CN102911079B - The method of-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate is prepared by ketoxime ether - Google Patents
The method of-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate is prepared by ketoxime ether Download PDFInfo
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Abstract
The present invention relates to a kind of method being prepared-oxyl amine hydrochlorate by ketoxime ether, the method comprises: acetoxime ether or Diacetylmonoxime ether are injected rectifying tower continuously from the first opening for feed, aqueous hydrochloric acid is injected rectifying tower continuously from the second opening for feed, and-oxyl amine hydrochlorate is isolated from liquid at the bottom of the tower of described rectifying tower, wherein, stage number at the bottom of described first opening for feed to tower or theoretical plate number D1 and at the bottom of described second opening for feed to tower stage number or theoretical plate number D2 account for total stage number of described rectifying tower or the 30-80% of theoretical plate number separately, and D1 < D2.Method according to the present invention, not only can not use extra organic solvent, and due to collection reaction be located away from one, therefore can also high purity, obtain target product with high yield, decrease the step be separated separately, thus reach the object reducing production cost.
Description
Technical field
The present invention relates to a kind of method being prepared-oxyl amine hydrochlorate by ketoxime ether, and a kind of preparation method of-oxyl amine hydrochlorate.
Background technology
-oxyl amine hydrochlorate has another name called O-substituted hydrocarbon radical oxammonium hydrochloride, and its general formula is H
2nOR
1hCl, wherein, R
1can be C
1-C
6alkyl, C
2-C
6thiazolinyl, C
7-C
13aryl and the halides (halogen can be such as Br, Cl etc.) of these groups.
-oxyl amine hydrochlorate is the of many uses and expensive organic synthesis intermediate of a class, this compounds can be used as the aminated reagent of alcoxyl, in organic synthesis and new drug are produced, alcoxyl amine groups is incorporated into ketone compounds (particularly steroide); Can be used as the intermediate that the weedicide such as medicine cefuroxime side chain and agricultural chemicals methoxyphenone, clethodim, sethoxydim is produced, also can be used as the intermediate in new pharmaceutical and New pesticides discovery field.
Method at present for the synthesis of alcoxyl amido hydrochloride has: season Yongxin (chemistry and bonding, 2001,5, the technological process of synthesis alcoxyl amido hydrochloride 200-202) introduced comprises: react with sodium bisulfite and sulfurous gas and Sodium Nitrite and generate azanol S-WAT, then through alkylation, hydrolysis, in and salify generation product.But, this technological process will use sulfur dioxide liquid and Sodium Nitrite, and toxicity is large and seriously polluted, produces one ton of product simultaneously and will produce more than the ten ton of waste water containing a large amount of sodium sulfate, and produce the waste gas such as a large amount of oxynitride, thus in safety, environmental protection, there is certain problem.
(fine chemical material and the intermediate such as Li Wenxiao; 2007,22-23,29) describe and utilize ethyl acetate and azanol to carry out oximation reaction; after protecting N, then carry out being hydrolyzed the technique preparing ethoxy amine again after ethylization generates ether with ethyl sulfate.Wherein, after ethylization, want underpressure distillation to remove the impurity such as N-ethyl-O-ethylamine, acid hydrolysis, neutralization, distillation obtain ethoxy amine, and yield is about 85%, but existence distillation removal of impurities is difficult to be effective, the unmanageable problems of processing condition such as ethylization.
Namely US 4981996A discloses the preparation method of a kind of O-substituted alkyl oxammonium hydrochloride (also alcoxyl amido hydrochloride), the method comprises to be made hydroxylamine-o-sulfonic acid and alkali metal alkoxide react in polar solvent directly to prepare O-substituted alkyl oxammonium hydrochloride.But the method needs to adopt more dangerous oleum, and the-oxyl amine generated needs underpressure distillation under a certain pressure, and operational condition relative difficult controls, and the method can produce more spent acid, brings very large pressure to follow-up refuse process.
In order to solve the problems of the technologies described above, those skilled in the art once attempted acetoxime ether or Diacetylmonoxime ether and hydrochloric acid contact reacts, and at the bottom of tower, isolated-oxyl amine hydrochlorate by distillation tower.But, be difficult to suitability for industrialized production because the method exists following shortcoming:
(1) in order to realize, the acetone in gained mixture after reaction or butanone are separated with-oxyl amine hydrochlorate in the method, need in reaction system, additionally add organic solvent (as toluene, hexane etc.), make the operating process of fractionation by distillation have higher danger;
(2) reaction times is longer, and side reaction is more, thus causes the yield of-oxyl amine hydrochlorate lower;
(3) the method can only implement batch production, causes production capacity lower.
Summary of the invention
There is the lower shortcoming of operational hazards and yield and productive rate in the preparation method that the object of the invention is to overcome existing-oxyl amine hydrochlorate, provides a kind of method being prepared-oxyl amine hydrochlorate by ketoxime ether newly.
The invention provides a kind of method being prepared-oxyl amine hydrochlorate by ketoxime ether, the method comprises: acetoxime ether or Diacetylmonoxime ether are injected rectifying tower continuously from the first opening for feed, aqueous hydrochloric acid is injected rectifying tower continuously from the second opening for feed, and-oxyl amine hydrochlorate is isolated from liquid at the bottom of the tower of described rectifying tower, wherein, stage number at the bottom of described first opening for feed to tower or theoretical plate number D1 and at the bottom of described second opening for feed to tower stage number or theoretical plate number D2 account for total stage number of described rectifying tower or the 30-80% of theoretical plate number separately, and D1 < D2.
