CN102634814A - Method for electrochemically synthesizing oxime - Google Patents
Method for electrochemically synthesizing oxime Download PDFInfo
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- CN102634814A CN102634814A CN2012101564784A CN201210156478A CN102634814A CN 102634814 A CN102634814 A CN 102634814A CN 2012101564784 A CN2012101564784 A CN 2012101564784A CN 201210156478 A CN201210156478 A CN 201210156478A CN 102634814 A CN102634814 A CN 102634814A
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Abstract
The invention relates to a method for electrochemically synthesizing oxime. The method comprises the following steps: adding a substrate of benzyl alcohol or similar structure, stannous chloride, and electrolyte aqueous solution containing nitrate radical into an electrolytic cell; at room temperature, applying a constant-current power supply on electrodes in the electrolytic cell for electrolysis; and then separating and purifying the solution to obtain oxime.
Description
Technical field
The invention belongs to organic chemistry compound method field, be meant a kind of method of electrochemical synthesis oxime especially.
Background technology
Oxime is a kind of important synthetics, not only can dewater to generate nitrile but also can reset through an acid catalysis Beckmann to generate acid amides.In addition, oxime is typical anti-inflammatory, antibacterial medicine.Usually, the traditional method of synthetic oxime is an aldehyde, the reaction of ketone and oxammonium hydrochloride.Although this method is generally used, using on the oxammonium hydrochloride safety has problem, particularly in a large amount of uses, has quite dangerous.Therefore original position generation oxammonium hydrochloride is the new challenge that chemists face in reaction system.The report that existing original position generates oxammonium hydrochloride has: generate oxammonium hydrochloride (J.Am.Chem.Soc.2001,123,8153 with dioxygen oxidation ammoniacal liquor original position; Catal.Today, 1998,41,443; J.Am.Chem.Soc.1980,102,1453), variously on the other hand non-ly all generate oxammonium hydrochloride report (J.Mol.Catal.A:Chem.1997,117,367 are also arranged to catalyst ammoniacal liquor and hydroperoxidation original position; Catal.Commun.2002,3,369; Appl.Catal.A, 2001,221,359; J.Catal.1997,168,400; Appl.Catal.A, 1996,136,69; Microporous Mesoporous Mater.2004,68,29; Ind.Eng.Chem.Res.2004,43,166; Chem.Eng.Technol.2004,27,176; Green Chem.2006,8,679).In addition, also can obtain oxime (Sodium salt of tungstic acids:Angew.Chem.1960,72,135 with hydrogen peroxide or atmospheric oxidation primary amine; B) Peroxo tungstophosphate:Chem.Lett.1992,289; C) [Mo (O) (O
2) (H
2O) (hmpa)] (hmpa=hexamethylphosphoramide): 1) J.Mol.Catal.1993,83,311; 2) Appl.Catal.A 1995,128, and 231; D) Titanium silicate:J.Chem.Soc. Perkin Trans.l 1993,2665; E) Methyltrioxorhenium (MTO): Bull.Chem.Soc.Jpn.1997,70,877; F) 1,1-diphenyl-2-picrylhydrazyl (DPPH) and WO
3/ Al
2O
3: Angew.Chem.Int.Ed.2008,47,2079).Recently, under the condition that various reductive agents exist, like the complex catalysis nitrogen protoxide of Co or Fe or alkyl nitrite alkene is carried out nitrosification and also can obtain oxime (J.Org.Chem., 1987,52,5089; J.Org.Chem., 1988,53,4897; Chem.Lett., 1990,19,1395; Chem.Lett., 1990,19,1917; Bull.Chem.Soc.Jpn., 1991,64,2948; Synlett, 1998,1270; Chem.Commun., 2009,45,1990).But up to the present, the nitrogenous source of original position synthesizing hydroxyamine is still very limited.
