CN104264156B - Perfluoroalkyl sulfonyloxy benzyl heterocyclic corrosion inhibitor as well as preparation method - Google Patents
Perfluoroalkyl sulfonyloxy benzyl heterocyclic corrosion inhibitor as well as preparation method Download PDFInfo
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- CN104264156B CN104264156B CN201410507881.6A CN201410507881A CN104264156B CN 104264156 B CN104264156 B CN 104264156B CN 201410507881 A CN201410507881 A CN 201410507881A CN 104264156 B CN104264156 B CN 104264156B
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Abstract
The invention discloses a perfluoroalkyl sulfonyloxy benzyl heterocyclic corrosion inhibitor as well as a preparation method and application thereof. A structural general formula of the fluorine-containing corrosion inhibitor is as shown in formula I, wherein Rf is either perfluoro butyl or perfluoro hexyl, and R is a heterocyclic group, including triazole, benzotriazole, benzothiazolethiol, benzimidazole, mercapto benzimidazole, imidazole, 2-methylimidazole, 1,4-dimethylimidazole, etc. The perfluoroalkyl sulfonyloxy benzyl heterocyclic corrosion inhibitor is prepared by the following steps: conducing sulfonic acid esterification on fluorine-containing precursor materials (perfluoro butyl sulfuryl fluoride and perfluoro hexyl sulfuryl fluoride) and para hydroxybenzene methanol, implementing chlorination with a halogenating reagent, and reacting with a heterocyclic compound. By introducing the fluorine-containing group to corrosion inhibitor molecules, the designed and synthesized fluorine-containing corrosion inhibitor disclosed by the invention is free of phosphor element harmful to the environment, and has excellent corrosion inhibiting effect at low concentration; and the partial fluorine-containing corrosion inhibitor disclosed by the invention can achieve a controlled-release effect more than 95% at concentration of 5*10＜-4＞M (as shown in specification).
Description
Technical field
The present invention relates to metal inhibitor is and in particular to a class per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter and its system
Preparation Method and application.
Background technology
Metal material occupies extremely important in departments such as modern industrial or agricultural, machinery, traffic, transport, national defence and science and technology
Status.Steel has the advantages that cheap, machining property is good, yield is big, is selection, with considering first during material
Metal, be also one of maximum, most widely used metal of current consumption.However, metal material easily corrodes, harm is very
Seriously.According to estimates, the iron and steel amount that the whole world is scrapped because of corrosion every year is equivalent to the 1/4-1/3 of annual production；Drawn by corrosion every year
The loss rising accounts for the 3.1%～4.5% of national economy total output value (GDP).Up to 500,000,000,000 yuan of the annual corrosion loss of China
Left and right.Greatly develop corrosion and protection technology the construction of propulsion conservation-minded society and friendly environment society is had very
Important meaning.
Corrosion inhibiter is a kind of material that can significantly reduce corrosion rate in corrosive medium for the metal, industrially applies
Existing many decades.Inhibitor molecular be typically made up of non-polar group and polar group (Int.J.Corros., 2011, doi:
10.1155/2011/548528).Central atom N, O, S of polar group etc. have unshared lone pair electrons, and metal surface is deposited
In empty d track, the lone pair electrons of center electron will form coordinate bond with the empty d rail interaction in metal, makes to delay
Erosion agent molecule is adsorbed in metal surface and forms one layer of fine and close chemical films；Non-polar group is often hydrophobic grouping, can be by gold
Metal surface is separated with corrosive medium, reduces metal erosion.Corrosion inhibiter is with its easy to use, applied widely, small investment, instant effect
The advantages of, it has also become one of maximally effective anticorrosion technique.Corrosion inhibiter is alternatively arranged as degreaser, water quality cleansing agent, antisludging agent, one-tenth
Film and resistance to compression additive etc. are widely used in the neck such as rubber, oil, agricultural, mining industry, medicine, environmental protection and analytical chemistry
Domain.
Research currently for corrosion inhibiter yet suffers from deficiency：1. with the enhancing of people's environmental consciousness, to corrosion inhibiter
Propose higher and higher requirement (J.Appl.Electrochem., 2005,35,879-888), environmental legislation is prohibited
The use of chromium corrosion inhibitor.Water treatment agent conventional in cooling water system both at home and abroad adopts series of phosphate (referred to as mostly at present
Phosphorus system), due to the degraded of phosphorous water treatment agent after discharge, the Phos discharging will cause the eutrophication of water proximate, promote
Enter the growth of bacterium algae and form " red tide ", bring huge harm to aquaculture and natural, ecological.From long term growth trend
See it is necessary to strictly limit production and the application of phosphorus family corrosion inhibitor, replace with non-phosphor corrosion inhibitor.2. it is used alone corrosion inhibiter
Inhibition efficiency is relatively low, current considerable part corrosion inhibiter need compounding can be only achieved certain corrosion mitigating effect (CN103774166A,
2014-05-07)；The corrosion inhibiter of document report just can reach reasonable corrosion mitigating effect mostly at higher concentrations
(Corros.Sci.,2014,85, 215–221).Therefore, design synthesis eco-friendly without phosphorus, the low consumption of one class, high inhibition
The corrosion inhibiter of efficiency is the direction of current corrosion inhibiter research.