Present invention also offers a kind of preparation method of-oxyl amine hydrochlorate, the method comprises the following steps:
(1) under ketone oxamidinating reaction conditions, under the existence of titanium-silicon molecular sieve catalyst, the acetone be dissolved in organic solvent or butanone, hydrogen peroxide and ammonia are fed to contact reacts in reactor, obtain acetoxime or Diacetylmonoxime, wherein, the mol ratio of hydrogen peroxide and acetone or butanone is 1-1.3;
(2) under substitution reaction condition, the acetoxime obtained or Diacetylmonoxime and halocarbon are reacted, and isolate acetoxime ether or Diacetylmonoxime ether the product obtained after this contact reacts in step (1);
(3) adopt the above-mentioned method being prepared-oxyl amine hydrochlorate by ketoxime ether the acetoxime ether obtained in step (2) or Diacetylmonoxime ether and aqueous hydrochloric acid to be injected separately continuously rectifying tower to carry out catalytic distillation and contact, and isolate-oxyl amine hydrochlorate from liquid at the bottom of the tower of described rectifying tower.
The method of-oxyl amine hydrochlorate is prepared by ketoxime ether by carrying out in catalytic distillation tower described in provided by the invention, and make different reaction raw materials from the different positions charging of catalytic distillation tower, not only can not use extra organic solvent, and owing to collecting reaction and being located away from one, therefore can also high purity, obtain target product with high yield, decrease the step be separated separately, thus reach the object reducing production cost.
Embodiment
According to a first aspect of the invention, the invention provides a kind of method being prepared-oxyl amine hydrochlorate by ketoxime ether, the method comprises: acetoxime ether or Diacetylmonoxime ether are injected rectifying tower continuously from the first opening for feed, aqueous hydrochloric acid is injected rectifying tower continuously from the second opening for feed, and-oxyl amine hydrochlorate is isolated from liquid at the bottom of the tower of described rectifying tower, wherein, stage number at the bottom of described first opening for feed to tower or theoretical plate number D1 and at the bottom of described second opening for feed to tower stage number or theoretical plate number D2 account for total stage number of described rectifying tower or the 30-80% of theoretical plate number separately, and D1 < D2.
According to described method provided by the invention, by the interlude of aqueous hydrochloric acid and ketoxime ether compound (i.e. acetoxime ether or Diacetylmonoxime ether) each comfortable rectifying tower is injected rectifying tower, and make the opening for feed of aqueous hydrochloric acid above the opening for feed of described ketoxime ether compound, the ketone compound making hydrochloric acid and described ketoxime ether compound react to produce can be discharged from the tower top of rectifying tower when not extra with an organic solvent (as toluene, hexane etc.); But also can realize, by aqueous hydrochloric acid and described ketoxime ether compound counter current contact, improve speed of response, thus shortening the reaction times, decrease the generation of side reaction; Continous way can also be realized in addition produce, improve the production capacity of whole technique.
According to described method provided by the invention, reaction and rectifying are carried out simultaneously, namely the interlude of aqueous hydrochloric acid and each comfortable rectifying tower of described ketoxime ether compound injects rectifying tower and reacts, simultaneous reactions product is also separated at the interlude of rectifying tower, result heavy constituent-oxyl amine hydrochlorate etc. falls into tower reactor, and light constituent ketone compound is then discharged as tower top light constituent.
In the preferred case, the difference between D1 and D2 accounts for total stage number of described rectifying tower or the 5-30% of theoretical plate number, is more preferably 5-20%.Under this preferable case, the yield of-oxyl amine hydrochlorate can be improved further.
According to described method provided by the invention, total stage number of described rectifying tower or theoretical plate number can be 20-100, are preferably 30-80.
According to described method provided by the invention, the column bottom temperature of described rectifying tower can be 70-110 DEG C, is preferably 85-95 DEG C; Tower top temperature can be 50-65 DEG C, is preferably 55-60 DEG C.
According to described method provided by the invention, the reaction of aqueous hydrochloric acid and acetoxime ether or Diacetylmonoxime ether can be represented by following reaction formula (1).
As can be seen from above-mentioned reaction formula (1), the mixed solution of the overhead distillate of described rectifying tower mainly ketone, water and unreacted HCl; Tower kettle product is-oxyl amine hydrochlorate, water and unreacted acetoxime ether or Diacetylmonoxime ether mainly, and the content of-oxyl amine hydrochlorate usually can up to 50-60 % by weight.
The mol ratio of the consumption of the HCl in described aqueous hydrochloric acid and acetoxime ether or Diacetylmonoxime ether can be 1.1-2.5: 1, is preferably 1.5-2: 1.The concentration of described aqueous hydrochloric acid can be 15-35 % by weight, is preferably 20-25 % by weight.
Be filled with filler in described rectifying tower, described filler can be the rectifying tower filler of various routine, such as, can be pottery and/or polytetrafluoro (as tetrafluoroethylene).
According to described method provided by the invention, described acetoxime ether is preferably acetoxime methyl ether or acetoxime ether.Described Diacetylmonoxime ether is preferably Diacetylmonoxime methyl ether or Diacetylmonoxime ether.In the present invention, described acetoxime ether can be commercially available, and also can prepare according to the method for routine.