In current society; Used a large amount of fertilizer and industry to go up a large amount of nitrate salt that use on the agricultural and caused the serious azotate pollution of water quality and industrial soil, and nitrate salt can change into deleterious nitrite under the reductive action of intravital some bacterium of the mankind.Therefore the denitrogenation development of science and technology is just becoming particularly important aspect protection environment and the human health.A series of denitride technology occurs like the mushrooms after rain, as: biological denitrificaion, IX r-o-and chemical reduction and catalytic reduction etc.Comparatively speaking and since electronics compared with conventional oxidation also original reagent be eco-friendly, the electrochemistry denitrogenation has obtained very big concern as a kind of environment-friendly method.Electrochemical reduction nitrate salt and nitrite all have report on various electrodes.According to existing report (For the selected references for electrochemical reduction of nitrate and nitrite:Chem.Commun., 2005,4534; Coord.Rev.Chem.2000,199,159; Electrochim.Acta, 2005,50,5237; Electrochim.Acta, 2007,52,6237; J.Electroanal.Chem., 2004,572,93; J.Am.Chem.Soc.2007,129,10171; J.Am.Chem.Soc.2009,131,10860), electrochemistry is reduced nitrate salt and is produced eight kinds of possible products on various electrodes, be respectively NO
2, NO
2 -, NO, N
2O, N
2, NH
2OH, NH
3And NH
2NH
2, and principal product is N
2, NH
4OH and NO.And saltpetre had not had report so far as the synthetic nitrogen-containing organic compound of nitrogenous source however.
The contriver is devoted to develop new organic electrosynthesis method (Org.Lett.2005,7,1903 always; Tetrahedron Lett.2010,51,1426; Synlett, 2010,13,1915; Chem.Commun.2010,46,7196; Chem.Commun.2011,47,5488).Contriver's design is as shown in Figure 1, is example with benzylalcohol as substrate, and at first, the benzylalcohol oxidation generates phenyl aldehyde on anode, on the negative electrode Sn takes place simultaneously
2+To the reduction of metallic tin, the saltpetre original position in the tin reducing solution that deposits generates azanol, thereby generates benzaldoxime with phenyl aldehyde.
Summary of the invention
The purpose of this invention is to provide a kind of technical scheme of synthetic oxime compounds of safe green, and realized effectively utilizing saltpetre to synthesize oxime from pure series electrical as nitrogenous source.
The present invention realizes through following technical scheme:
A kind of method of electrochemical synthesis oxime may further comprise the steps:
With benzylalcohol class or similar structures substrate, tindichloride, the aqueous electrolyte liquid that contains nitrate radical adds in the electrolyzer; At room temperature the electrode in the electrolyzer is fed the constant current power supply electrolysis; Reacted solution is separated the back of purifying obtain oxime.
In said synthetic oxime method, also be added with promotor.
The structural formula of said benzylalcohol class is R1-OH-R2, and wherein R1 includes: C6H5,4-CH3C6H5,4-CH3OC6H5,4-CF3C6H5,4-FC6H5,4-BrC6H5,4-ClC6H5,2-ClC6H5,3-ClC6H5, C6H5; R2 includes H, CH3; Said similar structures substrate includes: 1-phenylethyl alcohol, hexalin, Resorcinol.
The described aqueous electrolyte liquid that contains nitrate radical includes saltpetre, SODIUMNITRATE, zinc nitrate, an ammonium nitrate and other nitrate aqueous solution; Be preferably the saltpetre aqueous solution.
Said promotor includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, aqua ammonia; Said promotor is 3 with the ratio of the amount of substance of benzylalcohol class or similar structures substrate: 2-3: 1.
Described promotor is preferably hydrochloric acid.
Said benzylalcohol class or similar structures substrate are 1 with the ratio of the amount of substance of tindichloride: 1-2: 1.
The said aqueous electrolyte liquid that contains nitrate radical is preferably saturated aqueous solution.
The preferred platinum electrode of the electrode of said electrolyzer is as anode, and the indium tin oxide glass electrode is as negative electrode.
Described separate mode can be selected spinning, distillation, and extraction waits liquid liquid separate mode; Be preferably the extracting and separating mode.
The invention has the beneficial effects as follows:
1. saltpetre is used as the nitrogenous source of oxime first, and nitrate salt or nitrite all are not applied in the new reaction except in the long-pending nitrated in position reaction of classics, being used as the nitrogenous source always.
2. reaction conditions is gentle, does not need very expensive catalysts, can at room temperature carry out smoothly.So both reduce the energy consumption in the production process, also reduced the generation of side reaction.
