CN109824540A - A kind of technique that molecular oxygen oxidation method prepares ketazine - Google Patents
A kind of technique that molecular oxygen oxidation method prepares ketazine Download PDFInfo
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Abstract
The invention discloses the techniques that a kind of molecular oxygen oxidation method prepares ketazine, include the following steps: to prepare ketimide, ketone and ammonia are put into autoclave pressure according to the proportion, adjusting pressure limit is 1.0-5.0MPa, 30-180 DEG C of temperature range, reaction time 3-5 hour generates ketimide；Ammonia is 1:1-20:1 to the molar ratio range of ketone；Decrease temperature and pressure isolates the mixture of ketimide and ketone；By the mixture of ketimide and ketone, catalyst, desiccant investment reaction kettle in, be warming up to 30-80 DEG C, be passed through molecular oxygen carry out oxidation reaction, pressure limit 0-1.0Mpa, oxidation time 3-6 hours；Molecular oxygen includes: oxygen or air；Separating-purifying ketazine；This method is applicable not only to benzophenone and also achieves the few alkenolic ketazine synthesis of carbon atom number, and raw material sources are extensive, low in cost, Yi Huishou, and this method does not have brine waste, energy consumption and at low cost, environmentally protective.
Description
Technical field
The invention belongs to chemosynthesis technical field, in particular to a kind of technique for preparing ketazine.
Background technique
Ketazine is a kind of compound with one C=N-N=C, mono- structure, is mainly used in dyestuff, light-sensitive material, gathers
It closes in the synthesis of substances such as monomer and the intermediate of oxo-synthesis of hydrazine hydrate.The country generallys use urea method oxo-synthesis of hydrazine hydrate at present,
Its process recovery ratio is low, energy consumption is high, seriously polluted, and the ammonia nitrogen waste water discharged is worldwide improvement problem.As national environmental protection is anticipated
The reinforcement of knowledge, environment protection treating becomes the matter of utmost importance that can hydrazine hydrate production enterprise survive, and restricts the bottleneck of industry development.
And be technique more more advanced than urea method using ketazine hydrazine hydrate, current ketazine technique master has Bayer method and peroxide
Change hydrogen method, but Bayer method fails to promote there is also the only a small amount of producer's use at home of brine waste problem.And peroxide
Change hydrogen rule higher cost, the country there is no producer to produce.
Bayer method is the of exploitation the 1960s earliest by the subsidiary body Bergbau-of Germany coal mine association
Farsching proposes patent.Process modification is made by Bayer company and Whifen&Sons company respectively, in the 7O age in 20th century
Mid-term heavy industrialization simultaneously rapidly develops.It is in the presence of aliphatic ketone compounds, with chlorine or hypochlorite oxidation
Ammonia obtains ketazine.Its reaction principle is: ammonia, with chlorine or hypochlorite oxidation, generates ketazine, hydrazone in the presence of alkenolic
Or different hydrazone, when ketone surplus, hydrazone and different hydrazone can also be converted to ketazine.The method uses cheap raw material, yield close to theoretical value,
But Bayer method is using chlorine as oxidant.Environmental pollution is larger.Reaction equation is as follows:
2Na0H+Cl2—→NaClO+NaCl+H20,
NaCl0+2NH3+ 2 (CH3) 2C=O-→
(CH3)2C=N-N=C (CH3)2+NaCl+3H20
It is pollution caused by oxidant to solve chlorine, meets the trend that the world today focuses on environmental protection.