Content of the invention
It is an object of the invention to overcoming shortcoming and the deficiency of prior art, provide fluorine corrosion inhibiter.The present invention's
Purpose also resides in the preparation method providing above-mentioned fluorine-containing corrosion inhibiter.It is fluorine-containing with perfluoro butyl sulfonic acid fluoride, perfluoro hexyl sulfuryl fluoride
Precursor material, through carrying out sulfonic acid esterification, halo from p-Hydroxybenzylalcohol and reacting with different heterocycles, prepares fluorine-containing inhibition
Agent.
The purpose of the present invention is achieved through the following technical solutions：
A kind of fluorine-containing corrosion inhibiter, is per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter, its general structure is as shown in formula I：
Wherein：RfFor perfluoroalkyl, preferably perfluoro butyl or perfluoro hexyl；R is various heterocyclic groups, including three nitrogen
Azoles, BTA, mercaptobenzothiazoler, benzimidazole, mercaptobenzimidazole, imidazoles, 2-methylimidazole, 1,4- dimethyl miaow
Azoles etc..
Preferably, described per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter includes N- (4- perfluoro hexyl sulfonyloxy
Benzyl) BTA (A1), N- (4- perfluoro hexyl sulfonyloxy benzyl) benzimidazole (A2), N- (4- perfluoro hexyl sulphonyl oxygen
Base benzyl) -1,2,4- triazole (A3), N-4- perfluoro hexyl sulfonyloxy Benzylmercapto benzothiazole (A4), N-4- perfluoro hexyl
Sulfonyloxy Benzylmercapto benzimidazole (A5), N- (4- perfluoro hexyl sulfonyloxy benzyl) imidazoles (A6), N- (4- perfluoro hexyl
Sulfonyloxy benzyl) -1,4- methylimidazole (A7), N- (4- perfluoro hexyl sulfonyloxy benzyl) -2-methylimidazole (A8), N-
(4- perfluoro butyl sulfonyloxy benzyl) BTA (A9), N- (4- perfluoro butyl sulfonyloxy benzyl) benzimidazole
(A10), N- (4- perfluoro butyl sulfonyloxy benzyl) -1,2,4- triazole (A11), N-4- perfluoro butyl sulfonyloxy benzyl mercapto
Base benzothiazole (A12), N-4- perfluoro butyl sulfonyloxy Benzylmercapto benzimidazole (A13), N- (4- perfluoro butyl sulphonyl oxygen
Base benzyl) imidazoles (A14), N- (4- perfluoro butyl sulfonyloxy benzyl)-Isosorbide-5-Nitrae-methylimidazole (A15), N- (4- perfluoro butyl
Sulfonyloxy benzyl) -2-methylimidazole (A16), structural formula is respectively as shown in specific embodiment Chinese style 1～16.
The preparation method of above-mentioned per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter, comprises the steps：
(1) p-Hydroxybenzylalcohol, in the presence of acid binding agent, occurs nucleophilic to take with perfluoroalkyl sulfonyl fluoride in organic solvent
Generation reaction, obtains intermediate perfluoro alkyl sulfonic acid -4- (methylol) phenylester.
(2) perfluoro alkyl sulfonic acid -4- (methylol) phenylester is reacted with halogenating agent in organic solvent and obtains intermediate
Perfluoro alkyl sulfonic acid -4- (halomethyl) phenylester.
(3) perfluoro alkyl sulfonic acid -4- (halomethyl) phenylester is in the presence of acid binding agent, with heterocyclic compound in organic solvent
Thing reaction obtains per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter (A1～A16).
Acid binding agent described in step (1) and step (3) is preferably potassium carbonate, and described organic solvent is preferably acetonitrile.
Organic solvent described in step (2) is preferably Isosorbide-5-Nitrae-dioxane, and it is sub- that described halogenating agent is preferably dichloro
Sulfone.
Heterocyclic compound described in step (3) is preferably BTA, benzimidazole, 1,2,4- triazole, sulfydryl
Benzothiazole, mercaptobenzimidazole, 1,4- methylimidazole, 2-methylimidazole or imidazoles.