3. reaction is carried out at aqueous phase, compared with the more more environmental protection of green of system of organic solvent.
Description of drawings
Fig. 1 is from the synthetic oxime reaction of one pot of series electrical of alcohol synoptic diagram;
Fig. 2 is deposited on the XRD figure of the metallic tin on the Graphite Electrodes;
Fig. 3 is deposited on the XRD figure of the metallic tin on the ITO electrode;
Fig. 4 is deposited on the XRD figure of the metallic tin on the platinum electrode;
Fig. 5, the SEM that is deposited on the metallic tin on the ITO electrode schemes;
Fig. 6, the SEM that is deposited on the metallic tin on the Graphite Electrodes schemes;
Fig. 7, the SEM that is deposited on the metallic tin on the platinum electrode schemes;
Fig. 8, the SEM that is deposited on the metallic tin on the ITO electrode schemes;
Fig. 9, instance 1 gained H NMR figure;
Figure 10, instance 1 gained C NMR figure;
Figure 11, instance 2 gained H NMR figure;
Figure 12, instance 2 gained C NMR figure;
Figure 13, instance 3 gained H NMR figure;
Figure 14, instance 3 gained C NMR figure;
Figure 15, instance 4 gained H NMR figure;
Figure 16, instance 4 gained C NMR figure;
Figure 17, instance 5 gained H NMR figure;
Figure 18, instance 5 gained C NMR figure;
Figure 19, instance 6 gained H NMR figure;
Figure 20, instance 6 gained C NMR figure;
Figure 21, instance 7 gained H NMR figure;
Figure 22, instance 7 gained C NMR figure;
Figure 23, instance 8 gained H NMR figure;
Figure 24, instance 8 gained C NMR figure;
Figure 25, instance 9 gained H NMR figure;
Figure 26, instance 9 gained C NMR figure;
Figure 27, instance 10 gained H NMR figure;
Figure 28, instance 10 gained C NMR figure;
Figure 29, instance 11 gained H NMR figure;
Figure 30, instance 11 gained C NMR figure;
Figure 31, instance 12 gained H NMR figure;
Figure 32, instance 12 gained C NMR figure;
Embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings.Be exemplary through the embodiment that is described with reference to the drawings below, only be used to explain the present invention, and can not be interpreted as limitation of the present invention.
A kind of method of electrochemical synthesis oxime may further comprise the steps:
1), with benzylalcohol class or similar structures substrate, tindichloride, the aqueous electrolyte liquid that contains nitrate radical adds in the electrolyzer; Said electrolyzer can use whisking appliance according to the amount decision of producing, and preferably uses whisking appliance in order to improve reaction efficiency; Also consider to add promotor in order to improve speed of reaction.
The structural formula of said benzylalcohol class is R
1-OH-R
2, R wherein
1Include: C
6H
5, 4-CH
3C
6H
5, 4-CH
3OC
6H
5, 4-CF
3C
6H
5, 4-FC
6H
5, 4-BrC
6H
5, 4-ClC
6H
5, 2-ClC
6H
5, 3-ClC
6H
5, C
6H
5R
2Include H, CH
3Said similar structures substrate includes: 1-phenylethyl alcohol, hexalin, Resorcinol.
The described aqueous electrolyte liquid that contains nitrate radical includes saltpetre, SODIUMNITRATE, zinc nitrate, an ammonium nitrate and other nitrate aqueous solution; Be preferably the saltpetre aqueous solution; The said aqueous electrolyte liquid that contains nitrate radical is preferably saturated aqueous solution.
The preferred platinum electrode of the electrode of said electrolyzer is as anode, and the indium tin oxide glass electrode is as negative electrode.
Said promotor includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, aqua ammonia; Said promotor is 3 with the ratio of the amount of substance of benzylalcohol class or similar structures substrate: 2-3: 1.
Said benzylalcohol class or similar structures substrate are 1 with the ratio of the amount of substance of tindichloride: 1-2: 1.