According to described method provided by the invention, the method isolating-oxyl amine hydrochlorate liquid at the bottom of the tower of rectifying tower can adopt the separation method of various routine to implement, such as, this separation method can comprise: liquid underpressure distillation at the bottom of the tower of rectifying tower separated out to there being solid, be cooled to room temperature, then filter, the solids wash using lower alcohol (as methyl alcohol) to be obtained by suction filtration afterwards, then carries out drying.
According to a second aspect of the invention, present invention also offers a kind of preparation method of-oxyl amine hydrochlorate, the method comprises the following steps:
(1) under ketone oxamidinating reaction conditions, under the existence of titanium-silicon molecular sieve catalyst, the acetone be dissolved in organic solvent or butanone, hydrogen peroxide and ammonia are fed to contact reacts in reactor, obtain acetoxime or Diacetylmonoxime, wherein, the mol ratio of hydrogen peroxide and acetone or butanone is 1-1.3;
(2) under substitution reaction condition, the acetoxime obtained or Diacetylmonoxime and halocarbon are reacted, and isolate acetoxime ether or Diacetylmonoxime ether the product obtained after this contact reacts in step (1);
(3) according to the above-described described method being prepared-oxyl amine hydrochlorate by ketoxime ether, the acetoxime ether obtained in step (2) or Diacetylmonoxime ether and aqueous hydrochloric acid are injected separately continuously rectifying tower to carry out catalytic distillation and contact, and isolate-oxyl amine hydrochlorate from liquid at the bottom of the tower of described rectifying tower.
In step (1), described ketone oxamidinating reaction can be represented by following reaction formula (2),
According to described method provided by the invention, in step (1), there is no particular limitation for described ketone oxamidinating reaction conditions, and conventional ketone oxamidinating reaction conditions is all applicable to the present invention.In the preferred case, described ketone oxamidinating reaction conditions comprises: temperature of reaction is 45-85 DEG C, is more preferably 50-80 DEG C; Reaction times is 0.5-6 hour, is more preferably 1-5 hour.
According to described method provided by the invention, in step (1), the consumption of described titanium-silicon molecular sieve catalyst can feed intake by catalyst levels conveniently, but, in order to ensure that the catalyzer in reaction system has enough catalytic activitys, and the consumption reducing titanium-silicon molecular sieve catalyst is as far as possible to reduce production cost, the weight ratio of described titanium-silicon molecular sieve catalyst and acetone or butanone can be 0.03-0.15: 1, is preferably 0.05-0.1: 1.
According to described method provided by the invention, in step (1), there is no particular limitation for the charging capacity of ammonia, can conveniently ketone oxamidinating reaction in ammonia charging capacity feed intake.Under preferable case, the mol ratio of ammonia and acetone or butanone is 1-1.8: 1, is more preferably 1.5-1.7: 1.
According to described method provided by the invention, in step (1), described organic solvent can be the conventional various organic solvents used of ketone oxamidinating reaction, is preferably isopropylcarbinol or the trimethyl carbinol.The weight ratio of the add-on of the add-on of described organic solvent and acetone or butanone can be 1-10: 1, is preferably 1.5-5: 1.
In the present invention, ammonia can add with the form of ammonia, also can add with the form of ammoniacal liquor, and the concentration of ammoniacal liquor can be 20-50 % by weight, preferably adds with the form of ammonia.
In the present invention, hydrogen peroxide adds with the form of hydrogen peroxide usually, and the concentration of described hydrogen peroxide can be 28-50 % by weight, is preferably 28-30 % by weight.
In the present invention, in order to obtain the yield of higher ketoxime compounds (i.e. acetoxime or Diacetylmonoxime), described titanium-silicon molecular sieve catalyst preferably has the titanium-silicon molecular sieve catalyst of hollow structure.The radical length of the chamber portion of the hollow structure of described HTS is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this titanium-silicon molecular sieve catalyst and desorption isotherm.The described titanium-silicon molecular sieve catalyst with hollow structure can be commercially available, such as, can be commercially available TS-1 molecular sieve catalyst, also can prepare according to the method for routine, and its preparation method can with reference to CN1301599A, particularly embodiment 1-11 wherein.
According to described method provided by the invention, in step (1), described reactor can be the reactor of various routine, such as, can be reactor, slurry bed reactor etc.
In step (2), the contact reacts of acetoxime or Diacetylmonoxime and halohydrocarbon is preferably carried out under the existence of alkali metal hydroxide and solvent, and this contact reacts can be represented by following reaction formula (3).
According to described method provided by the invention, in step (2), there is no particular limitation for described substitution reaction condition, and the substitution reaction condition of the various routines of acetoxime or Diacetylmonoxime and halohydrocarbon generation substitution reaction can be made all to be applicable to the present invention.In the preferred case, described substitution reaction condition comprises: temperature of reaction is 20-70 DEG C, and the reaction times is 1-3 hour.
According to described method provided by the invention, in step (2), there is no particular limitation for the charging capacity of acetoxime or Diacetylmonoxime and halohydrocarbon, and the concrete consumption of acetoxime or Diacetylmonoxime and halohydrocarbon suitably can be selected in the amount ranges of routine.Under preferable case, the mol ratio of the consumption of described halohydrocarbon and acetoxime or Diacetylmonoxime is 1-1.3: 1, is preferably 1.05-1.2: 1.