Preferably, the perfluoroalkyl sulfonyl fluoride described in step (1) is perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfuryl fluoride,
Halogenating agent described in step (2) is thionyl chloride；Accordingly, the intermediate that step (1) obtains is perfluoro butyl sulfonic acid -4-
(methylol) phenylester (M1) or perfluoro hexyl sulfonic acid -4- (methylol) phenylester (M2), the intermediate that step (2) obtains is complete
Fluorine butyl sulfonic acid -4- (chloromethyl) phenylester (M3) or perfluoro hexyl sulfonic acid 4- (chloromethyl) phenylester (M4).
The present invention has the advantage that with respect to prior art and effect：
Fluoro-containing group is introduced inhibitor molecular by the present invention, and the fluorine-containing corrosion inhibiter of design synthesis does not contain harm environment phosphorus unit
Element, just has good corrosion mitigating effect under low concentration.The present invention partly fluorine-containing corrosion inhibiter 5 × 10-4Just can reach during the concentration of M
More than 95% slow release effect, has significant advantage compared with the novel corrosion inhibitor of document report, such as Ahmed A.Faragd etc.
The schiff bases corrosion inhibiter SB-III (Corros.Sci.2013,74 of people's report:168-177.), in concentration least concentration 0.5mM
It is only capable of reaching 89.5%；Bin Xu et al. reports heterocycle corrosion inhibiter (Corros.Sci.2013,74:206-213.) exist
Corrosion inhibition rate during concentration 0.5mM is 96%.
Specific embodiment
With reference to embodiment, the present invention does further detailed description, but embodiments of the present invention not limited to this.
Embodiment 1 intermediate (M1、M2) preparation
12.4g (0.1mol) p-Hydroxybenzylalcohol, 17.9g (0.13mol) carbonic acid is added in the 1000mL flask being dried
Potassium, 200mL acetonitrile, it is heated to reflux, is slowly added dropwise 52.26g (0.13mol) perfluoro butyl sulfonic acid fluoride, continue reaction 2.5h, TCL
Monitoring reaction end.Add 150mL ethyl acetate in reactant liquor, wash 3 times with saturated nacl aqueous solution, organic layer is through anhydrous sulphur
Sour sodium is dried, and precipitation obtains colourless transparent liquid intermediate perfluoro butyl sulfonic acid -4- (methylol) phenylester (M1) 35.7g, receive
Rate is 88%.1H NMR(400MHz,CDCl3):δ2.50(s,1H,OH),4.61(s,2H,CH2), 6.89 (d, 2H, J=
7.8Hz, phH), 7.33 (d, 2H, J=7.8Hz, phH)；19F NMR(376MHz,CDCl3):δ-128.827(2F),-
123.802(2F),-111.125(2F),-84.248(3F)；EI-MS m/z:406 (calculated values:405.99).
Addition 12.4g (0.1mol) p-Hydroxybenzylalcohol in 1000mL there-necked flask, 17.9g (0.13mol) potassium carbonate,
200mL acetonitrile, is heated to reflux, and is slowly added dropwise 65.3g (0.13mol) perfluoro hexyl sulfuryl fluoride, continues reaction 2.5h, and TCL monitors
Reaction end.Add 150mL ethyl acetate in reactant liquor, washed 3 times with saturated nacl aqueous solution, organic layer is through anhydrous sodium sulfate
It is dried, precipitation, obtain colourless liquid intermediate perfluoro hexyl sulfonic acid -4- (methylol) phenylester (M2) 44.53g, yield is
84%.1H NMR(400MHz,CDCl3):δ2.50(s,1H,-OH),4.61(s,2H,CH2), 6.89 (d, 2H, J=7.8Hz,
), phH 7.33 (d, 2H, J=7.8Hz, phH)；19F NMR(376MHz,CDCl3):δ-126.494(2F),-123.057
(2F),-122.182(2F),-120.690(2F),-112.682(2F),-81.136(3F)；EI-MS m/z:506.03 (calculate
Value:505.99).
Embodiment 2 intermediate (M3、M4) preparation
44.66g (0.11mol) perfluoro butyl sulfonic acid -4- (methylol) phenylester is added in the 1000mL flask being dried
(M1), 200mL Isosorbide-5-Nitrae-dioxane, it is slowly added dropwise 38.6g (0.22mmol) thionyl chloride under ice bath, react after dripping off
30min, is warmed up to 60 DEG C and continues reaction 1h, TLC monitors reaction end.It is poured slowly in frozen water, add 200mL ethyl acetate,
Wash three times with saturated nacl aqueous solution, organic layer, through anhydrous sodium sulfate drying, precipitation, obtains colourless liquid intermediate perfluoro butyl
Sulfonic acid -4- (chloromethyl) phenylester (M3) 37.7g, yield is 81%.1H NMR(400MHz,CDCl3):δ4.56(s,2H,
CH2), 6.90 (d, 2H, J=3.9Hz, phH), 7.40 (d, 2H, J=4.2Hz, phH)；19F NMR(376MHz,CDCl3):δ-
128.827(2F),-123.802(2F),-111.125(2F),-84.248(3F)；EI-MS m/z::424 (calculated values:
423.95).
