CN103193723B - Benzotriazole Schiff base compound and preparation method thereof - Google Patents
Benzotriazole Schiff base compound and preparation method thereof Download PDFInfo
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- CN103193723B CN103193723B CN201310109063.6A CN201310109063A CN103193723B CN 103193723 B CN103193723 B CN 103193723B CN 201310109063 A CN201310109063 A CN 201310109063A CN 103193723 B CN103193723 B CN 103193723B
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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 compound and preparation method thereof.
Background technology
Pickling has a wide range of applications in the industries such as metallic substance, machinery, metallurgy, electric power and chemical industry.Industrially pickling comprises the pickling descaling of pickling except removing iron scale, metallic substance and equipment.Pickling its not only can produce huge economic results in society, safety problem and environment protection are also significant.
Acid conventional in 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 take 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, thus reach and suppress the corrosion of metal in acidic medium, reduce the consumption of acid, promote pickling effect, and the object in extension device work-ing life.
Phase early 1950s, people just find that benzotriazole has good corrosion mitigating effect to copper and alloy thereof, and in order to strengthen the corrosion mitigating effect of benzotriazole further, the benzotriazole derivatives of synthesizing new has become the emphasis of people's research.With-C=N-functional group is the schiff base compounds indicated, itself is exactly a class has fine function of prevent erosion inhibiter to copper and iron.Both containing the atom N that the electronegativity of lone-pair electron is higher can be provided in Schiff's base molecular structure, again containing the double bond structure that can provide π-electron and unoccupied orbital, make it be easy to form self-assembled film in metallic surface, thus play the effect suppressing corrosion reaction.Schiff's base also has low, the easy synthesis of cost and purification, good water solubility, nontoxicity and the feature such as of a great variety.Up to now, existingly to report about Schiff bases compou nd synthesis and as the research of inhibiter in a large number.And Schiff's base functional group is combined with benzotriazole, its active centre can be increased structure, increase compound molecule and the interactional chance of steel surface, infer in theory and can obtain better corrosion mitigating effect.Actually rare about the report of Benzotriazole Schiff base compound 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 compound.
A kind of structural formula of Benzotriazole Schiff base compound is as follows:
The preparation method of this Benzotriazole Schiff base compound:
(1) in 100ml round-bottomed flask, add 3.26g (20mmol) 5-carboxyl benzotriazole, appropriate LiAlH
4and THF, control temperature at about 20 DEG C, to the TPAP/NMO that interior dropping is appropriate, CH after induction stirring 10h
2cl
2, THF, DMF normal-temperature reaction 12h, obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white after decompress filter.(productive rate: 89%)
(2) in 100ml round-bottomed flask, 2.62g (18mmol) A, 0.54g (18mmol) formaldehyde is added successively, 20ml acetic acid, 50ml water, stirs 1h, places 2h, decompress filter, obtains the thick product 1-methylol-5-aldehyde radical benzotriazole B2.88g of white.(productive rate: 90%)
(3) in 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 dissolve.The aqueous solution being dissolved with 1.60g (16mmol) chromium trioxide and the 2.4ml vitriol oil is slowly dropped in two-neck bottle, control temperature at about 52 DEG C, continue stir 1h, when solution colour from orange become blackish green time can stop.Separatory, inorganic layer sodium carbonate regulates pH ≈ 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, and rotary evaporation, except desolventizing, obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.92g (11mmol) C, then add ethanol in proper amount and make it to dissolve, then add 3.17g (22mmol) 6-quinolylamine, reflux 4h, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound D4.04g.(productive rate: 86%)
The building-up reactions equation of this Benzotriazole Schiff base compound is:
Benzotriazole Schiff base compound molecular formula of the present invention is C
26h
17n
7, molecular weight is 427.46; This target compound so far there are no bibliographical information, synthetic method is simple, and reaction conditions is gentle, and simple to operate, productive rate is higher, and product is easy to be separated, purify.
Described Benzotriazole Schiff base compound is in the application of carbon steel pickling corrosion inhibitor.The present invention is as the principle of inhibiter: containing heterocycle in Benzotriazole Schiff base compound molecule, nitrogen-atoms and-C=N-, when metal immerses corrosion inhibitor solution, lone-pair electron are inserted the unoccupied orbital of metal by these heteroatomss, inhibitor molecular and metallic surface is made to form firm and stable chemical bond, form constitutionally stable assembling film at steel surface, thus reach the object of inhibition.