According to described method provided by the invention, in step (2), there is no particular limitation for the substance classes of described halohydrocarbon, can be the halogenated hydrocarbon compound of various routine, under preferable case, described halohydrocarbon is methyl chloride, monochloroethane, monobromethane or monobromethane.
According to described method provided by the invention, in step (2), the weight ratio of the consumption of described solvent and acetoxime or Diacetylmonoxime can be 1-20: 1, is preferably 3-20: 1.
According to described method provided by the invention, in step (2), the mol ratio of described alkali metal hydroxide and acetoxime or Diacetylmonoxime can be 1-1.5: 1, is preferably 1.1-1.3: 1.
In the present invention, described base metal catalysts can be the water-soluble alkali oxyhydroxide of various routine, such as can for being selected from sodium hydroxide and/or potassium hydroxide.
In the present invention, solvent described in step (2) can for preparing by acetoxime or Diacetylmonoxime and halohydrocarbon the various organic solvents that in the technique of ketoxime ether compound, routine uses, such as can for being selected from least one in dimethyl sulfoxide (DMSO), tetramethylene sulfone, [BMIM] Cl ionic liquid and [BMIM] OH ionic liquid.
In step (2), the method isolating acetoxime ether or Diacetylmonoxime ether from reaction product can adopt conventional method to implement, such as can comprise: reaction product is cooled to room temperature, add water, extract as extraction solvent with ether, hexanaphthene, hexane etc. again, then extract layer solution is carried out rectifying separation, acetoxime ether or Diacetylmonoxime ether product after steaming solvent, can be obtained.
According to described method provided by the invention, in step (3), by acetoxime ether or Diacetylmonoxime ether prepare-oxyl amine hydrochlorate method can with describe above described in prepare the method for-oxyl amine hydrochlorate by ketoxime ether identical.
According to described method provided by the invention, as can be seen from above-mentioned reaction formula (1), another product (product except except-oxyl amine hydrochlorate) of step (3) is acetone or butanone, and in catalytic distillation process, acetone or butanone are discharged from the tower top of described rectifying tower; In addition, owing to there is no additional organic solvent in step (3), therefore the acetone in overhead distillate or butanone through or can be used in step (1) by direct circulation after concentrated, and in overhead distillate, the existence of a small amount of HCl also helps the middle hydrogen peroxide of stabilizing step (1).Therefore, according to another kind of preferred implementation of the present invention, described method also comprises: the acetone or the butanone that pass through the overhead distillate of described rectifying tower or be used as without concentrated Posterior circle at least part of step (1).In this preferred implementation, can realize being reacted the acetone that produces by aqueous hydrochloric acid and acetoxime ether or Diacetylmonoxime ether or butanone is recycled, solve the problem of outlet of acetone or the butanone produced by this reaction on the one hand, what also solve on the other hand step (1) acetone or butanone carrys out source problem, thus reduces production cost.
The invention will be further described with comparative example by the following examples.
In the following Examples and Comparative Examples, the yield of-oxyl amine hydrochlorate calculates according to following calculating formula:
The acetoxime ether of the mole number/charging of the-oxyl amine hydrochlorate of the yield=generation of-oxyl amine hydrochlorate or mole number × 100% of Diacetylmonoxime ether
Embodiment 1
The present embodiment for illustration of of the present invention described by ketoxime ether prepare-oxyl amine hydrochlorate method and.
(1) preparation of acetoxime
In the reactor of 200ml, add the TS-1 molecular sieve catalyst (prepared by the method according to embodiment in CN1301599A 1) of 1.2g, the acetone of 11.6g, the trimethyl carbinol of 35g and 22g concentration be 25 % by weight ammoniacal liquor.Mixture in reactor is fully mixed, good seal reactor, temperature of reaction is controlled to be 80 DEG C.The hydrogen peroxide that 26g concentration is 30 % by weight is added continuously with micro-fresh feed pump.Hydrogen peroxide is continuously pumped into 2 hours, continues reaction 1 hour.After reaction terminates, solid catalyst is separated from mixing liquid, and by the liquid cooling that obtains to room temperature, 3 times are extracted with zellon, merge extract layer liquid, then at about 65 DEG C, underpressure distillation is carried out, obtain acetoxime product after evaporate to dryness zellon, its fusing point is 58.2-60.1 DEG C, its infrared spectra and mass-spectrometric data as follows:
IR，v
max/cm
-1：3200，2920，2896，1681，1498，1371，1268，1072，949，81；
MS m/z(％)：73(M
+，100)，58(64)，54(21)，42(21)，41(21)，31(31)，28(42)，15(45)。
(2) preparation of acetoxime methyl ether
At room temperature in the four-hole boiling flask of 500ml belt stirrer, add 70.2g (0.96mol) acetoxime, 220g dimethyl sulfoxide (DMSO) (DMSO), 44.2g (1.1mol) NaOH, then under agitation at 25 DEG C, 56g (1.11mol) monochloro methane is passed into, pass into complete after, react 2 hours at 30-40 DEG C, be cooled to room temperature, add 220g water, with 150g n-hexane extraction 3 times, merge extract layer solution and extract layer solution is carried out fractionation by distillation, acetoxime methyl ether is obtained after steaming desolventizes, its nmr spectrum data and gas chromatography-mass spectrum (GC-MS) data as follows:
1H NMR(400MHz，DMSO-d6)δ：1.76～1.79(6H，d，CH
3)，3.71(3H，s，CH
3)；
MS m/z(％)：87(M
+，100)，72(17)，56(68)。
(3) preparation of methoxy amine hydrochlorate