55.6g (0.11mol) perfluoro hexyl sulfonic acid -4- (methylol) phenylester is added in the 1000mL flask being dried
(M2), 200mL Isosorbide-5-Nitrae-dioxane, it is slowly added dropwise 38.6g (0.22mmol) thionyl chloride under ice bath, react after dripping off
30min, is warmed up to 60 DEG C and continues reaction 1h, TLC monitors reaction end.It is poured slowly in frozen water, add 200mL ethyl acetate,
Wash three times with saturated nacl aqueous solution, organic layer, through anhydrous sodium sulfate drying, precipitation, obtains colourless liquid intermediate perfluoro hexyl
Sulfonic acid -4- (chloromethyl) phenylester (M4) 45.0g, yield is 78%.1H NMR(400MHz,CDCl3):δ4.56(s,2H,-
CH2-), 6.90 (d, 2H, J=3.9Hz, phH), 7.40 (d, 2H, J=4.2Hz, phH)；19F NMR(376MHz,CDCl3):δ-
126.494(2F),-123.057(2F),-122.182(2F),-120.690(2F),-112.682(2F),-81.136(3F)；
EI-MS m/z::524.02 (calculated values:523.95).
Embodiment 3 N- (4- perfluoro hexyl sulfonyloxy benzyl) BTA (A1) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.18g (0.0015mol) BTA, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight,
Then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by second
Acetoacetic ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A1) 0.88g, yield is 97%.1H
NMR(400MHz,DMSO)δ:6,10 (d, J=10.0Hz, 2H ,-CH2-), 7.40～7.58 (m, 6H, phH), 7.90 (d, J=
8.4Hz, 1H, phH), 8.09 (d, J=8.4Hz, 1H, phH)；19F NMR(376MHz,DMSO)δ:-126.17(2F),-
122.86(2F),-121.82(2F),-120.27(2F),-109.40(2F),-80.71(3F)；EI-MS m/z: 607.24
(calculated value:607.02),；Anal.Calcd for C19H10F13N3O3S:C,37.57；H,1.66；N,6.92；S,5.28；
Found:C,37.81；H,1.76；N,7.14；S,5.01.
Embodiment 4 N- (4- perfluoro hexyl sulfonyloxy benzyl) benzimidazole (A2) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.18g (0.0015mol) benzimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight, so
Use ethyl acetate (3 × 20mL) to extract afterwards, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by acetic acid
Ethyl ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A2) 0.87g, yield is 96%.1H
NMR(400MHz,DMSO)δ:5.58(s,2H,-CH2-), 7.19～7.22 (m, 2H, phH), 7.44 (m, 4H, phH), 7.68
(d, J=2.4Hz, 1H, phH), 7.52 (d, J=4.0Hz, 1H, phH), 8.09 (s, 1H, Ar-H)；19F NMR(376MHz,
DMSO)δ:-125.94(2F),-122.67(2F),-121.63(2F),-120.07(2F),-109.24(2F),-80.42
(3F)；EI-MS m/z:606.34 (calculated values:606.03)；Anal.Calcd for C20H11F13N2O3S:C,36.92；H,
1.83；N,4.62；S,5.29；Found:C,39.50；H,1.64；N,4.58；S,5.31.
Embodiment 5 N- (4- perfluoro hexyl sulfonyloxy benzyl) -1,2,4- triazole (A3) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.1g (0.0015mol) 1,2,4- triazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight,
Then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by second
Acetoacetic ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A3) 0.79g, yield is 94%.1H
NMR(400MHz,DMSO)δ:5.46(s,2H,-CH2-), 7.32～7.41 (m, 4H, phH), 7.98 (s, 1H, Ar-H), 8.66
(s,1H,Ar-H)；19F NMR(376MHz,DMSO)δ:-126.94(2F),-123.44(2F),-122.37(2F),-120.74
(2F),-109.89(2F),-81.75(3F)；EI-MS m/z:557.29 (calculated values:557.01)；Anal.Calcd for
C15H8F13N3O3S:C,32.33；H,1.45；N,7.54；S,5.75；Found:C,32.29；H,1.56；N,7.48；S,5.76.
Embodiment 6 N-4- perfluoro hexyl sulfonyloxy Benzylmercapto benzothiazole (A4) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.25g (0.0015mol) mercaptobenzothiazoler, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A4) 0.93g, yield is 95%.1H NMR(400MHz,DMSO)δ:4.71(s,2H,-CH2-), 7.13～7.48 (m, 4H, phH), 7.69 (d, J=8,4Hz, 1H,
), phH 7.88 (d, J=8.0Hz, 1H, phH), 8.00 (d, J=8.0Hz, 1H, phH)；19FNMR(376MHz,DMSO)δ:-
125.97(2F),-122.67(2F),-121.66(2F),-120.10(2F),-109.28(2F),-80.42(3F)；EI-MS
m/z:655.33 (calculated values:654.96)；Anal.Calcd for C20H10F13NO3S3:C,36.65；H,1.54；N,2.14；S,
14.68；Found:C,36.80；H,1.55；N,2.22；S,14.94.
