will be dissolved with 1.60g (16mmol) chromium trioxide and the 2.4ml vitriol oil slowly drops in the two-neck bottle, and the control temperature continue to stir 1h about 52 ℃, when solution colour can be stopped when blackish green by orange becoming.Separatory, inorganic layer is regulated pH ≈ 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.92g (11mmol) C, add then an amount of ethanol make it the dissolving, add 3.17g (22mmol) 6-quinolylamine again, reflux 4h, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound D4.04g.(productive rate: 86%)
The ultimate yield of target product is 48%, and fusing point is: 182-185 ℃.
Through Infrared spectroscopy and nuclear magnetic resonance spectroscopy, the result is as follows:
Infrared spectra (KBr, cm
-1): 3057 (C-H); 1646 (C=N).
1H?NMR(400MHZ,CDCl
3,ppm)：δ=9.32(2H,CH=N);δ=8.90～7.00(15H,aryl?group).
13C?NMR(400MHZ,CDCl
3,ppm):δ=163.05(C=N);δ=120.08-155.02(aromatic?carbons).
Ultimate analysis: calculated value C
26H
17N
7: C, 73.05; H, 4.01; N, 22.94; Measured value C, 74.18; H, 4.66; N, 23.32%.
Embodiment 2: preparation benzotriazole schiff base compounds:
(1) in the 100ml round-bottomed flask, adds 3.26g (20mmol) 5-carboxyl benzotriazole, an amount of LiAlH
4And THF, the control temperature is about 40 ℃.Behind induction stirring 12h, inwardly drip an amount of TPAP/NMO, CH
2Cl
2, THF, DMF normal-temperature reaction 8h obtains the thick product 5-aldehyde radical benzotriazole A2.14g of white behind the decompress filter.(productive rate: 73%)
(2) in the 100ml round-bottomed flask, add 2.14g (14.5mmol) A successively, 0.45g (15mmol) formaldehyde, 20ml ethanol, 50ml water stirs 1.5h, places 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole B2.00g.(productive rate: 78%)
(3) in the 100ml two-neck bottle, add 1.95g (11mmol) B, 21ml CHCl successively
3With 1.1g phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving.The aqueous solution that will be dissolved with 1.10g (11mmol) chromium trioxide and the 1.7ml vitriol oil slowly drops in the two-neck bottle, and the control temperature continue to stir 1h about 52 ℃, when solution colour can be stopped when blackish green by orange becoming.Separatory, inorganic layer is regulated pH ≈ 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.35g.(productive rate: 70%)
(4) in flask, add 1.35g (7.7mmol) C, add then an amount of ethanol make it the dissolving, add 2.22g (15.4mmol) 6-quinolylamine again, reflux 4h, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound D2.83g.(productive rate: 86%)
The ultimate yield of target product is 34%, and fusing point is: 182-185 ℃.
Embodiment 3: preparation benzotriazole schiff base compounds:
(1) in the 100ml round-bottomed flask, adds 3.26g (20mmol) 5-carboxyl benzotriazole, an amount of LiAlH4 and THF, the control temperature is about 20 ℃, behind induction stirring 10h, inwardly drip an amount of TPAP/NMO, CH2Cl2, THF, DMF normal-temperature reaction 12h obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white behind the decompress filter.(productive rate: 89%)
(2) in the 100ml round-bottomed flask, add 2.62g (18mmol) A successively, 0.54g (18mmol) formaldehyde, 20ml acetic acid, 50ml water stirs 1h, places 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole B2.88g.(productive rate: 90%)
(3) in the 100ml two-neck bottle, add 2.83g (16mmol) B, 30ml CHCl successively
3With 1.0g phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving.The aqueous solution that will be dissolved with 1.00g (10mmol) chromium trioxide and the 1.0ml vitriol oil slowly drops in the two-neck bottle, and the control temperature continues to stir 0.5h about 20 ℃.Separatory, inorganic layer is regulated pH to 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.12g.(productive rate: 40%)
(4) in flask, add 1.05g (6mmol) C, add then an amount of ethanol make it the dissolving, add 1.73g (12mmol) 6-quinolylamine again, reflux 4h, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound D2.21g.(productive rate: 86%)
The ultimate yield of target product is 28%, and fusing point is: 182-185 ℃.