Late 1970s France Ugin-e Kuhlman company's developmental researches hydrogen peroxide method, is ketazine synthesis methodology
One leap is same.This method is first to be generated after ketimide is oxidized to the different hydrazone of oxa- with hydrogen peroxide again by ketone and ammonia reaction, then ammonification
Generate ketazine.Hydrogen peroxide method has used clean oxidant H2O2, and no salt by-product, sewage is easy to handle, ammonia it is excessive compared with
It is few；The quality of ketazine product is improved simultaneously.But product cost is restrained by hydrogen peroxide price, and catalyst recycles energy consumption
Height, investment cost are higher compared with Bayer method.Reaction equation are as follows:
Japan Report in 1974 prepares benzophenone azine using air oxidation process.This reaction is first sub- with air oxidation
Amine makes benzophenone and ammonia carry out dehydrating condensation, produces NSC 334072, then make imines oxygen under cuprous chloride catalyst effect
Change coupling and generates benzophenone azine.This method is under test, and yield is also lower, some problems are to be resolved；Reaction equation are as follows:
And be solid under benzophenone room temperature, boiling point is again very high, and benzophenone azine hydrolyzes hydrazine difficulty processed, and energy consumption is in high yield
It is low.And as then there are no the precedents for preparing ketazine with dioxygen oxidation method for the lower ketones such as acetone, butanone.
Market needs a kind of synthesis for being able to solve the relatively small number of alkenolic ketazine of carbon atom number, overcomes molecule
Oxygen oxidizing process prepares the difficult point of ketazine, and the process environmentally protective without brine waste；The present invention solves such problems.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of molecular oxygen oxidation method synthesizing ketazines
Method, this method are applicable not only to benzophenone and also achieve the few alkenolic ketazine synthesis of carbon atom number, raw material sources
Extensively, low in cost, Yi Huishou, this method does not have brine waste, energy consumption and at low cost, environmentally protective.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of molecular oxygen oxidation method prepares the technique of ketazine, includes the following steps:
Ketimide is prepared, ketone and ammonia are put into autoclave pressure according to the proportion, adjusting pressure limit is 1.0-5.0MPa, temperature
30-180 DEG C of range, reaction time 3-5 hour generates ketimide；Ammonia is 1:1-20:1 to the molar ratio range of ketone；
Decrease temperature and pressure isolates the mixture of ketimide and ketone；
By in the mixture of ketimide and ketone, catalyst, desiccant investment reaction kettle, it is warming up to 30-80 DEG C, is passed through molecule
Oxygen progress oxidation reaction, pressure limit 0-1.0Mpa, oxidation time 3-6 hours；Molecular oxygen includes: oxygen or air；
Separating-purifying ketazine.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, prepares ketimide, and ketone and ammonia are thrown according to the proportion
Enter in autoclave pressure, adjusting pressure limit is 1.0-5.0MPa, and 30-180 DEG C of temperature range, reaction time 3-5 hour, it is sub- to generate ketone
Amine；Ammonia is 2:1 to 5:1 to the molar ratio range of ketone.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, prepares ketimide, and ketone and ammonia are thrown according to the proportion
Enter in autoclave pressure, adjusting pressure limit is 2.0-4.0MPa, and 50-100 DEG C of temperature range, reaction time 3-5 hour, it is sub- to generate ketone
Amine；Ammonia is 1:1-20:1 to the molar ratio range of ketone.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, prepares ketimide, and ketone, ammonia, catalyst are put into
In autoclave pressure, adjusting pressure limit is 1.0-5.0MPa, and 30-180 DEG C of temperature range, reaction time 3-5 hour, it is sub- to generate ketone
Amine；Ammonia is 1:1-20:1 to the molar ratio range of ketone；Catalyst is ammonia salt.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, prepares ketimide, by aliphatic ketone, ammonia, desiccant
It puts into autoclave pressure, adjusting pressure limit is 1.0-5.0MPa, and 30-180 DEG C of temperature range, reaction time 3-5 hour generates ketone
Imines；Ammonia is 1:1-20:1 to the molar ratio range of ketone；Desiccant includes: zeolite molecular sieve, activated alumina, anhydrous slufuric acid
Sodium, silica gel.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, by the mixture of ketimide and ketone, catalyst, does
Drying prescription is put into reaction kettle, is warming up to 40-60 DEG C, is passed through air and is carried out oxidation reaction, pressure limit 0.2-0.6Mpa, oxidation
Reaction time 3-6 hour.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, by the mixture of ketimide and ketone, catalyst, does
Drying prescription is put into reaction kettle, is warming up to 30-80 DEG C, is passed through molecular oxygen and is carried out oxidation reaction, pressure limit 0-1.0Mpa, oxidation
Reaction time 3-6 hour；Catalyst is metal salt, and desiccant includes: zeolite molecular sieve, activated alumina, anhydrous sodium sulfate；It urges
The amount ranges of agent are 0.1%-20%.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, by the mixture of ketimide and ketone, catalyst, does
Drying prescription is put into reaction kettle, is warming up to 30-80 DEG C, is passed through molecular oxygen and is carried out oxidation reaction, pressure limit 0-1.0Mpa, oxidation
Reaction time 3-6 hour；Catalyst is halide, and desiccant includes: zeolite molecular sieve or activated alumina；The dosage of catalyst
Range is 1%-8%.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, separating-purifying ketazine；First separation organic phase with
Catalyst, catalyst recycling uses, then by organic phase distilation, isolates ketazine, and the ketone steamed is reused for synthesis ketone
Imines.