Embodiment 7 N-4- perfluoro hexyl sulfonyloxy Benzylmercapto benzimidazole (A5) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.23g (0.0015mol) mercaptobenzimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A5) 0.91g, yield is 95%.1H NMR(400MHz,DMSO)δ:4.56(s,2H,-CH2-), 7.17 (d, J=6.6Hz, 2H, phH), 7.34～7.49 (m, 4H,
), phH 7.45 (d, J=6.6Hz, 2H, phH), 7.56 (s, 1H, NH)；19F NMR(376MHz,DMSO)δ:-12.59(2F),-
123.18(2F),-122.15(2F),-120.43(2F),-109.28(2F),-81.26(3F)；EI-MS m/z:638.22 (meters
Calculation value:638.00)；Anal.Calcd forC20H11F13N2O3S2:C,37.43；H,1.74；N,4.39；S,10.05；Found:
C,37.68；H,1.75；N,4.25；S,10.12.
Embodiment 8 N- (4- perfluoro hexyl sulfonyloxy benzyl) imidazoles (A6) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.1g (0.0015mmol) imidazoles, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight, Ran Houyong
Ethyl acetate (3 × 20mL) extracts, and merges organic phase, with anhydrous sodium sulfate drying, filters, and reduce pressure precipitation, by ethyl acetate
With petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A6) 0.78g, yield is 93%.1HNMR
(600MHz,DMSO)δ:5.27(s,2H,-CH2-), 6.93 (s, 1H, Ar-H), 7.20 (s, 1H, Ar-H), 7.39 (d, J=
7.8Hz, 2H, phH), 7.45 (d, J=7.8Hz, 2H, phH), 7.78 (s, 1H, Ar-H)；19F NMR(376MHz,DMSO)δ:-
125.97(2F),-122.67(2F),-121.66(2F),-120.10(2F),-109.28(2F),-80.42(3F)；EI-MS
m/z:556.01 (calculated values:556.01)；Anal.Calcd for C16H9F13N2O3S:C,34.54；H,1.63；N,5.04；S,
5.76；Found:C,35.43；H,1.54；N,5.01；S,5.84.
Embodiment 9 N- (4- perfluoro hexyl sulfonyloxy benzyl) -1,4- methylimidazole (A7) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.14g (0.0015mol) Isosorbide-5-Nitrae-methylimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A7) 0.84g, yield is 96%.1H
NMR(400MHz,DMSO)δ:2.18(s,3H,-CH3),2.29(s,3H,-CH3),5.01(s,2H,-CH2-),6.53(s,1H,
), Ar-H 7.11 (d, J=6.0Hz, 2H, phH), 7.25 (d, J=6.0Hz, 2H, phH)；19F NMR(376MHz,DMSO)δ:-
125.99(2F),-123.15(2F),-122.19(2F),-120.40(2F),-109.15(2F),-81.26(3F)；EI-MS
m/z:584.49 (calculated values:584.04)；Anal.Calcd for C18H13F13N2O3S:C,37.00；H,2.24；N,4.79；S,
5.49；Found:C,36.98；H,2.34；N,5.11；S,5.67.
Embodiment 10 N- (4- perfluoro hexyl sulfonyloxy benzyl) -2-methylimidazole (A8) synthesis
0.79g (0.0015mol) perfluoro hexyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M3), 0.12 (0.0015mol) 2-methylimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight,
Then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by second
Acetoacetic ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A8) 0.79g, yield is 91%.1H
NMR(400MHz,DMSO)δ:2.34(s,3H,-CH3),5.10(s,2H,-CH2-),6.84(s,1H,Ar-H),6.99(s,1H,
), Ar-H 7.11 (d, J=6.0Hz, 2H, phH), 7.27 (d, J=6.0Hz, 2H, phH)；19F NMR(376MHz,DMSO)δ:-
126.56(2F),-123.15(2F),-122.11(2F),-120.40(2F),-109.11(2F),-81.26(3F)；EI-MS
m/z:570.26 (calculated values:570.03)；Anal.Calcd for C17H11F13N2O3S:C,35.80；H,1.94；N,4.91；S,
5.62；Found:C,36.00；H,1.78；N,5.07；S,5.63.