Embodiment
Embodiment 1: preparation Benzotriazole Schiff base compound:
(1) in 100ml round-bottomed flask, add 3.26g (20mmol) 5-carboxyl benzotriazole, appropriate LiAlH
4and THF, control temperature at about 20 DEG C, to the TPAP/NMO that interior dropping is appropriate, CH after induction stirring 10h
2cl
2, THF, DMF normal-temperature reaction 12h, obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white after decompress filter.(productive rate: 89%)
(2) in 100ml round-bottomed flask, 2.62g (18mmol) A, 0.54g (18mmol) formaldehyde is added successively, 20ml acetic acid, 50ml water, stirs 1h, places 2h, decompress filter, obtains the thick product 1-methylol-5-aldehyde radical benzotriazole B2.88g of white.(productive rate: 90%)
(3) in 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 dissolve.The aqueous solution being dissolved with 1.60g (16mmol) chromium trioxide and the 2.4ml vitriol oil is slowly dropped in two-neck bottle, control temperature at about 52 DEG C, continue stir 1h, when solution colour from orange become blackish green time can stop.Separatory, inorganic layer sodium carbonate regulates pH ≈ 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, and rotary evaporation, except desolventizing, obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.92g (11mmol) C, then add ethanol in proper amount and make it to dissolve, then add 3.17g (22mmol) 6-quinolylamine, reflux 4h, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound D4.04g.(productive rate: 86%)
The ultimate yield of target product is 48%, and fusing point is: 182-185 DEG C.
Through Infrared spectroscopy and nuclear magnetic resonance spectroscopy, 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 compound:
(1) in 100ml round-bottomed flask, add 3.26g (20mmol) 5-carboxyl benzotriazole, appropriate LiAlH
4and THF, control temperature is at about 40 DEG C.To the TPAP/NMO that interior dropping is appropriate, CH after induction stirring 12h
2cl
2, THF, DMF normal-temperature reaction 8h, obtains the thick product 5-aldehyde radical benzotriazole A2.14g of white after decompress filter.(productive rate: 73%)
(2) in 100ml round-bottomed flask, 2.14g (14.5mmol) A, 0.45g (15mmol) formaldehyde is added successively, 20ml ethanol, 50ml water, stirs 1.5h, places 2h, decompress filter, obtains the thick product 1-methylol-5-aldehyde radical benzotriazole B2.00g of white.(productive rate: 78%)
(3) in 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 dissolve.The aqueous solution being dissolved with 1.10g (11mmol) chromium trioxide and the 1.7ml vitriol oil is slowly dropped in two-neck bottle, control temperature at about 52 DEG C, continue stir 1h, when solution colour from orange become blackish green time can stop.Separatory, inorganic layer sodium carbonate regulates pH ≈ 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, and rotary evaporation, except 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, then add ethanol in proper amount and make it to dissolve, then add 2.22g (15.4mmol) 6-quinolylamine, reflux 4h, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound D2.83g.(productive rate: 86%)
The ultimate yield of target product is 34%, and fusing point is: 182-185 DEG C.
Embodiment 3: preparation Benzotriazole Schiff base compound:
(1) in 100ml round-bottomed flask, add 3.26g (20mmol) 5-carboxyl benzotriazole, appropriate LiAlH4 and THF, control temperature is at about 20 DEG C, to the TPAP/NMO that interior dropping is appropriate after induction stirring 10h, CH2Cl2, THF, DMF normal-temperature reaction 12h, obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white after decompress filter.(productive rate: 89%)
(2) in 100ml round-bottomed flask, 2.62g (18mmol) A, 0.54g (18mmol) formaldehyde is added successively, 20ml acetic acid, 50ml water, stirs 1h, places 2h, decompress filter, obtains the thick product 1-methylol-5-aldehyde radical benzotriazole B2.88g of white.(productive rate: 90%)
(3) in 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 dissolve.Slowly dropped in two-neck bottle by the aqueous solution being dissolved with 1.00g (10mmol) chromium trioxide and the 1.0ml vitriol oil, control temperature, at about 20 DEG C, continues to stir 0.5h.Separatory, inorganic layer sodium carbonate regulates pH to 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, and rotary evaporation, except desolventizing, obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.12g.(productive rate: 40%)
(4) in flask, add 1.05g (6mmol) C, then add ethanol in proper amount and make it to dissolve, then add 1.73g (12mmol) 6-quinolylamine, reflux 4h, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound D2.21g.(productive rate: 86%)
The ultimate yield of target product is 28%, and fusing point is: 182-185 DEG C.