2), at room temperature the electrode in the electrolyzer was fed the constant current power supply electrolysis more than 4 hours; Said room temperature is 20 degrees centigrade-35 degrees centigrade.Constant current power supply is according to producing and different improvement of experiment, and the electrolytic time is inversely proportional to the power that the amount of producing is directly proportional with power supply; Constant current is generally with the constant current power supply of 20mA-30mA; In the industrial production of reality; According to the variation of the electrolyzer of selecting for use and the requirement of output, electric current has corresponding variation, and constant current is the requirement of technical scheme in the present technique scheme; But the concrete magnitude of current is not done concrete standard, all belongs to the scope of present technique scheme as long as can realize the magnitude of current of the purpose of this patent.
3), after being separated purification operations, reacted solution obtains oxime.Lock out operation can be selected spinning in the present invention, distillation, and extraction waits liquid liquid separate mode; Be preferably the extracting and separating mode.
What select in an embodiment of the present invention is the extracting and separating mode; And adopt extracting operation three times; In the production of reality; In order to increase work efficiency, with the solution of extraction for the third time as the extraction agent for the first time of round-robin next time, only with the first time in each circulation with the second time extraction solution carry out extraction agent and separate; The extraction agent of selecting for use in this application is an ETHYLE ACETATE, and this is not that other extraction agent is not the application's requirement just, all can use as long as meet the extraction agent of extracted character.
The equation of reaction is:
The application has realized effectively utilizing saltpetre to synthesize oxime as nitrogenous source from pure series electrical first.Preliminary study result shows that sedimentary hollow ball tin is the key factor of reduction saltpetre to azanol, and reaction system is clean, and by product seldom.High efficiency of this method and environment friendly become the good method of synthetic oxime by it.
Concrete implementation procedure is following: initial, the condition optimizing of system is carried out in this reaction, and as shown in table 1.Mmol refers to mmole in this application; On an indiscrete electrolyzer, is furnished with a pair of graphite rod electrode; With benzylalcohol (2mmol), tindichloride (1mmol) and saturated potassium nitrate solution (6mL) are put into electrolyzer respectively, continuous current 25mA electrolysis 4 hours under the condition of stirring at room.After reaction finishes, with ethyl acetate extraction three times (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards.Obtained 47% product oxime (table 1, the 1st row).In order to improve the productive rate of reaction, in system, add hydrochloric acid, electrolysis time extends to 6 hours, and at this moment reaction yield has been brought up to 73% (table 1, the 2nd row).Nitrogenous source Sodium Nitrite and ammonium chloride that it should be noted that traditional generation azanol do not obtain product oxime (table 1, the 8th and 9 row) in the application's system.Also using sulfuric acid, nitric acid, acetic acid to replace hydrochloric acid to participate in being reflected in this application also has oxime to generate (table 1,3-5 is capable) in the system.At last, through the influence of analyzing electrode, the result shows that platinum electrode is suitable as anodic oxidation alcohol, and indium tin oxide glass electrode (ITO; Nan Bo group, Shenzhen, China) be more suitable for as cathodic reduction tindichloride (table 1,10-13 is capable).The entire reaction tindichloride is necessary.When not adding tindichloride in the system, almost there is not oxime to produce (table 1, the 14th row).That is to say that direct reduction saltpetre almost can not get azanol on electrode.The metallic tin that this explanation deposits out generates azanol for reduction saltpetre original position has very crucial effect.In addition, we have also attempted the promoted oximation reaction of metallic zinc under the alkaline condition, can obtain the oxime (table 1,15 row) of moderate yield.In sum, the standard conditions of reaction are confirmed as: saltpetre is as nitrogenous source, and platinum electrode is as anode, and the ITO electrode is as negative electrode.
One pot in table 1 is from the synthetic oxime condition optimizing form of pure series electrical
Under optimal conditions, in order to expand the scope of reaction substrate, the application has attempted various substituted alcohol, and is as shown in table 2.The aromatic alcohol that on phenyl ring, has weak electron-donating group or halogenic substituent can well react, and the yield of product is all at (table 2, the 1st, 2,5-9 is capable) more than 80%.When strong electron-donating group or strong electron-withdrawing group are arranged on the phenyl ring, be unfavorable for reaction, corresponding oxime product obtains moderate yield (table 2,3-4 is capable).When halogens chlorine is substituted on the phenyl ring different positions, can observe slight steric hindrance effect.When chlorine during at the ortho position reaction yield reduction (table 2,7-9 is capable) is a little arranged.In addition, the application has also attempted the secondary alcohol substrate.The 1-phenylethyl alcohol obtains ketoxime moderate yield (table 2, the 10th row).Fat secondary alcohol hexalin has also obtained moderate yield (table 2, the 11st row).Attempted Resorcinol at last, the anodic oxidation Resorcinol generates the benzoquinone, and obtaining the ketoxime productive rate at last is 52% (table 2, the 12nd row).