A kind of molecular oxygen oxidation method above-mentioned prepares the technique of ketazine, and ketone includes: aliphatic ketone, aromatic ketone.
The invention has the beneficial effects that:
This method is applicable not only to benzophenone and also achieves the few alkenolic ketazine synthesis of carbon atom number, for hydration
Hydrazine and ADC foaming agent industry open variation route；
With molecular oxygen (oxygen or air) for oxidant, raw material sources are extensive, low in cost；
The easy recycling at low cost of catalyst stannous chloride is reused, and low energy consumption；
This method does not have brine waste, environmentally protective.
Specific embodiment
Below in conjunction with detailed description of the invention by specific embodiments.
A kind of molecular oxygen oxidation method prepares the technique of ketazine, includes the following steps:
One, ketimide is prepared, ketone and ammonia are put into autoclave pressure according to the proportion, adjusting pressure limit is 1.0-5.0MPa,
Preferably 2.0-4.0MPa, 30-180 DEG C of temperature range, preferably 50-100 DEG C, reaction time 3-5 hour generate ketimide；
Ammonia is 1:1-20:1 to the molar ratio range of ketone；Pressure controlled process is the pressure using ammonia itself, if the pressure of ammonia itself
Inert gas pressurization not enough can be then added in power；If desired, catalyst can be used, preferred ammonium salt, such as ammonium chloride or ammonium sulfate.
The moisture content of desiccant elimination reaction generation can also be added in this step, make to react the propulsion of balancing objective direction.Desiccant includes: zeolite point
Son sieve, activated alumina, anhydrous sodium sulfate, the water-absorbent materials such as silica gel.
Two, decrease temperature and pressure isolates the mixture of ketimide and ketone；Detailed process is: it cools to room temperature, pressure
Lower first to stand the moisture content for dividing dereaction to generate, then slow release, organic phase is the mixture of ketimide and ketone, and mixture is directly used
It is reacted in next step.Release after this step first can also cool to 0-10 DEG C takes out reactant and carries out water-oil separating, but effect does not exist
Separator well under pressure.
Three, by the mixture of ketimide and ketone, catalyst, desiccant investment reaction kettle in (because oxidation reaction has water generation,
And imines and water facile hydrolysis, so desiccant need to be added to remove the moisture content generated), it is warming up to 30-80 DEG C, preferably 40-60 DEG C, is passed through
Molecular oxygen carries out oxidation reaction, and reaction can be carried out under normal pressure, can also be carried out under elevated pressure, and pressure is controlled in 0-
1.0Mpa, preferably 0.2-0.6Mpa；Oxidation time 3-6 hours；
Molecular oxygen includes: oxygen or air, preferably air；
Catalyst includes: the salt of metallic copper, palladium, chromium, manganese, iron, cobalt, nickel, titanium, lead, silver, preferably its halide, especially
The derivative of copper such as stannous chloride or cuprous bromide, it is excellent catalytic effect, cheap；Catalyst can be independent or be used in combination, directly
It connects and is added in reaction solution or is applied on carrier；Weight of the dosage of catalyst from 0.1 to 20%, preferably from 1% to 8%
Weight.