Embodiment 4: preparation benzotriazole schiff base compounds:
(1) in the 100ml round-bottomed flask, adds 3.26g (20mmol) 5-carboxyl benzotriazole, an amount of LiAlH
4And THF, the control temperature is about 20 ℃.Behind induction stirring 10h, inwardly drip an amount of TPAP/NMO, CH
2Cl
2, THF, DMF normal-temperature reaction 12h obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white behind the decompress filter.(productive rate: 89%)
(2) in the 100ml round-bottomed flask, add 2.62g (18mmol) A successively, 0.54g (18mmol) formaldehyde, 20ml acetic acid, 50ml water stirs 1h, places 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole B2.88g.(productive rate: 90%)
(3) in the 100ml two-neck bottle, add 2.88g (16mmol) B, 30ml CHCl successively
3With 1.5g phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving.The aqueous solution that will be dissolved with 1.60g (16mmol) chromium trioxide and the 20ml vitriol oil slowly drops in the two-neck bottle, and the control temperature continue to stir 1h about 52 ℃, when solution colour can be stopped when blackish green by orange becoming.Separatory, inorganic layer is regulated pH to 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.96g (11mmol) C, add then an amount of ethanol make it the dissolving, add 3.17g (25mmol) 6-quinolylamine again, react 10h under the normal temperature, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound D2.73g.(productive rate: 58%)
The ultimate yield of target product is 33%, and fusing point is: 182-185 ℃.
Test example 1:
Pickle solution is dilute hydrochloric acid, and concentration is 0.5mol/L, and the pickle solution consumption is 100L, adds target compound 10g, at ambient temperature steel to be cleaned is immersed in 4h in the pickle solution.
The highest inhibition efficiency of test acquisition is 99% by experiment, is shown as high-efficient corrosion inhibitor.
Test example 2:
Pickle solution is dilute sulphuric acid, and concentration is 0.5mol/L, and the pickle solution consumption is 100L, adds target compound 10g, at ambient temperature steel to be cleaned is immersed in 4h in the pickle solution.
The highest inhibition efficiency of test acquisition is 98% by experiment, is shown as high-efficient corrosion inhibitor.
Claims (3)
1. benzotriazole category schiff base compounds, the structural formula of this compound is:
2. the synthetic method of benzotriazole schiff base compounds as claimed in claim 1 may further comprise the steps successively:
(1) in round-bottomed flask, adds 5-carboxyl benzotriazole, an amount of LiAlH
4And THF, the control temperature inwardly drips an amount of TPAP/NMO, CH behind induction stirring 10h about 20 ℃
2Cl
2, THF, DMF normal-temperature reaction 12h obtains the thick product 5-aldehyde radical benzotriazole of white behind the decompress filter;
(2) add 5-aldehyde radical benzotriazole and the formaldehyde that mol ratio is 1:1 successively in round-bottomed flask, an amount of acetic acid and water stir 1h, place 2h, and decompress filter obtains the thick product 1-methylol of white-5-aldehyde radical benzotriazole;
(3) in two-neck bottle, add 1-methylol-5-aldehyde radical benzotriazole, The addition of C HCl successively
3With phase-transfer catalyst Tetrabutyl amonium bromide TBAB, be heated to dissolving, slowly drop to the aqueous solution that is dissolved with chromium trioxide and the vitriol oil in the two-neck bottle, the control temperature continue to stir 1h about 52 ℃, when solution colour can be stopped when blackish green by orange becoming, separatory, inorganic layer is regulated pH ≈ 8 with yellow soda ash, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, the rotary evaporation desolventizing obtains orange red thick product 1,5-dialdehyde-based benzotriazole;
(4) in flask, add 1,5-dialdehyde-based benzotriazole, add an amount of ethanol then and make it dissolving, add and 1 the 6-quinolylamine of 5-dialdehyde-based benzotriazole equivalent, reflux 4h again, cold filtration, and in ethanol recrystallization, obtain faint yellow target compound.
3. the benzotriazole schiff base compounds is characterized in that in the application of carbon steel pickling corrosion inhibitor according to claim 1: scavenging solution is acid solution, and the amount that adds inhibiter in every liter of acid solution is 10g, and the submergence temperature is room temperature, and the time is 4h; Wherein: acid solution is dilute hydrochloric acid or dilute sulphuric acid, and concentration is 0.5mol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103849878A (en) * | 2014-03-18 | 2014-06-11 | 怀化学院 | Corrosion inhibitor of preventing metal from being corroded |
| CN103992284A (en) * | 2014-06-03 | 2014-08-20 | 如皋市金陵化工有限公司 | Preparation method of 1-hydroxymethyl benzotriazole |
| CN104073807A (en) * | 2014-04-04 | 2014-10-01 | 怀化学院 | Method for improving copper corrosion inhibition effect in alkaline medium |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103849878A (en) * | 2014-03-18 | 2014-06-11 | 怀化学院 | Corrosion inhibitor of preventing metal from being corroded |
| CN104073807A (en) * | 2014-04-04 | 2014-10-01 | 怀化学院 | Method for improving copper corrosion inhibition effect in alkaline medium |
| CN104073807B (en) * | 2014-04-04 | 2017-03-15 | 怀化学院 | A kind of method for improving copper corrosion inhibition in alkaline medium |
| CN103992284A (en) * | 2014-06-03 | 2014-08-20 | 如皋市金陵化工有限公司 | Preparation method of 1-hydroxymethyl benzotriazole |
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