CN105524016B - The synthetic method and application of phenthazine and/or its derivative - Google Patents
The synthetic method and application of phenthazine and/or its derivative Download PDFInfo
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- CN105524016B CN105524016B CN201510767227.3A CN201510767227A CN105524016B CN 105524016 B CN105524016 B CN 105524016B CN 201510767227 A CN201510767227 A CN 201510767227A CN 105524016 B CN105524016 B CN 105524016B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention discloses the synthetic method of a kind of phenthazine and/or its derivative, including：Diphenylamines and/or diphenylamine derivatives, sulphur and solid acid catalyst are mixed to be placed in protective atmosphere and fully reacted, then is post-treated and obtain phenthazine and/or phenothiazine derivative.The invention also discloses the purposes of the phenthazine and/or its derivative.The synthetic method of phenthazine and/or its derivative provided by the invention is a kind of energy-saving safe, environmentally protective technique; its technological operation is simple; mild condition; reaction time is short; convenient for control; technical process is safe, and low energy consumption for production process, and yield is high; product purity is high; water, organic solvent etc. need not be added in reaction process, post processing is simple, and in addition raw material and solid acid catalyst etc. derive from a wealth of sources; it is cheap and easy to get; and the also recyclable recycling of solid acid catalyst, it is at low cost, suitable for large-scale production.
Description
Technical field
The present invention is more particularly directed to the synthetic methods and application of a kind of phenthazine and/or its derivative.
Background technology
In use, because of the effect of heat, light or oxygen, the chemical bond in molecule can occur for oil product, plastics, rubber etc.
Fracture, generates active free radical and hydroperoxides, and hydroperoxides are further decomposed reaction, and it is free to generate hydrocarbon oxygen
Base and hydroxyl radical free radical.These free radicals can cause a series of free chain reaction, lead to the structure of organic compound
Basic change occurs with property.Traditional solution is that one or more antioxidant are added in oil product, plastics, rubber (again
Claim anti-aging agent), decomposition of the nationality to eliminate active free radical or promote hydroperoxides prevents the progress of chain reaction, from
And delay or the progress of inhibiting substances oxidation process, it prevents the aging of substance and extends its service life.
Phenthazine, alias phenothiazine are the one kind for commonly using antioxidant, can be applied in lubricating oil, it can also be used to
Drug, the synthesis of dyestuff and synthetic material used additives etc. (such as the polymerization inhibitor of vinyl acetate, the original of rubber anti-aging agent
Material)；Also serve as livestock anthelmintic, fruit tree insecticide etc..
At present, phenthazine and its derivative are mainly the work for passing through diphenylamines and its derivative and sulphur in different catalysts
With lower synthesis, there are mainly three types of existing catalyst：Elemental iodine, alchlor, active soil.For example, US2360295A,
US2415363A、US2433658A、US2587662A、US2781318A、US3536706A、US5413737A、US5520848A、
CN101234315B, CN104496938A etc. disclose the method that phenthazine and derivative are synthesized using elemental iodine as catalyst,
But iodine catalyst is expensive, while last handling process need to use the operations such as distillation, benzene recrystallization, therefore energy consumption is higher, production
It is of high cost.In another example the patent documents such as US5520848A, CN104496938A and some non-patent literatures (such as Tian Lieguang etc.,
Synthesis lubriation material the 4th phases of .2000 page 20) etc. disclose using alchlor as catalyst synthesis phenthazine and its derivative
Method, although the aluminum trichloride catalyst used in these methods is more cheap than iodine catalyst, process conditions are harsh, and can draw
Enter halide, and lead to more serious environmental pollution, because due to be eliminated.In another example Tian Lieguang etc. (synthesis lubriation material,
4th phase page 20 in 2000) and JP3273271957A etc. disclose the method that phenthazine is synthesized using active soil as catalyst,
Catalyst is made using active soil in these techniques, it is more cheap and easy to get and environmental-friendly, but its post processing is still needed to using distillation
With benzene recrystallization method, cost and energy consumption are still higher.