Desiccant can select zeolite molecular sieve, activated alumina, anhydrous sodium sulfate etc., preferred zeolite molecular sieve or activity
Aluminium oxide；
Reaction equation is as follows:
Four, separating-purifying ketazine；Organic phase and catalyst are first separated, catalyst recycling uses, then organic phase is distilled
Purification, isolates ketazine, and the ketone steamed is reused for synthesis ketimide.
Ketone can be aliphatic ketone or aromatic ketone, it is contemplated that the factor of hydrolysis hydrazine processed, preferably butanone, methyl tertbutyl
Ketone, the lower aliphatics ketone such as 2 pentanone.
Experimental verification is used below:
Embodiment 1:
50 grams of (0.5mol) methyl tertbutyl ketone and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure, are then added
68 grams of (4mol) ammoniacal liquors, ketone are 1:8 to the molar ratio range of ammonia；Mixture is heated to 80 DEG C, and pressure is increased to nitrogen
3.0MPa.The mixture stirs 2 hours at 80 DEG C.The slow pressure release of after reactant is cooled to 0 DEG C.Reaction mixture pours into
Separatory funnel carries out two-phase laminated flow.Water phase 5.5g, organic phase (on): 48.3 grams, gas chromatography: 39.5% ketone and 59.8%
Methyl tertbutyl ketimide.Gained mixture and 2 grams of stannous chlorides and 20 grams of zeolite molecular sieves put into reaction kettle at room temperature.
Mixture is heated to 40 DEG C, and air passes through mixture and stirs 5 hours.Reaction solution is poured out after cooling, is divided and is removed desiccant and catalysis
Agent, obtains 43 grams of product, the pinacolone azine of GC detection level 58.3% and 40.8% methyl tertbutyl ketone.It is dry with sodium sulphate
Dry, filtering is evaporated under reduced pressure to 26.1 grams of methyl tertbutyl ketazines, the methyl tertbutyl ketone of G/C content 94.7% and 2.5%.
Embodiment 2:
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
35 grams of (2mol) ammoniacal liquors are then added, ketone is 1:4 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen pressure
Power is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom aqueous phase
8.1 grams, slow pressure release obtains organic phase: 47.8 grams；Gas chromatographic detection: 24.1% ketone and 75.5% methyl tertbutyl ketone it is sub-
Amine；47.8 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of stannous chlorides
Reaction kettle is put at room temperature with 20 grams of activated aluminas.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is poured out after cooling
Reaction solution, point removes desiccant and catalyst, obtains 45 grams of product, the pinacolone azine of GC detection level 74.8% and 24.5% first
Base tert-butyl ketone.
Embodiment 3:
50 grams of (0.69mol) butanone and 0.5 gram of ammonium chloride (0.01) put into one 0.2 liter of autoclave pressure, are then added
43 grams of (2.5mol) ammoniacal liquors, ketone are 1:3.6 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, and pressure is mentioned with nitrogen
Height arrives 3.0MPa.The mixture stirs 2 hours at 90 DEG C.15 DEG C are cooled in reactant, stands to divide and goes bottom aqueous phase 11.4
Gram, slow pressure release obtains upper organic phase: 47.3 grams；Gas chromatographic detection: 22.9% butanone and 76.7% butanone imines；Institute
It obtains 47.3 grams of reaction mixtures and 2 grams of stannous chlorides and 20 grams of zeolite molecular sieve desiccant puts into autoclave pressure at room temperature.Heating
It is passed through under the pressure of oxygen holding 0.5Mpa and reacts 4 hours to 50 DEG C, under stirring.Reaction solution is poured out after cooling, is divided and is removed desiccant
And catalyst, obtain 44.6 grams of product, the pinacolone azine of GC detection level 75.5% and 23.8% butanone.It is evaporated under reduced pressure to
33.5 grams of butanone azines, the butanone of G/C content 97.8 and 1.3%.