Be that the aqueous hydrochloric acid (flow is 320kg/h) of 25 % by weight is respectively since the first opening for feed of rectifying tower and the second opening for feed add in rectifying tower by the acetoxime methyl ether of preparation in step (2) and concentration, the theoretical plate number of this rectifying tower is 80, and filler is Mellapak
tM500 (purchased from Sulzer (Sulzer) companies), tower diameter is 400mm, tower height is 35m, theoretical plate number between at the bottom of first opening for feed to tower is 32, theoretical plate number between at the bottom of second opening for feed to tower is 48, and the add-on of acetoxime methyl ether and aqueous hydrochloric acid makes the mol ratio of the acetoxime methyl ether in charging and HCl be 1: 1.5.By the column bottom temperature of this rectifying tower is controlled as about 120 DEG C, tower top temperature is controlled, for about 57 DEG C, the material in this rectifying tower is reacted, and makes reaction product carry out rectifying separation in this rectifying tower.Overhead distillate is concentrated, obtains the aqueous acetone that acetone content is about 55 % by weight, and this aqueous acetone is added in reactor as the acetone raw material in step (1); Liquid underpressure distillation at the bottom of tower being separated out to there being solid, being cooled to room temperature, suction filtration, by methanol wash, then carry out vacuum-drying, obtain methoxy amine hydrochlorate product, its fusing point is 150-152 DEG C, and the mass-spectrometric data of its infrared spectra and the rear extraction liquid product of neutralization is as follows:
IR，v
max/cm
-1：3014，3003，2986，2860，2739，2713，2620，1578，1507，1403，1189，1146，1036，882，455；
MS m/z(％)：47(M
+，100)，32(42)，31(41)，29(17)，17(13)。
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 93.0%, and the yield of acetone is 93.2%.This shows, often produce the methoxy amine hydrochlorate of 1 ton, need the external acetone consumed to be 0.051 ton.
Comparative example 1
Method according to embodiment 1 prepares methoxy amine hydrochlorate, difference is, in the preparation process of the methoxy amine hydrochlorate of step (3) be: by the acetoxime methyl ether of preparation in step (2), concentration be 25 % by weight aqueous hydrochloric acid and toluene be added in the tower reactor of rectifying tower, the theoretical plate number of rectifying tower is 80, the add-on of acetoxime methyl ether and aqueous hydrochloric acid makes the mol ratio of the acetoxime methyl ether in charging and HCl be 1: 1.5, and the weight ratio of the add-on of toluene and acetoxime methyl ether is 2: 1.The column bottom temperature of this rectifying tower is controlled for about 110 DEG C, tower top temperature is controlled, for about 90 DEG C, make the material in this rectifying tower carry out reaction 16 hours, and make reaction product carry out rectifying separation in this rectifying tower.Liquid underpressure distillation at the bottom of tower being separated out to there being solid, being cooled to room temperature, suction filtration, by methanol wash, then carry out vacuum-drying, obtain methoxy amine hydrochlorate product, its fusing point is 149-151 DEG C.
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 78.5%.
The Comparative result of embodiment 1 with comparative example 1 can be found out, the yield of higher-oxyl amine hydrochlorate can be obtained according to method of the present invention.Although employ organic solvent (i.e. toluene) in comparative example 1, because in comparative example 1, reactant is fed directly in tower reactor, thus make the target product yield of comparative example 1 relatively low.
Comparative example 2
Method according to embodiment 2 prepares methoxy amine hydrochlorate, and difference is, in the preparation process of the methoxy amine hydrochlorate of step (3), does not add toluene.
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 67.3%.
The Comparative result of embodiment 1 with comparative example 2 can be found out, the yield of higher-oxyl amine hydrochlorate can be obtained according to method of the present invention.In comparative example 2, on the one hand not with an organic solvent (as toluene), on the other hand, reactant is fed directly in tower reactor, thus makes the target product yield of comparative example 2 obviously lower.
Comparative example 3
Method according to embodiment 1 prepares methoxy amine hydrochlorate, difference is, in the preparation process of the methoxy amine hydrochlorate of step (3), in step (2), the acetoxime methyl ether of preparation adds in described rectifying tower by the second opening for feed of described rectifying tower, concentration be 25 % by weight aqueous hydrochloric acid add in described rectifying tower by the first opening for feed of described rectifying tower, also namely the opening for feed of acetoxime methyl ether above the opening for feed of aqueous hydrochloric acid.
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 87.6%.
Comparative example 4
Method according to embodiment 1 prepares methoxy amine hydrochlorate, difference is, in the preparation process of the methoxy amine hydrochlorate of step (3), the acetoxime methyl ether of preparation in step (2) and concentration be 25 % by weight aqueous hydrochloric acid all add in described rectifying tower by the second opening for feed of described rectifying tower, also namely the opening for feed of acetoxime methyl ether is identical with the opening for feed of aqueous hydrochloric acid.
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 90.4%.
The Comparative result of embodiment 1 with comparative example 3 and 4 can be found out, the yield of higher-oxyl amine hydrochlorate can be obtained according to method of the present invention.In comparative example 3 and 4, because the opening for feed of aqueous hydrochloric acid is not above the opening for feed of ketoxime ether, thus make the target product yield of comparative example 3 and 4 relatively low.