Invention content
It is existing to overcome it is a primary object of the present invention to provide the synthetic method of a kind of phenthazine and/or its derivative
Deficiency in technology.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of phenthazine and/or the synthetic method of its derivative are provided in some embodiments, including：By diphenylamines
And/or diphenylamine derivatives, sulphur and solid acid catalyst mixing are placed in protective atmosphere and fully react, then post-treated
And obtain phenthazine and/or phenothiazine derivative.
Wherein, the solid acid catalyst include the Emathlite containing free acid, with dissociate acid activation Emathlite,
Silica gel, montmorillonite, diatomite, activated carbon, zeolite, molecular sieve, porous ceramics, aluminium oxide, zirconium oxide, silicon nitride, silicon carbide and
Any one in graphite or two or more combinations, and it is without being limited thereto.
In some more specific case study on implementation, the post processing includes：After the completion of the reaction, to obtained thick production
Object carry out purification process, the purification process include the crude product dissolve with organic solvent, alkali liquid washing and remove solvent
Combination step.
Another object of the present invention also reside in the phenthazine and/or its derivative and its synthetic method be provided should
With.
Compared with prior art, beneficial effects of the present invention at least that：
(1) solid acid catalyst and remaining raw material that synthetic method provided by the invention uses during the reaction are cheap
It is easy to get, derives from a wealth of sources, and synthetic reaction can be made to carry out generation that is more thorough, and effectively reducing side reaction, and then make mesh
The yield of mark product is substantially improved, while also make the technological operation of synthetic reaction more simple, and process conditions are more mild controllable,
Technical process safety higher, energy consumption are lower；
(2) synthetic method provided by the invention need not add water, organic solvent etc., postprocessing working procedures letter during the reaction
It is single easy to operate, especially by alkali liquid washing process is used, the yield and purity of target product can be also further promoted, in addition also
Solid acid catalyst etc. can be recycled and reused, help to further reduce the cost.
In short, the phenthazine of the present invention and/or the synthetic method of its derivative are that a kind of have energy-saving safe, environmentally protective
And the technique of many advantages, such as low cost, suitable for large-scale production.
Description of the drawings
Fig. 1 is HPLC (high performance liquid chromatography) figure that embodiment 2 obtains final products.
Specific embodiment
As previously mentioned, in view of deficiency of the prior art, for inventor through studying for a long period of time and largely putting into practice, spy proposes this
The technical solution of invention, and obtain unexpected good technique effect.Technical scheme of the present invention will be carried out as follows compared with
For detailed explanation.
One aspect of the present invention provides a kind of phenthazine and/or the synthetic method of its derivative, is mainly based upon
Solid acid catalyst and implement.
In some embodiments, the synthetic method includes：By diphenylamines and/or diphenylamine derivatives, sulphur and solid
Acid catalyst mixing is placed in protective atmosphere and fully reacts, then post-treated and obtain phenthazine and/or phenthazine derives
Object.
It particularly, in some embodiments, will preferably under the conditions of completely without existing for organic solvent, water equal solvent
Diphenylamines and/or diphenylamine derivatives, sulphur and solid acid catalyst mixing are placed in protective atmosphere and fully react, then pass through
It post-processes and obtains phenthazine and/or phenothiazine derivative.
Wherein, described " fully reaction " refers to not continue to generate hydrogen sulfide in reaction to hybrid reaction system.
Wherein, the structure of the diphenylamines and/or diphenylamine derivatives is shown below：
Wherein R1, R2, R3Independent is selected from hydrogen, halogen, aromatic rings, C1~C10 linear or branched alkyl groups, and m, n are selected from 1~4
In arbitrary integer, R1, R2, R3It is identical or different.
Wherein, the solid acid catalyst include the Emathlite containing free acid, with dissociate acid activation Emathlite,
Silica gel, montmorillonite, diatomite, activated carbon, zeolite, molecular sieve, porous ceramics, aluminium oxide, zirconium oxide, silicon nitride, silicon carbide, stone
Any one in ink or two or more combinations, and it is without being limited thereto.
Preferably, the solid acid catalyst is selected from the Emathlite for the acid activation that dissociates, wherein the free acid can wrap
Include inorganic acid and/or organic acid.