Embodiment 4:
50 grams of (0.69mol) butanone and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure, are then added 43 grams
(2.5mol) ammoniacal liquor, ketone are 1:3.6 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, and pressure is increased to nitrogen
3.0MPa.The mixture stirs 2 hours at 90 DEG C.Reactant, which stands to divide after being cooled to 15 DEG C, goes 11.2 grams of bottom aqueous phase, delays
Slow pressure release, obtains upper organic phase: 47.5 grams；Gas chromatographic detection: 23.6% butanone and 75.9% butanone imines；Gained 47.5
Gram reaction mixture and 1.5 grams of copper bromides and 20 grams of activated aluminas put into autoclave pressure at room temperature.It is heated to 50 DEG C, under stirring
It is passed through under the pressure of oxygen holding 0.2Mpa and reacts 3 hours.Reaction solution is poured out after cooling, is divided and is removed desiccant and catalyst, must produce
44.3 grams of object, the butanone azine of GC detection level 75.9% and 23.4% butanone.
Embodiment 5:
50 grams of (0.58mol) 2 pentanones and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure, are then added 40 grams
(2.35mol) ammoniacal liquor, ketone are 1:4 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, and pressure is increased to nitrogen
3.0MPa.The mixture stirs 2 hours at 90 DEG C.Reactant, which stands to divide after being cooled to 15 DEG C, goes 9.2 grams of bottom aqueous phase, slowly
Pressure release, obtains upper organic phase: 47.5 grams；Gas chromatographic detection: 22.7% 2 pentanone and 76.9% 2 pentanone imines；Gained
47.5 grams of reaction mixtures and 1.5 grams of copper chlorides and 20 grams of activated aluminas put into autoclave pressure at room temperature.50 DEG C are heated to, is stirred
It mixes down and is reacted 3 hours under the pressure for being passed through oxygen holding 0.2Mpa.Reaction solution is poured out after cooling, is divided and is removed desiccant and catalyst,
45.1 grams of product, the 2 pentanone azine of GC detection level 75.8% and 23.5% 2 pentanone.
Below with experimental verification ketone to the molar ratio preferred scope of ammonia；
Embodiment 6:
Only have ketone different to the molar ratio range of ammonia compared with Example 2, other are all identical；
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
9 grams of (10mol) ammoniacal liquors are then added, ketone is 1:1 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen pressure
Power is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom aqueous phase
8.1 grams, slow pressure release obtains organic phase: 48.2 grams；Gas chromatographic detection: 57.5% ketone and 42.1% methyl tertbutyl ketone it is sub-
Amine；48.2 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of stannous chlorides
Reaction kettle is put at room temperature with 20 grams of activated aluminas.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is poured out after cooling
Reaction solution, point removes desiccant and catalyst, obtain 45.7 grams of product, the pinacolone azine of GC detection level 41.3% and 58.1%
Methyl tertbutyl ketone.
Embodiment 7:
Only have ketone different to the molar ratio range of ammonia compared with Example 2, other are all identical；
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
26 grams of (1.5mol) ammoniacal liquors are then added, ketone is 1:3 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen handle
Pressure is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom water
8.1 grams of phase, slow pressure release obtains organic phase: 48.0 grams；Gas chromatographic detection: 27.5% ketone and 72.0% methyl tertbutyl ketone
Imines；48.0 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of protochlorides
Copper and 20 grams of activated aluminas put into reaction kettle at room temperature.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is fallen after cooling
Reaction solution out divides and removes desiccant and catalyst, obtains 45.5 grams of product, the pinacolone azine of GC detection level 71.3% and 28.1%
Methyl tertbutyl ketone.
Embodiment 8:
Only have ketone different to the molar ratio range of ammonia compared with Example 2, other are all identical；
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
43 grams of (2.5mol) ammoniacal liquors are then added, ketone is 1:5 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen handle
Pressure is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom water
8.1 grams of phase, slow pressure release obtains organic phase: 47.9 grams；Gas chromatographic detection: 23.9% ketone and 75.7% methyl tertbutyl ketone
Imines；47.9 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of protochlorides
Copper and 20 grams of activated aluminas put into reaction kettle at room temperature.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is fallen after cooling
Reaction solution out divides and removes desiccant and catalyst, obtains 45.3 grams of product, the pinacolone azine of GC detection level 75.0% and 24.3%
Methyl tertbutyl ketone.