Comparative example 5
The present embodiment prepares the method for-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate by ketoxime ether described in provided by the invention.
Method according to embodiment 1 prepares methoxy amine hydrochlorate, difference is, in the preparation process of the methoxy amine hydrochlorate of step (3), in rectifying tower, acetoxime methyl ether by the first throat-fed, and at the bottom of the first opening for feed to tower between theoretical plate number be 20; Concentration be the aqueous hydrochloric acid of 25 % by weight by the second throat-fed, and at the bottom of the second opening for feed to tower between theoretical plate number be 72.
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle acetoxime methyl ether of step (3) is 83.2%.
The Comparative result of embodiment 1 with comparative example 5 can be found out, the yield of higher-oxyl amine hydrochlorate can be obtained according to method of the present invention.In comparative example 5, because the theoretical plate number between the opening for feed of aqueous hydrochloric acid is at the bottom of tower is greater than 80% of the theoretical plate number of described rectifying tower, and at the bottom of the opening for feed of ketoxime ether to tower between theoretical plate number be less than 30% of the theoretical plate number of described rectifying tower, thus make the target product yield of comparative example 5 relatively low.
Embodiment 2
The present embodiment prepares the method for-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate by ketoxime ether described in provided by the invention.
(1) preparation of acetoxime
Acetoxime is prepared according to the method for step (1) in embodiment 1.
(2) preparation of acetoxime ether
At room temperature in the four-hole boiling flask of 500ml belt stirrer, add 70.2g (0.96mol) acetoxime, 220g dimethyl sulfoxide (DMSO) (DMSO), 44.2g (1.1mol) NaOH, then under agitation at 25 DEG C, 77.4g (1.2mol) monochlorethane is added dropwise to, after dripping, react 1 hour at 60 DEG C, be cooled to room temperature, add 220g water, with 150g n-hexane extraction 3 times, merge extract layer solution and extract layer solution is carried out fractionation by distillation, obtain acetoxime ether after steaming desolventizes, its nmr spectrum data and GC-MS data as follows:
1H NMR(400MHz，DMSO-d6)δ：1.17(3H，t，CH
2CH
3)，1.77～1.79(6H，d，CH
3)，3.95～4.00(2H，m，CH
2)；
MS m/z(％)：101(M
+，52)，73(100)，58(58)，56(66)。
(3) preparation of ethoxy amine hydrochloride
By the acetoxime ether of preparation in step (2) and concentration be the aqueous hydrochloric acid of 25 % by weight respectively since the first opening for feed of rectifying tower and the second opening for feed add in rectifying tower, the theoretical plate number of this rectifying tower is 80, and filler is Mellapak
tM500 (purchased from Sulzer (Sulzer) companies), tower diameter is 400mm, tower height is 35m, theoretical plate number between at the bottom of first opening for feed to tower is 32, theoretical plate number between at the bottom of second opening for feed to tower is 48, and the add-on of acetoxime ether and aqueous hydrochloric acid makes the mol ratio of the acetoxime ether in charging and HCl be 1: 2.By the column bottom temperature of this rectifying tower is controlled as about 120 DEG C, tower top temperature is controlled, for about 60 DEG C, the material in this rectifying tower is reacted, and makes reaction product carry out rectifying separation in this rectifying tower.Overhead distillate is concentrated, obtains the aqueous acetone that acetone content is about 55 % by weight, and this aqueous acetone is added in reactor as the acetone raw material in step (1); Liquid underpressure distillation at the bottom of tower being separated out to there being solid, being cooled to room temperature, suction filtration, by methanol wash, then carry out vacuum-drying, obtain ethoxy amine hydrochloride product, its fusing point is 131-133 DEG C, and the mass-spectrometric data of its infrared spectra and the rear extraction liquid product of neutralization is as follows:
IR，v
max/cm
-1：3426，2987，2701，2280，1978，1612，1403，1153，1102，1034，835，485；
MS m/z(％)：61(M
+，19)，43(13)，33(100)，29(47)，27(28)。
The yield calculating ethoxy amine hydrochloride according to the output of ethoxy amine hydrochloride and the charging capacity of the middle acetoxime ether of step (3) is 93.5%, and the yield of acetone is 94.8%.This shows, often produce the ethoxy amine hydrochloride of 1 ton, need the external acetone consumed to be 0.033 ton.
Embodiment 3
The present embodiment prepares the method for-oxyl amine hydrochlorate and the preparation method of-oxyl amine hydrochlorate by ketoxime ether described in provided by the invention.