Wherein, the inorganic acid may include sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, hydrogen cyanide, sulfurous acid, phosphoric acid, poly phosphorus
Any one in acid, phosphotungstic acid, hydrofluoric acid, perchloric acid, boric acid, bromic acid, carbonic acid or two or more combinations, and be not limited to
This.
Wherein, the organic acid may include formic acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, uncle penta
Any one in acid, alkyl benzene sulphonate or two or more combinations, and it is without being limited thereto.
Preferably, the alkyl of the alkyl benzene sulphonate is selected from the straight chained alkyl of C1~C28 or the alkyl with branch,
Middle alkyl is distributed in ortho position, meta or para position.
In some preferable case study on implementation, the preparation method of the Emathlite of the free acid activation can include：With trip
Sour processing is carried out to carclazyte from acid, and the mass ratio of free acid and carclazyte is 0.3~5：1, treatment temperature is 15~120 DEG C, the time
It for 0.5~7h, dries later, and 1.5~5h is roasted at 100~300 DEG C.
In some embodiments, the reaction temperature used in the synthetic method is 50 DEG C~500 DEG C, preferably 110 DEG C
~300 DEG C, especially preferably 110 DEG C~250 DEG C.
In some embodiments, include inert gas (such as argon gas), two to form the gas of the protective atmosphere
Any one of carbonoxide and nitrogen or two or more combinations, and it is without being limited thereto.
In some embodiments, the synthetic method may also include：With the hydrogen sulfide gas generated in lye absorbing reaction.
In some embodiments, the molar ratio of the diphenylamines and/or diphenylamine derivatives and sulphur is 1: 0.5~6, especially
Preferably 1: 1~4.
In some embodiments, the mass ratio of the diphenylamines and/or diphenylamine derivatives and solid acid catalyst is 1:
0.02~0.65, preferably 1: 0.1~0.4.
Further, the phenthazine and/or phenothiazine derivative have structure shown in following formula：
Wherein, R1, R2, R3It is independent selected from hydrogen, halogen, aromatic rings, C1~C10 linear or branched alkyl groups, m, n be selected from 1~
Arbitrary integer in 4, R1, R2, R3It is identical or different.
In some embodiments, the post processing includes：After the completion of the reaction, obtained crude product is carried out at purifying
Reason, the purification process include the crude product dissolve with organic solvent, alkali liquid washing and removing solvent combination step.
Further, the organic solvent includes ketone (such as acetone), esters, alkyl halide hydro carbons, alcohols, ethers, virtue
Any one in fragrant hydrocarbon solvent or two or more combinations, and it is without being limited thereto.Preferably, the organic solvent includes third
Any one in ketone, ethyl acetate, ethyl alcohol, methanol, toluene, dimethylbenzene, petroleum ether, dichloromethane or two or more groups
It closes.
Further, the lye is selected from comprising sodium hydroxide, sodium carbonate, calcium hydroxide, potassium hydroxide, ammonium hydroxide and thio
Any one in sodium sulphate or the solution of two or more combinations, and it is without being limited thereto.
In some more specific case study on implementation, the post processing includes：Obtained crude product, which is dissolved in, at normal temperatures has
In solvent, and insoluble matter therein is removed using modes such as filterings, after remaining clear liquid is with alkali liquid washing, isolates organic phase,
And organic solvent therein is distilled off, then through being dried, and then obtain target product.
Wherein, the mode of drying process can select any suitable method known to industry, such as vacuum drying or red
Outer drying.
The temperature of the drying process is 20 DEG C~180 DEG C, especially preferably 20 DEG C~120 DEG C, further preferably 50
DEG C~100 DEG C.
The time of the drying process is 0.5h~20h, further preferably especially preferably 2h~10h, 3h~8h.
Wherein it is possible to the organic solvent in organic phase is removed using modes such as distillations.
In some particularly specific case study on implementation, the synthetic method can include：
(1) crude product is synthesized
Diphenylamines and its derivative, sulphur and solid acid catalyst are added in reaction vessel, inert gas is passed through, normal
It is fully reacted under pressure and suitable temperature, obtains crude product, and the hydrogen sulfide gas generated is passed through lye absorption plant and is allowed to and lye
Reaction.