One pot of substrate from the synthetic oxime of pure series electrical of table 2 is expanded
For the key of the mechanism of understanding reaction and the reaction of the one-tenth oxime in the proof diagram 1 is to have generated azanol, azanol is caught, the result has confirmed this imagination.As mentioned above, if in the application's system, do not add tindichloride, and, be (table 1, the 14th row) that does not almost have oxime to produce, so the tin that electrolysis produces is the key factor of reduction saltpetre directly at electrode surface reduction saltpetre.In addition, in electrolytic process, the pattern of the tin that deposition is come out on the negative electrode of differing materials is different.That on graphite and platinum electrode, separates out has metalluster, to such an extent as to and the tin of on the ITO electrode, separating out is too little distinguishes with eyes unable.The tin that on three kinds of electrodes, deposits sem (SEM) and X-ray diffraction (XRD) have been tested.The X-ray diffraction result shows that these tin all are β phase tin, like Fig. 2, and Fig. 3 and shown in Figure 4.Sem result shows that be deposited on the ITO electrode surface is dispersive spherical (Fig. 5), on the platinum electrode is the ball (Fig. 7) of reunion and to be deposited on Graphite Electrodes be rock-like (Fig. 6) with being deposited on.In further studying, prolong depositing time, find that the tin ball of ITO electrode surface is hollow (Fig. 8); So; Under the condition of deposition equivalent metallic tin, the specific surface area of the spherical tin of dispersive is spherical big more a lot of than rock-like and reunion, and the specific surface area difference causes the catalytic reaction activity that a great difference is arranged; Perhaps, this is exactly the major cause (table 1,10-13 is capable) of these three kinds of electrode reaction productive rate differences.
It below is the application's specific embodiment; Employed in an embodiment all material is the AR of direct purchase; Use preceding without other processing; What the catalyzer that uses was selected for use is that concentration of hydrochloric acid is 12mol/L, also can select other concentration for use, carries out corresponding calculated and guarantees that amount of substance gets final product.In actual production, each material can be selected industrial grade purity or other purity for use, does not influence the realization of patent art scheme.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.Benzylalcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 1 (Fig. 9 and Figure 10).Send the nuclear-magnetism test with pure article,
1H NMR (NMR spectrum) shows the productive rate 87% of compound benzaldoxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.75(s,1H),8.17(s,1H),7.60-7.50(m,2H),7.40-7.30(m,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=150.5,130.2,128.9,127.2;IR(liquid?film,cm
-1):v=3304,3063,1498,1449,1302,1210,953,870,756,692.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.To xylyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 2 (Figure 11 and Figure 12).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 89% of compound p-tolyl aldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.13(s,1H),7.47(d,J=7.8Hz,2H),7.19(d,J=7.8Hz,2H),2.36(s,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=151,140,131,129,127,21.6;IR(liquid?film,cm
-1):v=3289,2922,1448,1300,1112,?960,816,714.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.P-methoxybenzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 3 (Figure 13 and Figure 14).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 68% of compound aubepine oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.11(s,1H),7.52(d,J=8.7Hz,2H),6.91(d,J=8.7Hz,2H),3.84(s,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=150,129,114,55;IR(liquid?film,cm
-1):v=3353,2929,1606,1513,1303,1253,1174,1030,956,874,831.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.To trifluoromethyl-benzyl-alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 4 (Figure 15 and Figure 16).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 57% of compound to the trifluoromethylated benzaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.18(s,1H),8.00(s,1H),7.80-7.50(m,4H);
13C-NMR(CDCl
3,75MHz,ppm):δ=149.2,127.4,125.9,125.9,125.8,125.8;IR(liquid?film,cm
-1):v=3355,2928,1618,1412,1325,1168,1128,1067,?968,837.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.To fluoro benzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 5 (Figure 17 and Figure 18).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 81% of compound p-Fluorobenzenecarboxaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.12(s,1H),7.60-7.50(m,2H),7.20-7.00(m,2H);
13C-NMR(CDCl
3,75MHz,ppm):δ=165.0,162.5,149.3,128.9,128.8,116.0,115.8;IR(liquid?film,cm
-1):v=3262,1605,1511,1323,1294,1241,972,878,827.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.To bromobenzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 6 (Figure 19 and Figure 20).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 87% of compound p-bromobenzaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.09(s,1H),7.70-7.30(m,4H);?