(1) preparation of Diacetylmonoxime
In the reactor of 200ml, add the TS-1 molecular sieve catalyst (prepared by the method according to embodiment in CN1301599A 1) of 1.2g, the butanone of 14.2g, the trimethyl carbinol of 35g and 25g concentration be 25 % by weight ammoniacal liquor.Mixture in reactor is fully mixed, good seal reactor, temperature of reaction is controlled to be 90 DEG C.The hydrogen peroxide that 26g concentration is 30 % by weight is added continuously with micro-fresh feed pump.Hydrogen peroxide is continuously pumped into 4 hours, continues reaction 1 hour.After reaction terminates, solid catalyst is separated from mixing liquid, and by the liquid cooling that obtains to room temperature, 3 times are extracted with zellon, merge extract layer liquid, then at about 65 DEG C, underpressure distillation is carried out, the Diacetylmonoxime product obtained after evaporate to dryness zellon, its infrared spectra and mass-spectrometric data as follows:
IR，v
max/cm
-1：3246，2973，2941，2922，2881，1665，1460，1372，1369，1328，1271，1242，1220，1098，1072，977，935，800，795，788，771，611，523；
MS m/z(％)：87(M
+，98)，86(26)，58(38)，42(100)，41(26)，29(31)，28(28)，27(29)。
(2) preparation of Diacetylmonoxime methyl ether
At room temperature in the four-hole boiling flask of 500ml belt stirrer, add 83.6g (0.96mol) Diacetylmonoxime, 220g dimethyl sulfoxide (DMSO) (DMSO), 44.2g (1.1mol) NaOH, then under agitation at 25 DEG C, 53g (1.05mol) monochloro methane is added dropwise to, after dripping, react 3 hours at 50 DEG C, be cooled to room temperature, add 220g water, with 150g n-hexane extraction 3 times, merge extract layer solution and extract layer solution is carried out fractionation by distillation, Diacetylmonoxime methyl ether (having along anti-two kinds of structures) is obtained after steaming desolventizes, its nmr spectrum data and GC-MS data are distinguished as follows:
1H NMR(400MHz，DMSO-d6)(I)δ：1.03(3H，t，CH
2CH
3)，1.77(3H，s，CH
3)，2.25(2H，m，CH
2CH
3)，3.72(3H，s，OCH
3)；(II)δ：0.98(3H，t，CH
2CH
3)，1.75(3H，s，CH
3)，2.14(2H，m，CH
2CH
3)，3.72(3H，s，OCH
3)；
MS m/z(％)：101(M
+，99)，86(17)，68(40)，56(23)，42(100)，29(27)。
(3) preparation of methoxy amine hydrochlorate
By the Diacetylmonoxime methyl ether of preparation in step (2) and concentration be the aqueous hydrochloric acid of 25 % by weight respectively since the first opening for feed of rectifying tower and the second opening for feed add in rectifying tower, the theoretical plate number of this rectifying tower is 80, and filler is Mellapak
tM500 (purchased from Sulzer (Sulzer) companies), tower diameter is 400mm, tower height is 35m, theoretical plate number between at the bottom of first opening for feed to tower is 32, theoretical plate number between at the bottom of second opening for feed to tower is 48, and the add-on of Diacetylmonoxime methyl ether and aqueous hydrochloric acid makes the mol ratio of the Diacetylmonoxime methyl ether in charging and HCl be 1: 1.8.By the column bottom temperature of this rectifying tower is controlled as about 120 DEG C, tower top temperature is controlled, for about 60 DEG C, the material in this rectifying tower is reacted, and makes reaction product carry out rectifying separation in this rectifying tower.Overhead distillate is concentrated, obtains the moisture butanone that butanone content is about 55 % by weight, and this moisture butanone is added in reactor as the butanone raw material in step (1); Liquid underpressure distillation at the bottom of tower being separated out to there being solid, being cooled to room temperature, suction filtration, by methanol wash, then carry out vacuum-drying, obtain methoxy amine hydrochlorate product, its fusing point is 150-152 DEG C, and the mass-spectrometric data of its infrared spectra and the rear extraction liquid product of neutralization is as follows:
IR，v
max/cm
-1：3014，3003，2986，2860，2739，2713，2620，1578，1507，1403，1189，1146，1036，882，455；
MS m/z(％)：47(M
+，100)，32(42)，31(41)，29(17)，17(13)。
The yield calculating methoxy amine hydrochlorate according to the output of methoxy amine hydrochlorate and the charging capacity of the middle Diacetylmonoxime methyl ether of step (3) is 92.5%, and the yield of butanone is 91.3%.This shows, often produce the methoxy amine hydrochlorate of 1 ton, need the external butanone consumed to be 0.081 ton.
Above embodiment is only for describing the preferred embodiment of the present invention; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (20)
1. prepared the method for-oxyl amine hydrochlorate by ketoxime ether for one kind, the method comprises: acetoxime ether or Diacetylmonoxime ether are injected rectifying tower continuously from the first opening for feed, aqueous hydrochloric acid is injected rectifying tower continuously from the second opening for feed, and-oxyl amine hydrochlorate is isolated from liquid at the bottom of the tower of described rectifying tower, wherein, stage number at the bottom of described first opening for feed to tower or theoretical plate number D1 and at the bottom of described second opening for feed to tower stage number or theoretical plate number D2 account for total stage number of described rectifying tower or the 30-80% of theoretical plate number separately, and D1<D2, wherein, difference between D1 and D2 accounts for total stage number of described rectifying tower or the 5-30% of theoretical plate number.
2. method according to claim 1, wherein, the difference between D1 and D2 accounts for total stage number of described rectifying tower or the 5-20% of theoretical plate number.
3. method according to claim 1 and 2, wherein, total stage number of described rectifying tower or theoretical plate number are 20-100.
4. method according to claim 3, wherein, total stage number of described rectifying tower or theoretical plate number are 30-80.
5. method according to claim 1, wherein, the column bottom temperature of described rectifying tower is 70-110 DEG C; Tower top temperature is 50-65 DEG C.
6. method according to claim 5, wherein, the column bottom temperature of described rectifying tower is 85-95 DEG C; Tower top temperature is 55-60 DEG C.
7. method according to claim 1, wherein, the mol ratio of the consumption of the HCl in described aqueous hydrochloric acid and acetoxime ether or Diacetylmonoxime ether is 1.1-2.5:1; The concentration of described aqueous hydrochloric acid is 15-35 % by weight.