(2) purifying post processing
By crude product normal-temperature dissolution, add alkali liquid washing, liquid separation, organic solvent, vacuum or infrared baking is distilled off in filtering
It is dry, obtain target product.
Another aspect of the present invention additionally provides the phenthazine prepared by the synthetic method and/or phenthazine derives
Object.
An additional aspect of the present invention additionally provides the phenthazine and/or the application of its derivative.
For example, providing a kind of composition in some embodiments, it includes the phenthazine and/or phenthazine to derive
Object.
For example, a kind of preparation method of composition is provided in some embodiments, including：
Phenthazine and/or phenothiazine derivative are prepared using the synthetic method；
The phenthazine and/or phenothiazine derivative with more than one auxiliary substances are assembled and form the composition.
Wherein, the composition includes arbitrary in additive composition for lubricant oil, lubricant oil composite, plastics, rubber
It is a kind of.
More specifically, for example, the phenthazine and/or phenothiazine derivative can be answered as the active component of antioxidant
For in lubricant oil composite.In another example the phenthazine and/or phenothiazine derivative can be as the active components of antiager
Applied in plastics or rubber composition.
The technical solution in the embodiment of the present invention is described in detail below in conjunction with several embodiments, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill all other embodiments obtained under the premise of creative work is not made, belong to this hair
The range of bright protection.
The solid acid catalyst used in following examples is selected from the Emathlite containing free acid, with the acid activation that dissociates
Emathlite, silica gel, montmorillonite, diatomite, activated carbon, zeolite, molecular sieve, porous ceramics, aluminium oxide, zirconium oxide, silicon nitride,
Silicon carbide, graphite, particularly with the Emathlite for the acid activation that dissociates.For example, the Emathlite of wherein typical free acid activation can
It prepares in the following manner：Sour processing carries out carclazyte with free acid, the mass ratio of free acid and carclazyte is 0.3~5：1, processing temperature
It is 15~120 DEG C to spend, and the time is 0.5~7h, is dried later, and roasts 1.5~5h at 100~300 DEG C, wherein the free acid
It may include inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, hydrogen cyanide, sulfurous acid, phosphoric acid, polyphosphoric acids, phosphotungstic acid, hydrogen
Fluoric acid, perchloric acid, boric acid, bromic acid, carbonic acid or organic acid, such as formic acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzene
Formic acid, methanesulfonic acid, trimethylacetic acid, alkyl benzene sulphonate etc., wherein alkyl are selected from the straight chained alkyl of C1~C28 or the alkane with branch
Base, wherein alkyl are distributed in ortho position, meta or para position.
Embodiment 1 takes about 3.0~3.5 grams of diphenylamines, about 1.4~1.5 grams of sulphur, about 0.5~0.7 gram of solid acid catalyst
It adds in three-necked flask, is heated to about 50 DEG C~75 DEG C reactions, until hydrogen sulfide gas is not generated, in reaction process always
Inert gas is passed through, phenthazine crude product is obtained after the completion of reaction.The crude product purity is tested, as a result it is found that crude product purity
Average about 80.0%.
Embodiment 2 takes about 3.0~3.5 grams of diphenylamines, about 1.8~2.0 grams of sulphur, about 0.8~1.0 gram of solid acid catalyst
110~145 DEG C of reactions are heated in the three-necked flask of 100ml, until hydrogen sulfide gas is not generated, in reaction process always
Inert gas is passed through, phenthazine crude product is obtained after the completion of reaction.The crude product with 25ml-30ml ethyl acetate is dissolved, is filtered, it will
Filtrate is washed with hypo solution, and liquid separation takes organic phase, and ethyl acetate is distilled off, and 60 DEG C of vacuum drying chambers dry 5h, obtain
Final products, yield averagely about 80.0%, purity is up to more than 98% (as shown in Figure 1), fusing point about 182.49~184.13
℃。
Embodiment 3 takes about 15.0~17.5 grams of diphenylamines, about 9.0~10.0 grams of sulphur, and about 4.0~5.0 grams of solid acids are urged
Agent is heated to about 110~145 DEG C of reactions, until hydrogen sulfide gas is not generated, reaction in the three-necked flask of 500ml
It is passed through inert gas always in the process, obtains crude product after reaction, be re-dissolved in the petroleum ether of 125ml~150ml, filter, take
Filtrate washs it with sodium hydroxide solution, and liquid separation takes organic phase, and petroleum ether is distilled off, and 60 DEG C of vacuum drying chambers dry 5h,
Obtain phenthazine.Yield averagely about 81.1%, purity averagely about 92.3%.