13C-NMR(CDCl
3,75MHz,ppm):δ=149.5,132.1,128.5;IR(liquid?film,cm
-1):v=3202,2922,1493,1393,1317,1067,970,871,820.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.P-Chlorobenzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 7 (Figure 21 and Figure 22).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 90% of compound 4-chloro-benzaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.13(s,1H),8.11(s,1H),7.55-7.50(m,2H),7.40-7.30(m,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=149.5,129.2,128.4;IR(liquid?film,cm
-1):v=3312,2924,1494,1089,972,874,825,696,506.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.Adjacent chlorobenzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 8 (Figure 23 and Figure 24).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 83% of compound o-chlorobenzaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.57(s,1H),7.84(d,J=2.0Hz,1H),7.83-7.20(m,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=147,133,130,129,127,126;IR(liquid?film,cm
-1):v=3288,2929,1483,1436,1316,1279,1206,1045,973,749,705.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.Between chlorobenzyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 9 (Figure 25 and Figure 26).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 92% of compound m chlorobenzaldehyde oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=8.11(s,1H),7.58(s,1H),7.57-7.30(m,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=149.4,135,134,130,127,125;IR(liquid?film,cm
-1):v=3303,2925,1566,1481,1317,1208,1077,954,873,781,710,675.
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.1-xylyl alcohol (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 10 (Figure 27 and Figure 28).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 54% of compound acetophenone oxime.
1H-NMR(CDCl
3,300MHz,ppm):δ=7.80-7.50(m,2H),7.50-7.20(m,3H),2.30(s,3H);
13C-NMR(CDCl
3,75MHz,ppm):δ=156.2,136.7,129.4,128.7,126.2,12.5;IR(liquid?film,cm
-1):v=3249,1449,1370,1302,1005,925,764.
Instance 11
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.Hexalin (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 11 (Figure 29 and Figure 30).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 47% of compound OxiKhim-Styrol.
1H-NMR(CDCl
3,300MHz,ppm):δ=2.54-2.49(m,2H),2.30-2.10(m,2H),1.80-1.60(m,6H);
13C-NMR(CDCl
3,75MHz,ppm):δ=161,32.3,27.0,25.9,25.7,24.6;IR(liquid?film,cm
-1):v=3188,3112,2932,2860,1664,1449,993,962,900,794.
Instance 12
Use the non-electrolyzer that separates, platinum electrode is a working electrode, and the ITO electrode is a counter electrode, one of magnetic agitation.Pyrogentisinic Acid (2mmol), tindichloride (1mmol), hydrochloric acid (0.25mL) and saltpetre saturated solution (6mL) add electrolyzer.At room temperature, while electrolysis 6 hours (2.8F/mol) is stirred in electrolysis under continuous current 25mA condition.After reaction finishes, with ethyl acetate extraction (3 * 10mL), with Rotary Evaporators solvent is revolved and to do chromatographic separation afterwards, promptly get product compound 12 (Figure 31 and Figure 32).Send the nuclear-magnetism test with pure article,
1H NMR shows the productive rate 52% of compound benzoquinones ketoxime.
1H-NMR(CD
3COCD
3,300MHz,ppm):δ=7.74(s,2H),6.76(s,4H);?
13C-NMR(CD
3COCD
3,75MHz,ppm):δ=151,116;IR(liquid?film,cm
-1):v=3161,3030,1513,1460,1194,832,760,524.