8. method according to claim 7, wherein, the mol ratio of the consumption of the HCl in described aqueous hydrochloric acid and acetoxime ether or Diacetylmonoxime ether is 1.5-2:1; The concentration of described aqueous hydrochloric acid is 20-25 % by weight.
9. the method according to claim 1 or 7 or 8, wherein, described acetoxime ether is acetoxime methyl ether or acetoxime ether, and described Diacetylmonoxime ether is Diacetylmonoxime methyl ether or Diacetylmonoxime ether.
10. a preparation method for-oxyl amine hydrochlorate, the method comprises the following steps:
(1) under ketone oxamidinating reaction conditions, under the existence of titanium-silicon molecular sieve catalyst, the acetone be dissolved in organic solvent or butanone, hydrogen peroxide and ammonia are fed to contact reacts in reactor, obtain acetoxime or Diacetylmonoxime, wherein, the mol ratio of hydrogen peroxide and acetone or butanone is 1-1.3;
(2) under substitution reaction condition, the acetoxime obtained or Diacetylmonoxime and halocarbon are reacted, and isolate acetoxime ether or Diacetylmonoxime ether the product obtained after this contact reacts in step (1);
(3) adopt the method in claim 1-9 described in any one the acetoxime ether obtained in step (2) or Diacetylmonoxime ether and aqueous hydrochloric acid to be injected separately continuously rectifying tower to carry out catalytic distillation and contact, and isolate-oxyl amine hydrochlorate from liquid at the bottom of the tower of described rectifying tower.
11. methods according to claim 10, wherein, in step (1), described ketone oxamidinating reaction conditions comprises: temperature of reaction is 45-85 DEG C; Reaction times is 0.5-6 hour.
12. methods according to claim 11, wherein, in step (1), described ketone oxamidinating reaction conditions comprises: temperature of reaction is 50-80 DEG C; Reaction times is 1-5 hour.
13. methods according to claim 10, wherein, in step (1), the weight ratio of described titanium-silicon molecular sieve catalyst and acetone or butanone is 0.03-0.15:1; The mol ratio of ammonia and acetone or butanone is 1-1.8:1.
14. methods according to claim 13, wherein, in step (1), the weight ratio of described titanium-silicon molecular sieve catalyst and acetone or butanone is 0.05-0.1:1; The mol ratio of ammonia and acetone or butanone is 1.5-1.7:1.
15. methods according to claim 10, wherein, in step (2), described acetoxime or Diacetylmonoxime and halocarbon react and carry out under the existence of alkali metal hydroxide and solvent, and described alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide; Described solvent is at least one in dimethyl sulfoxide (DMSO), tetramethylene sulfone, [BMIM] Cl ionic liquid and [BMIM] OH ionic liquid.
16. methods according to claim 15, wherein, the weight ratio of the consumption of described solvent and described acetoxime or Diacetylmonoxime is 1-20:1; The mol ratio of described alkali metal hydroxide and described acetoxime or Diacetylmonoxime is 1-1.5:1; The mol ratio of the consumption of described halohydrocarbon and described acetoxime or Diacetylmonoxime is 1-1.3:1.
17. methods according to claim 16, wherein, the weight ratio of the consumption of described solvent and described acetoxime or Diacetylmonoxime is 3-20:1; The mol ratio of described alkali metal hydroxide and described acetoxime or Diacetylmonoxime is 1.1-1.3:1; The mol ratio of the consumption of described halohydrocarbon and described acetoxime or Diacetylmonoxime is 1.05-1.2:1.
18. methods according to claim 10,15 or 16 or 17, wherein, in step (2), described substitution reaction condition comprises: temperature of reaction is 20-70 DEG C, and the reaction times is 1-3 hour.
19. methods according to claim 10 or 16, wherein, in step (2), described halohydrocarbon is methyl chloride, monochloroethane, monobromethane or monobromethane.
20. methods according to claim 10, wherein, in step (3), described method also comprises: the described acetone or the butanone that pass through the overhead distillate of described rectifying tower or be used as without concentrated Posterior circle at least part of step (1).
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| CN103304442B (en) * | 2013-06-14 | 2014-08-13 | 浙江大学 | Process for synthesizing diacetylmonoxime ethyl ether by continuous reactions in microtube |
| CN104478757A (en) * | 2014-12-18 | 2015-04-01 | 烟台奥东化学材料有限公司 | Method for safely preparing pure N, O-dimethylhydroxyamine hydrochloride |
| CN104610094B (en) * | 2015-01-30 | 2016-06-15 | 湖北仙粼化工有限公司 | A kind of method preparing diacetylmonoxime |
| CN106478450A (en) * | 2016-09-23 | 2017-03-08 | 定州旭阳科技有限公司 | A kind of method of purification of acetone oxime |
| CN106588700B (en) * | 2016-12-06 | 2019-01-25 | 盐城辉煌化工有限公司 | A kind of improved cymoxanil synthetic method |
| CN113083189B (en) * | 2021-03-02 | 2023-01-13 | 北京化工大学 | System for preparing methoxylamine hydrochloride by coupling supergravity with microwave and ultrasound |
| CN113429313B (en) * | 2021-06-09 | 2022-07-12 | 浙江锦华新材料股份有限公司 | Preparation method of acetone oxime methyl ether |
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