Embodiment 4 takes about 27.0~28.5 gram 4,4,Di-t-butyl-diphenylamines, about 15.0~17.0 grams of sulphur, about 9.5
~11.0 grams of solid acid catalysts are heated to about 275~300 DEG C of reactions, until not generating hydrogen sulfide in the there-necked flask of 500ml
Until gas, inert gas is passed through in reaction process always, obtains crude product after reaction, be re-dissolved in 200~250ml just oneself
Alkane, filtering, takes filtrate, it is washed with sodium carbonate liquor, and liquid separation takes organic phase, and n-hexane, 60 DEG C of vacuum drying are distilled off
Case dries about 5h, obtains 3,7- di-t-butyls-phenthazine.Yield averagely about 81.0%, purity averagely about 91.0%.
Embodiment 5 takes about 37.80~39.30 gram 4,4,- two (1,1,3,3- tetramethyl-butyl)-diphenylamines, about 17.0~
18.0 grams of sulphur, about 9.05~11.33 grams of solid acid catalysts are heated to about 480~500 DEG C instead in the there-necked flask of 500ml
Should, until hydrogen sulfide gas is not generated, inert gas is passed through in reaction process always, obtains crude product after reaction, then
The toluene of 200-250ml is dissolved in, is filtered, is taken filtrate, it is washed with potassium hydroxide solution, liquid separation takes organic phase, is distilled off
Toluene, 60 DEG C of vacuum drying chambers dry about 5h, obtain 3,7- bis- (1,1,3,3- tetramethyl-butyl)-phenthazine.Yield is averagely about
78.0%, purity averagely about 88.0%.
Reference examples 1：This reference examples is substantially the same manner as Example 2, but solid acid catalysis therein is substituted using active soil
Agent, obtains the average purity about 60.4% of crude product, and crude product after purification, obtains the average yield of product about by 2 scheme of embodiment
60.0%, average purity about 68.0%.
Reference examples 2：This reference examples is substantially the same manner as Example 2, but is not operated in last handling process using alkali liquid washing, institute
Obtain the average yield about 82.0% of product, average purity about 88.0%.
It should be noted that various reaction partners and process conditions are more typical used by example is performed as described above
Example, but by the verification of inventor a large number of experiments, in the other different types of reaction partners of those listed above and its
Its process conditions etc. are also applicable, and also equal attainable cost invents claimed technique effect.
Postscript, herein, term " comprising ", "comprising" or its any other variant are intended to the packet of nonexcludability
Contain so that process, method, article or equipment including a series of elements not only include those elements, but also including
It other elements that are not explicitly listed or further includes as elements inherent to such a process, method, article, or device.
It should be appreciated that the above is only the specific embodiment of the present invention, it is noted that for the general of the art
For logical technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these improve and
Retouching also should be regarded as protection scope of the present invention.
Claims (21)
1. a kind of synthetic method of phenthazine and/or its derivative, it is characterised in that including：Diphenylamines and/or diphenylamines are spread out
Biology, sulphur and solid acid catalyst mixing are placed in protective atmosphere and fully react, then post-treated and obtain phenthazine
And/or phenothiazine derivative；
The phenthazine or phenothiazine derivative have structure shown in following formula：
Wherein, R1, R2, R3Independent is selected from hydrogen, halogen, aromatic rings, C1~C10 linear or branched alkyl groups, and m, n are in 1~4
Arbitrary integer, R1, R2, R3It is identical or different；
The structure of the diphenylamines and/or diphenylamine derivatives is shown below：
Wherein, R1, R2, R3Independent is selected from hydrogen, halogen, aromatic rings, C1~C10 linear or branched alkyl groups, and m, n are in 1~4
Arbitrary integer, R1, R2, R3It is identical or different；
The solid acid catalyst is selected from the Emathlite for the acid activation that dissociates, the preparation of the Emathlite of the free acid activation
Method is：Sour processing carries out carclazyte with free acid, the mass ratio of free acid and carclazyte is 0.3~5：1, treatment temperature for 15~
120 DEG C, the time is 0.5~7h, is dried later, and 1.5~5h is roasted at 100~300 DEG C, and the free acid is used to toluene sulphur
Acid.