Embodiment 4: preparation Benzotriazole Schiff base compound:
(1) in 100ml round-bottomed flask, add 3.26g (20mmol) 5-carboxyl benzotriazole, appropriate LiAlH
4and THF, control temperature is at about 20 DEG C.To the TPAP/NMO that interior dropping is appropriate, CH after induction stirring 10h
2cl
2, THF, DMF normal-temperature reaction 12h, obtains the thick product 5-aldehyde radical benzotriazole A2.62g of white after decompress filter.(productive rate: 89%)
(2) in 100ml round-bottomed flask, 2.62g (18mmol) A, 0.54g (18mmol) formaldehyde is added successively, 20ml acetic acid, 50ml water, stirs 1h, places 2h, decompress filter, obtains the thick product 1-methylol-5-aldehyde radical benzotriazole B2.88g of white.(productive rate: 90%)
(3) in 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 dissolve.The aqueous solution being dissolved with 1.60g (16mmol) chromium trioxide and the 20ml vitriol oil is slowly dropped in two-neck bottle, control temperature at about 52 DEG C, continue stir 1h, when solution colour from orange become blackish green time can stop.Separatory, inorganic layer sodium carbonate regulates pH to 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, and rotary evaporation, except desolventizing, obtains orange red thick product 1,5-dialdehyde-based benzotriazole C1.96g.(productive rate: 70%)
(4) in flask, add 1.96g (11mmol) C, then add ethanol in proper amount and make it to dissolve, then add 3.17g (25mmol) 6-quinolylamine, 10h is reacted under normal temperature, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound D2.73g.(productive rate: 58%)
The ultimate yield of target product is 33%, and fusing point is: 182-185 DEG C.
Test example 1:
Pickle solution is dilute hydrochloric acid, and concentration is 0.5mol/L, and pickle solution consumption is 100L, adds target compound 10g, at ambient temperature steel to be cleaned is immersed in 4h in pickle solution.
The highest inhibition efficiency that test obtains by experiment is 99%, is shown as high-efficient corrosion inhibitor.
Test example 2:
Pickle solution is dilute sulphuric acid, and concentration is 0.5mol/L, and pickle solution consumption is 100L, adds target compound 10g, at ambient temperature steel to be cleaned is immersed in 4h in pickle solution.
The highest inhibition efficiency that test obtains by experiment is 98%, is shown as high-efficient corrosion inhibitor.
Claims (3)
1. a benzotriazole category schiff base compounds, the structural formula of this compound is:
2. the synthetic method of Benzotriazole Schiff base compound as claimed in claim 1 comprises the following steps successively:
(1) in round-bottomed flask, 5-carboxyl benzotriazole, LiAlH is added
4and THF, control temperature at 20 DEG C, to interior dropping TPAP/NMO, CH after induction stirring 10h
2cl
2,tHF, DMF normal-temperature reaction 12h, obtains the thick product 5-aldehyde radical benzotriazole of white after decompress filter;
(2) in round-bottomed flask, add 5-aldehyde radical benzotriazole and formaldehyde that mol ratio is 1:1, then add acetic acid and water, stir 1h, place 2h, decompress filter, obtain the thick product 1-methylol-5-aldehyde radical benzotriazole of white;
(3) in two-neck bottle, 1-methylol-5-aldehyde radical benzotriazole is added successively, CHCl
3with phase-transfer catalyst TBAB, be heated to dissolve, the aqueous solution being dissolved with chromium trioxide and the vitriol oil is slowly dropped in two-neck bottle, control temperature at 52 DEG C, continue stir 1h, when solution colour from orange become blackish green time can stop, separatory, inorganic layer sodium carbonate regulates pH ≈ 8, and chloroform extraction merges organic layer, anhydrous magnesium sulfate drying, rotary evaporation, except desolventizing, obtains orange red thick product 1,5-dialdehyde-based benzotriazole;
(4) in flask, add 1,5-dialdehyde-based benzotriazole, then add ethanol and make it to dissolve, add the 6-quinolylamine with 1,5-dialdehyde-based benzotriazole, 2 times of amount of substances, reflux 4h again, cold filtration, and recrystallization in ethanol, obtain faint yellow target compound.
3. Benzotriazole Schiff base compound, in the application of carbon steel pickling corrosion inhibitor, is characterized in that as claimed in claim 1: scavenging solution is acid solution, and the amount adding inhibiter in often liter of acid solution is 10g, and submergence temperature is room temperature, and the time is 4h; Wherein: acid solution is dilute hydrochloric acid or dilute sulphuric acid, concentration is 0.5mol/L.
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| CN103849878A (en) * | 2014-03-18 | 2014-06-11 | 怀化学院 | Corrosion inhibitor of preventing metal from being corroded |
| 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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| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| CN101747322A (en) * | 2010-01-20 | 2010-06-23 | 贵州大学 | Pyridazinone derivatives with 1,2,4-triazole schiff base, preparation method and application thereof |
| CN102329273A (en) * | 2011-07-15 | 2012-01-25 | 中国科学院海洋研究所 | Schiff base containing nitrogenous heterocyclic compound and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1832629A1 (en) * | 2006-03-10 | 2007-09-12 | MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
| CN101747322A (en) * | 2010-01-20 | 2010-06-23 | 贵州大学 | Pyridazinone derivatives with 1,2,4-triazole schiff base, preparation method and application thereof |
| CN102329273A (en) * | 2011-07-15 | 2012-01-25 | 中国科学院海洋研究所 | Schiff base containing nitrogenous heterocyclic compound and preparation method and application thereof |
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