Embodiment 11 N- (4- perfluoro butyl sulfonyloxy benzyl) BTA (A9) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.18g (0.0015mol) BTA, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight,
Then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by second
Acetoacetic ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A9) 0.70g, yield is 92%.1H
NMR(400MHz,DMSO)δ:6.08(s,2H,-CH2-), 7.44～7.59 (m, 6H, phH), 7.93 (d, J=3.2Hz, 1H,
), phH 7.94 (d, J=1.6Hz, 1H, phH)；19F NMR(376MHz,DMSO)δ:-125.81(2F),-121.14(2F),-
109.50(2F),-80.45(3F)；EI-MS m/z:507.56 (calculated values:507.03)；Anal.Calcd
forC17H10F9N3O3S:C,40.25；H,1.99；N,8.28；S,6.32；Found:C,40.49；H,1.96；N,8.06；S,
6.54.
Embodiment 12 N- (4- perfluoro butyl sulfonyloxy benzyl) benzimidazole (A10) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.18g (0.0015mol) benzimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight, so
Use ethyl acetate (3 × 20mL) to extract afterwards, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by acetic acid
Ethyl ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A10) 0.73g, yield is 96%.1H
NMR(600MHz,DMSO)δ:5.60(s,2H,-CH2-), 7.22 (d, J=2.4Hz, 3H, phH), 7.48 (s, 4H, phH),
7.53 (d, J=6.6Hz, 1H, phH), 7.68 (d, J=7.2Hz, 1H, phH), 8.45 (s, 1H, Ar-H)；19F NMR
(376MHz,DMSO)δ:-125.81(2F),-121.14(2F),-109.50(2F),-80.45(3F)；EI-MSm/z:506.25
(calculated value:506.03)；Anal.Calcd for C18H11F9N2O3S:C,42.70；H,2.19；N,5.53；S,6.33；
Found:C,39.68；H,1.90；N,5.12；S,6.14.
Embodiment 13 N- (4- perfluoro butyl sulfonyloxy benzyl) -1,2,4- triazole (A11) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.1g (0.0015mol) 1,2,4- triazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight,
Then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by second
Acetoacetic ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A11) 0.66g, yield is 96%.1H
NMR(600MHz,DMSO)δ:5.51(s,2H,-CH2-), 7.45 (q, J=7.8Hz, 4H, phH), 8.02 (s, 1H, Ar-H),
8.71(s,1H,Ar-H)；19F NMR(376MHz,DMSO)δ:-125.81(2F),-121.14(2F),-109.50(2F),-
80.45(3F)；EI-MS m/z:457.20 (calculated values:457.01)；Anal.Calcd for C20H11F13N2O3S:C,34.15；
H,1.76；N,9.19；S,7.01；Found:C,34.35；H,1.63；N,9.03；S,7.31.
Embodiment 14 N-4- perfluoro butyl sulfonyloxy Benzylmercapto benzothiazole (A12) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.25g (0.0015mol) mercaptobenzothiazoler, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A12) 0.76g, yield is 91%.1H NMR(600MHz,DMSO)δ:4.72(s,2H,-CH2-), 7.36～7.48 (m, 4H, phH), 7.71 (d, J=7.8Hz, 1H,
), phH 7.89 (d, J=7.8Hz, 1H, phH), 8.01 (d, J=7.8Hz, 1H, phH)；19F NMR(376MHz,DMSO)δ:-
125.81(2F),-121.14(2F),-109.50(2F),-80.45(3F)；EI-MS m/z:555.20 (calculated values:
554.97)；Anal.Calcd for C18H10F9NO3S3:C,38.92；H,1.81；N,2.52；S,17.32； Found:C,
38.74；H,1.82；N,2.52；S,17.11.
Embodiment 15 N-4- perfluoro butyl sulfonyloxy Benzylmercapto benzimidazole (A13) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.23g (0.0015mol) mercaptobenzimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A13) 0.74g, yield is 92%.1H NMR(400MHz,DMSO)δ:4.55(s,2H,-CH2-), 7.16 (d, J=6.4Hz, 2H, phH), 7.36～7.48 (m, 4H,
), phH 7.44 (d, J=6.4Hz, 2H, phH), 7.52 (s, 1H, NH)；19F NMR(376MHz,DMSO)δ:-126.59(2F),-
121.12(2F),-109.55(2F),-80.33(3F)；EI-MS m/z:538.11 (calculated values:538.01)；Anal.Calcd
for C18H11F9N2O3S2:C,40.15；H,2.06；N,5.20；S,11.91；Found:C,40.11；H,2.13；N,5.32；S,
12.07.