2. synthetic method according to claim 1, it is characterised in that：The reaction temperature used in the synthetic method is 50
DEG C~500 DEG C.
3. synthetic method according to claim 2, it is characterised in that：The reaction temperature used in the synthetic method for
110 DEG C~300 DEG C.
4. synthetic method according to claim 3, it is characterised in that：The reaction temperature used in the synthetic method for
110 DEG C~250 DEG C.
5. synthetic method according to claim 1, it is characterised in that：Gas to form the protective atmosphere is selected from
Any one of argon gas, carbon dioxide and nitrogen or two or more combinations.
6. synthetic method according to claim 1, which is characterized in that the synthetic method further includes：It is absorbed with lye anti-
It should the middle hydrogen sulfide gas generated.
7. synthetic method according to claim 1, it is characterised in that：The diphenylamines and/or diphenylamine derivatives and sulphur
The molar ratio of sulphur is 1:0.5~6.
8. synthetic method according to claim 7, it is characterised in that：The diphenylamines and/or diphenylamine derivatives and sulphur
The molar ratio of sulphur is 1:1~4.
9. synthetic method according to claim 1, it is characterised in that：The diphenylamines and/or diphenylamine derivatives are with consolidating
The mass ratio of body acid catalyst is 1:0.02~0.65.
10. synthetic method according to claim 9, it is characterised in that：The diphenylamines and/or diphenylamine derivatives are with consolidating
The mass ratio of body acid catalyst is 1:0.1~0.4.
11. synthetic method according to claim 1, which is characterized in that the post processing includes：It is completed in the reaction
Afterwards, purification process is carried out to obtained crude product, the purification process is included so that organic solvent dissolves the crude product, lye is washed
Wash and remove the combination step of solvent.
12. synthetic method according to claim 11, which is characterized in that the post processing includes：It will be obtained at normal temperatures
Crude product is dissolved in organic solvent, and removes insoluble matter therein, after remaining clear liquid is with alkali liquid washing, isolates organic phase, and
Evaporation removes organic solvent therein, then through being dried, and then obtains target product.
13. synthetic method according to claim 12, it is characterised in that：The temperature of the drying process is 20 DEG C~180
℃。
14. synthetic method according to claim 13, it is characterised in that：The temperature of the drying process is 20 DEG C~120
℃。
15. synthetic method according to claim 14, it is characterised in that：The temperature of the drying process is 50 DEG C~100
℃。
16. synthetic method according to claim 12, it is characterised in that：The time of the drying process is 0.5h~20h.
17. synthetic method according to claim 16, it is characterised in that：The time of the drying process is 2h~10h.
18. synthetic method according to claim 17, it is characterised in that：The time of the drying process is 3h~8h.
19. synthetic method according to claim 18, it is characterised in that：The organic solvent using acetone, ethyl acetate,
Any one in ethyl alcohol, methanol, toluene, dimethylbenzene, petroleum ether, dichloromethane or two or more combinations.
20. the synthetic method according to claim 11 or 12, it is characterised in that：The lye be selected from comprising sodium hydroxide,
Any one in sodium carbonate, calcium hydroxide, potassium hydroxide, ammonium hydroxide and sodium thiosulfate or the solution of two or more combinations.
21. a kind of preparation method of composition, it is characterised in that including：
Phenthazine and/or phenothiazine derivative are prepared using the method described in any one of claim 1-20；
The phenthazine and/or phenothiazine derivative with more than one auxiliary substances are assembled and form the composition.
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| CN112724103A (en) * | 2020-12-16 | 2021-04-30 | 广安凯特制药有限公司 | Isopromazine specific impurity and analysis method and removal method thereof |
| CN116425637A (en) | 2022-01-01 | 2023-07-14 | 中国石油化工股份有限公司 | Method and device for preparing diphenylamine and phenothiazine from aniline |
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