Embodiment 9:
Only have ketone different to the molar ratio range of ammonia compared with Example 2, other are all identical；
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
68 grams of (4mol) ammoniacal liquors are then added, ketone is 1:8 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen pressure
Power is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom aqueous phase
8.1 grams, slow pressure release obtains organic phase: 47.7 grams；Gas chromatographic detection: 23.7% ketone and 75.9% methyl tertbutyl ketone it is sub-
Amine；47.7 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of stannous chlorides
Reaction kettle is put at room temperature with 20 grams of activated aluminas.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is poured out after cooling
Reaction solution, point removes desiccant and catalyst, obtain 45.2 grams of product, the pinacolone azine of GC detection level 75.2% and 24.1%
Methyl tertbutyl ketone.
Embodiment 10:
Only have ketone different to the molar ratio range of ammonia compared with Example 2, other are all identical；
50 grams of (0.5mol) methyl tertbutyl ketone (pinacolone) and 0.5 gram of ammonium chloride are put into one 0.2 liter of autoclave pressure,
170 grams of (10mol) ammoniacal liquors are then added, ketone is 1:20 to the molar ratio range of ammonia；Mixture is heated to 90 DEG C, with nitrogen handle
Pressure is increased to 3.0MPa.The mixture stirs 2 hours at 90 DEG C.After reactant is cooled to 15 DEG C, stands to divide and go bottom water
8.1 grams of phase, slow pressure release obtains organic phase: 47.6 grams；Gas chromatographic detection: 23.6% ketone and 76.0% methyl tertbutyl ketone
Imines；47.6 grams of reaction mixtures of gained (mixture of methyl tertbutyl ketimide and methyl tertbutyl ketone) and 2 grams of protochlorides
Copper and 20 grams of activated aluminas put into reaction kettle at room temperature.50 DEG C are heated to, oxygen is passed through under stirring 4 hours.It is fallen after cooling
Reaction solution out divides and removes desiccant and catalyst, obtains 45.1 grams of product, the pinacolone azine of GC detection level 75.3% and 24.0%
Methyl tertbutyl ketone.
The results are shown in Table 1 by embodiment 2,6-10,
Interpretation of result: as shown in Table 1, ketone to the molar ratio range of ammonia between 1:1-1:20 when, can obtain
To ketazine, the more more then conversion ratios of ammonia dosage are higher, ammonia to the molar ratio of ketone be more than after 3 conversion ratios increase slowly, more than 8 with
Afterwards, conversion ratio almost no longer increases, then adds ammonia and be equal to increase cost of material, thus ketone to the molar ratio of ammonia 1:3-1:8 it
Between when, the content of obtained ketazine is more, and ammonia dosage is reasonable, thus this range be preferred scope.
The present invention provides a kind of method of molecular oxygen oxidation method synthesizing ketazine, and this method is applicable not only to benzophenone also
The few alkenolic ketazine synthesis of carbon atom number is realized, raw material sources are extensive, and low in cost, Yi Huishou, this method does not have
Brine waste, energy consumption and at low cost, it is environmentally protective.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the above embodiments do not limit the invention in any form, all obtained by the way of equivalent substitution or equivalent transformation
Technical solution is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of technique that molecular oxygen oxidation method prepares ketazine, which comprises the steps of:
Ketimide is prepared, ketone and ammonia are put into autoclave pressure according to the proportion, adjusting pressure limit is 1.0-5.0MPa, temperature range
30-180 DEG C, reaction time 3-5 hour generates ketimide；Ammonia is 1:1-20:1 to the molar ratio range of ketone；
Decrease temperature and pressure isolates the mixture of ketimide and ketone；
By the mixture of ketimide and ketone, catalyst, desiccant investment reaction kettle in, be warming up to 30-80 DEG C, be passed through molecular oxygen into
Row oxidation reaction, pressure limit 0-1.0Mpa, oxidation time 3-6 hours；Molecular oxygen includes: oxygen or air；Separation
Purify ketazine.
2. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that prepare ketone Asia
Amine puts into ketone and ammonia in autoclave pressure according to the proportion, adjusting pressure limit be 1.0-5.0MPa, 30-180 DEG C of temperature range, instead
3-5 hours between seasonable, ketimide is generated；Ammonia is 2:1 to 5:1 to the molar ratio range of ketone.
3. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that prepare ketone Asia
Amine puts into ketone and ammonia in autoclave pressure according to the proportion, adjusting pressure limit be 2.0-4.0MPa, 50-100 DEG C of temperature range, instead
3-5 hours between seasonable, ketimide is generated；Ammonia is 1:1-20:1 to the molar ratio range of ketone.
4. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that prepare ketone Asia
Amine, by ketone, ammonia, catalyst investment autoclave pressure, adjusting pressure limit is 1.0-5.0MPa, 30-180 DEG C of temperature range, is reacted
Time 3-5 hour generates ketimide；Ammonia is 1:1-20:1 to the molar ratio range of ketone；The catalyst is ammonia salt.
5. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that prepare ketone Asia
Amine, by aliphatic ketone, ammonia, desiccant investment autoclave pressure in, adjustings pressure limit be 1.0-5.0MPa, 30-180 DEG C of temperature range,
Reaction time 3-5 hour generates ketimide；Ammonia is 1:1-20:1 to the molar ratio range of ketone；The desiccant includes: zeolite point
Son sieve, activated alumina, anhydrous sodium sulfate, silica gel.
6. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that by ketimide
In mixture, catalyst, desiccant the investment reaction kettle of ketone, it is warming up to 40-60 DEG C, air is passed through and carries out oxidation reaction, pressure
Power range be 0.2-0.6Mpa, oxidation time 3-6 hours.
7. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that by ketimide
In mixture, catalyst, desiccant the investment reaction kettle of ketone, it is warming up to 30-80 DEG C, molecular oxygen is passed through and carries out oxidation reaction,
Pressure limit is 0-1.0Mpa, oxidation time 3-6 hours；The catalyst is metal salt, and desiccant includes: zeolite molecules
Sieve, activated alumina, anhydrous sodium sulfate；The amount ranges of catalyst are 0.1%-20%.
8. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that by ketimide
In mixture, catalyst, desiccant the investment reaction kettle of ketone, it is warming up to 30-80 DEG C, molecular oxygen is passed through and carries out oxidation reaction,
Pressure limit is 0-1.0Mpa, oxidation time 3-6 hours；The catalyst is halide, and desiccant includes: zeolite molecules
Sieve or activated alumina；The amount ranges of catalyst are 1%-8%.
9. the technique that a kind of molecular oxygen oxidation method according to claim 1 prepares ketazine, which is characterized in that separating-purifying
Ketazine；Organic phase and catalyst are first separated, catalyst recycling uses, then by organic phase distilation, isolates ketazine, steams
Ketone out is reused for synthesis ketimide.
10. a kind of -9 described in any item molecular oxygen oxidation methods prepare the technique of ketazine according to claim 1, feature exists
In ketone includes: aliphatic ketone, aromatic ketone.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0153168A2 (en) * | 1984-02-17 | 1985-08-28 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing a hydrazine hydrohalide |
| JPS60239450A (en) * | 1984-05-14 | 1985-11-28 | Otsuka Chem Co Ltd | Preparation of benzophenonazine |
| US4751326A (en) * | 1982-08-25 | 1988-06-14 | Mitsubishi Gas Chemical Company, Inc. | Process for producing benzophenone-azine |
| US20020013495A1 (en) * | 2000-07-19 | 2002-01-31 | Manfred Jautelat | Process for preparing hydrazodicarbonamide via ketimines |
-
2019
- 2019-04-03 CN CN201910265501.5A patent/CN109824540A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751326A (en) * | 1982-08-25 | 1988-06-14 | Mitsubishi Gas Chemical Company, Inc. | Process for producing benzophenone-azine |
| EP0153168A2 (en) * | 1984-02-17 | 1985-08-28 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing a hydrazine hydrohalide |
| JPS60239450A (en) * | 1984-05-14 | 1985-11-28 | Otsuka Chem Co Ltd | Preparation of benzophenonazine |
| US20020013495A1 (en) * | 2000-07-19 | 2002-01-31 | Manfred Jautelat | Process for preparing hydrazodicarbonamide via ketimines |
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