Embodiment 16 N- (4- perfluoro butyl sulfonyloxy benzyl) imidazoles (A14) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.1g (0.0015mmol) imidazoles, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight, Ran Houyong
Ethyl acetate (3 × 20mL) extracts, and merges organic phase, with anhydrous sodium sulfate drying, filters, and reduce pressure precipitation, by ethyl acetate
With petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A14) 0.64g, yield is 94%.1H NMR
(600MHz,DMSO)δ:5.28(s,2H,-CH2-), 6.93 (s, 1H, Ar-H), 7.22 (s, 1H, Ar-H), 7.40 (d, J=
8.4Hz, 2H, phH), 751 (d, J=8.4Hz, 2H, phH), 7.79 (s, 1H, Ar-H)；19F NMR(376MHz,DMSO)δ:-
125.81(2F),-121.14(2F),-109.50(2F),-80.45(3F)；EI-MS m/z:456.22 (calculated values:
456.02)；Anal.Calcd for C14H9F9N2O3S:C,36.85；H,2.00；N,6.14；S,7.03；Found:C,37.96；
H,2.27；N,6.15；S,6.94.
Embodiment 17 N- (4- perfluoro butyl sulfonyloxy benzyl) -1,4- methylimidazole (A15) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.14g (0.0015mol) Isosorbide-5-Nitrae-methylimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C were reacted
At night, then use ethyl acetate (3 × 20mL) to extract, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, passes through
Ethyl acetate and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A15) 0.70g, yield is 97%.1H NMR(400MHz,DMSO)δ:2.19(s,3H,-CH3),2.30(s,3H,-CH3),5.04(s,2H,-CH2-),6.53(s,
1H, Ar-H), 7.11 (d, J=6.0Hz, 2H, phH), 7.28 (d, J=6.0Hz, 2H, phH)；19F NMR(376MHz,DMSO)
δ:-126.39(2F),-121.43(2F),-109.40(2F),-81.23(3F)；EI-MS m/z:484.24 (calculated values:
484.05)；Anal.Calcd for C16H13F9N2O3S:C,39.68；H,2.71；N,5.78；S,6.62；Found:C,
39.76；H,2.66；N,5.53；S,6.60.
Embodiment 18 N- (4- perfluoro butyl sulfonyloxy benzyl) -2-methylimidazole (A16) synthesis
0.64g (0.0015mol) perfluoro butyl sulfonic acid -4- (chloromethyl) phenylester is added in the 250mL flask being dried
(M4), 0.12 (0.0015mol) 2-methylimidazole, 4.14g (0.03mol) potassium carbonate, 150mL acetonitrile, 50 DEG C are reacted overnight, so
Use ethyl acetate (3 × 20mL) to extract afterwards, merge organic phase, with anhydrous sodium sulfate drying, filter, reduce pressure precipitation, by acetic acid
Ethyl ester and petroleum ether column chromatography for separation, finally obtaining white solid is target compound (A16) 0.63g, yield is 89%.1H
NMR(400MHz,DMSO)δ:2.33(s,3H,-CH3),5.09(s,2H,-CH2-),6.84(s,1H,Ar-H),6.99(s,1H,
), Ar-H 7.11 (d, J=6.0Hz, 2H, phH), 7.27 (d, J=6.0Hz, 2H, phH)；19F NMR(376MHz,DMSO)δ:-
125.81(2F),-121.14(2F),-109.50(2F),-80.45(3F)；EI-MS m/z:470.28 (calculated values:
470.03)；Anal.Calcd for C15H11F9N2O3S:C,38.31；H,2.36；N,5.96；S,6.82；Found:C,
38.67；H,2.27；N,5.93；S,6.81.
Embodiment 19 weight-loss method tests inhibition efficiency
Add the above-mentioned fluorine-containing corrosion inhibiter of variable concentrations in the solution of 1M HCl, Q235 steel disc is cut into 1cm2, use successively
600#, 1000#, 5000# sand papering polishes, and then deionized water is ultrasonic, and EtOH Sonicate degreasing is deoiled, and nitrogen dries up title
Weight, is then placed in the fluorine-containing corrosion inhibitor solution that 40mL prepares, with the solution of 1M HCl as blank.Title is taken out after 24 hours
Weight.Three parallel laboratory tests are done in experiment every time, calculate the inhibition efficiency of corrosion inhibiter using following equation：
Inhibition efficiency=(△ W.- △ W)/△ W.× 100%
Wherein △ W is that the coupon weight before and after the steel disc experiment in fluorine-containing corrosion inhibitor solution is poor, △ W.Molten for 1M HCl
Weight difference before and after steel disc experiment in liquid.
The corrosion mitigating effect of the fluorine-containing corrosion inhibiter of table 1
The result of weight-loss method test shows, such corrosion inhibiter has excellent corrosion inhibition, in low concentration 5 × 10-4M's is slow
Erosion rate can reach more than 80%, when perfluoroalkyl is benzheterocycle and miscellaneous former containing 3 for perfluoro hexyl or perfluoro butyl, heterocycle
The fluorine-containing corrosion inhibiter of son, in low concentration 5 × 10-4During M, more than 95% can be reached to the sustained release rate of carbon steel Q235.With document report
The corrosion inhibiter in road is compared, and has significant advantage, such as the schiff bases corrosion inhibiter SB-III of Ahmed A.Faragd et al. report
(Corros.Sci.2013,74:168-177.), it is only capable of reaching 89.5% in concentration least concentration 0.5mM；Bin Xu et al.