In other embodiment of the application, benzylalcohol class or other similar substrate with the ratio of the amount of substance of tindichloride 1: 1-1: between 2, the application can't all embodiment of limit, only can select representational limited embodiment to do the application's explanation.
Although illustrated and described embodiments of the invention; For those of ordinary skill in the art; Be appreciated that under the situation that does not break away from principle of the present invention and spirit and can carry out multiple variation, modification, replacement or modification to these embodiment, scope of the present invention is limited accompanying claims and equivalent thereof.
Claims (10)
1. the method for an electrochemical synthesis oxime is characterized in that, may further comprise the steps:
With benzylalcohol class or similar structures substrate, tindichloride, the aqueous electrolyte liquid that contains nitrate radical adds in the electrolyzer; Electrode in the electrolyzer is fed the constant current power supply electrolysis; Reacted solution is separated the back of purifying obtain oxime.
2. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that, also add promotor in the said step.
3. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that the structural formula of said benzylalcohol class is R1-OH-R2, wherein R1 includes: C6H5; 4-CH3C6H5,4-CH3OC6H5,4-CF3C6H5; 4-FC6H5,4-BrC6H5,4-ClC6H5; 2-ClC6H5,3-ClC6H5, C6H5; R2 includes H, CH3; Said similar structures substrate includes: 1-phenylethyl alcohol, hexalin, Resorcinol.
4. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that the described aqueous electrolyte liquid that contains nitrate radical includes saltpetre, SODIUMNITRATE, zinc nitrate, an ammonium nitrate and other nitrate aqueous solution; Be preferably the saltpetre aqueous solution.
5. according to the method for the electrochemical synthesis oxime described in the claim 2, it is characterized in that said promotor includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, aqua ammonia; Said promotor is preferably hydrochloric acid; Said promotor is 3 with the ratio of the amount of substance of benzylalcohol class or similar structures substrate: 2-3: 1.
6. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that said benzylalcohol class or similar structures substrate are 1 with the ratio of the amount of substance of tindichloride: 1-2: 1.
7. according to the method for the electrochemical synthesis oxime described in claim 1 or 4, it is characterized in that the said aqueous electrolyte liquid that contains nitrate radical is preferably saturated aqueous solution.
8. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that the preferred platinum electrode of the electrode of said electrolyzer is as anode, the indium tin oxide glass electrode is as negative electrode.
9. according to the method for the electrochemical synthesis oxime described in the claim 1, it is characterized in that: described separate mode can be selected spinning, distillation, and extraction waits liquid liquid separate mode; Be preferably the extracting and separating mode.
10. according to the method for the electrochemical synthesis oxime described in the claim 9, it is characterized in that described extraction agent is preferably ETHYLE ACETATE.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106757137A (en) * | 2016-12-14 | 2017-05-31 | 重庆紫光化工股份有限公司 | The clean preparation method and system of a kind of methylmercaptan ethyl aldoxime |
| CN107986987A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method of hexamethylene ammoxidation from methanol |
| CN109136972A (en) * | 2017-06-28 | 2019-01-04 | 中国科学技术大学 | A kind of preparation method of substituted phosphoramide types compound |
| WO2023198025A1 (en) * | 2022-04-11 | 2023-10-19 | 中山大学 | Synthesis method and synthesis device for organic nitrogen-containing compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986987A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method of hexamethylene ammoxidation from methanol |
| CN107986987B (en) * | 2016-10-27 | 2020-12-04 | 中国石油化工股份有限公司 | Cyclohexanol ammoxidation method |
| CN106757137A (en) * | 2016-12-14 | 2017-05-31 | 重庆紫光化工股份有限公司 | The clean preparation method and system of a kind of methylmercaptan ethyl aldoxime |
| CN106757137B (en) * | 2016-12-14 | 2018-10-26 | 重庆紫光化工股份有限公司 | A kind of clean preparation method and system of methylmercaptan ethyl aldoxime |
| CN109136972A (en) * | 2017-06-28 | 2019-01-04 | 中国科学技术大学 | A kind of preparation method of substituted phosphoramide types compound |
| WO2023198025A1 (en) * | 2022-04-11 | 2023-10-19 | 中山大学 | Synthesis method and synthesis device for organic nitrogen-containing compound |
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