Report heterocycle corrosion inhibiter (Corros.Sci.2013,74:206-213.) corrosion inhibition rate in concentration 0.5mM is 96%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (7)
1. a class per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter is it is characterised in that general structure is as shown in formula I：
Wherein：RfFor perfluoroalkyl, R is heterocyclic group；Described perfluoroalkyl is perfluoro butyl or perfluoro hexyl；Described is miscellaneous
Cyclic group includes triazole, BTA, mercaptobenzothiazoler, benzimidazole, mercaptobenzimidazole, imidazoles, 2- methyl miaow
Azoles, 1,4- methylimidazole.
2. per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter according to claim 1 it is characterised in that：Described perfluor
Alkylsulfonyloxy benzyl heterocycle corrosion inhibiter includes N- (4- perfluoro hexyl sulfonyloxy benzyl) BTA, N- (4- perfluor
Hexyl sulfonyloxy benzyl) benzimidazole, N- (4- perfluoro hexyl sulfonyloxy benzyl) -1,2,4- triazoles, N-4- perfluor is own
Base sulfonyloxy Benzylmercapto benzothiazole, N-4- perfluoro hexyl sulfonyloxy Benzylmercapto benzimidazole, N- (4- perfluoro hexyl
Sulfonyloxy benzyl) imidazoles, N- (4- perfluoro hexyl sulfonyloxy benzyl)-Isosorbide-5-Nitrae-methylimidazole, N- (4- perfluoro hexyl sulphonyl
Oxy-benzyl) -2-methylimidazole, N- (4- perfluoro butyl sulfonyloxy benzyl) BTA, N- (4- perfluoro butyl sulphonyl oxygen
Base benzyl) benzimidazole, N- (4- perfluoro butyl sulfonyloxy benzyl) -1,2,4- triazoles, N-4- perfluoro butyl sulfonyloxy
Benzylmercapto benzothiazole, N-4- perfluoro butyl sulfonyloxy Benzylmercapto benzimidazole, N- (4- perfluoro butyl sulfonyloxy benzyl
Base) imidazoles, N- (4- perfluoro butyl sulfonyloxy benzyl)-Isosorbide-5-Nitrae-methylimidazole, N- (4- perfluoro butyl sulfonyloxy benzyl)-
2-methylimidazole.
3. the preparation method of the per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter described in claim 1 or 2 is it is characterised in that wrap
Include following steps：
(1) p-Hydroxybenzylalcohol, in the presence of acid binding agent, occurs nucleophilic displacement of fluorine anti-with perfluoroalkyl sulfonyl fluoride in organic solvent
Should, obtain intermediate perfluoro alkyl sulfonic acid -4- (methylol) phenylester；
(2) perfluoro alkyl sulfonic acid -4- (methylol) phenylester is reacted with halogenating agent in organic solvent and obtains intermediate perfluor
Alkyl sulfonic acid -4- (halomethyl) phenylester；
(3) perfluoro alkyl sulfonic acid -4- (halomethyl) phenylester is in the presence of acid binding agent, anti-with heterocyclic compound in organic solvent
Per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter should be obtained.
4. per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter according to claim 3 preparation method it is characterised in that：
Acid binding agent described in step (1) and step (3) is potassium carbonate, and described organic solvent is acetonitrile.
5. per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter according to claim 3 preparation method it is characterised in that：
Organic solvent described in step (2) is Isosorbide-5-Nitrae-dioxane, and described halogenating agent is thionyl chloride.
6. per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter according to claim 3 preparation method it is characterised in that：
Heterocyclic compound described in step (3) is BTA, benzimidazole, 1,2,4- triazole, mercaptobenzothiazoler, sulfydryl
Benzimidazole, 1,4- methylimidazole, 2-methylimidazole or imidazoles.
7. per-fluoroalkyl sulfonyl oxy-benzyl heterocycle corrosion inhibiter according to claim 3 preparation method it is characterised in that：
Perfluoroalkyl sulfonyl fluoride described in step (1) is perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfuryl fluoride, the centre obtaining
Body is perfluoro butyl sulfonic acid -4- (methylol) phenylester or perfluoro hexyl sulfonic acid -4- (methylol) phenylester；
Halogenating agent described in step (2) is thionyl chloride, and the intermediate obtaining is perfluoro butyl sulfonic acid -4- (chloromethyl) benzene
Base ester or perfluoro hexyl sulfonic acid 4- (chloromethyl) phenylester.
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