CN104387338A - Preparation method of promethazine hydrochloride - Google Patents
Preparation method of promethazine hydrochloride Download PDFInfo
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- CN104387338A CN104387338A CN201410689269.5A CN201410689269A CN104387338A CN 104387338 A CN104387338 A CN 104387338A CN 201410689269 A CN201410689269 A CN 201410689269A CN 104387338 A CN104387338 A CN 104387338A
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- Prior art keywords
- toluene
- reaction
- water
- diethylamino
- promethazine hydrochloride
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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
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
- C07D279/26—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom without other substituents attached to the ring system
Abstract
The invention discloses a preparation method of promethazine hydrochloride. The preparation method comprises the following steps of reacting diethyl amine and epoxypropane to obtain 1-diethylamino-2-propanol, reacting 1-diethylamino-2-propanol, chloride sulfoxide and toluene to obtain 1-diethylamino-2-chloropropane, reacting 1-diethylamino-2-chloropropane and phenothiazine to obtain crude promethazine free body, purifying crude promethazine free body and then salifying purified promethazine and hydrochloric acid to obtain promethazine hydrochloride. The promethazine hydrochloride prepared by the preparation method, which is disclosed by the invention, has the advantages of good quality and high yield and the preparation method is simple and low in both energy consumption and cost.
Description
Technical field
The present invention relates to the preparation method of organic compound, specifically a kind of preparation method of promethazine hydrochloride.
Background technology
Promethazine hydrochloride (Promethazine Hydrochloride) is powder that is white or almost white or particle; Almost odorless, bitter; With the passing of time blueness is become in atmosphere.Promethazine hydrochloride to the telangiectasis caused by antihistamine, can reduce its permeability, and alleviate panting caused by bronchial smooth muscle contraction, comparatively Vena effect is lasting by force.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of promethazine hydrochloride, and its cost is low, and yield is high.
Technical scheme of the present invention is:
1, a preparation method for promethazine hydrochloride, comprises the steps:
(1), diethylamide and propylene oxide are joined in reaction vessel and stirs, then water is added, heat temperature raising, make stirring reaction 46h between temperature maintenance 40-50 DEG C, again reaction solution is heated after 46h, its temperature is made to keep 50-60 DEG C of reaction 21h, after again heat up, make maintenance 60-70 DEG C of stirring reaction 6h, temperature is made to heat up after 70-80 DEG C of stirring reaction 6h afterwards more again, make at 80-100 DEG C of stirring reaction 6h, to be allowed to condition at after 100-128 DEG C of stirring reaction 12h stirring reaction 2.5h between 128-130 DEG C more again, reaction solution is made to naturally cool to less than 50 DEG C after end, by reaction solution underpressure distillation, collect main distillate fraction 1-diethylamino-2-propyl alcohol,
(2), sulfur oxychloride and toluene are put in reaction vessel and stirs, then 1-diethylamino-2-propyl alcohol step (1) obtained and toluene by 1: 1.15-1.2 mass ratio mixed be incorporated in be less than 20 DEG C of conditions under be added dropwise in reaction vessel, dropwise, be warming up to 80-90 DEG C of stirring reaction 2h, cool after reaction terminates, water is being dripped when being cooled to 15-20 DEG C, dropwise, after keeping 10-20 DEG C to stir 30min, layering, water layer is after washing, pour toluene into wherein, ice bath is cooled to less than 5 DEG C, drip sodium hydroxide solution wherein, dropwise, insulation leaves standstill, layering, water layer toluene wash, combining methylbenzene layer, then at room temperature in toluene layer, diatomite is added, stir 15min, filter, Anhydrous potassium carbonate is added in filtrate, stir 15min, filter, 1-diethylamino-2 cbloropropane isopropyl chloride is obtained after concentrated,
(3), by thiodiphenylamine, toluene is put in reaction vessel and is stirred, then potassium hydroxide is poured into wherein, heating makes it backflow, after backflow 2h, keeping under reflux state, dripping the obtained 1-diethylamino-2 cbloropropane isopropyl chloride of step (2) wherein, dropwise and continue backflow 1h, cooling down to 30 DEG C, add first part's water vibration, layering, then sulfamic acid solution is dripped to toluene layer, after dropwising, stirring at normal temperature, layering, toluene layer washes with water, combining water layer, second section water is added in water layer, control temperature is less than 20 DEG C, drip sodium hydroxide solution wherein, dropwise rear stirring 10min, then water layer toluene wash, combining methylbenzene layer, wash three times with water, gained toluene layer concentrating under reduced pressure removes toluene, obtain the thick episome of promethazine,
(4), put in vacuum distillation apparatus by thick for promethazine episome, nitrogen heats under bad border, underpressure distillation, collects lower than 180 DEG C of front-end volatiles respectively, collects 180-199 DEG C of main distillate fraction, collects higher than 200 DEG C of after cut;
(5), episome main distillate fraction is put in reaction vessel, then water is added in stirring at room temperature, oil bath heating again, temperature is made to regulate PH to be less than 3 at 50-55 DEG C, heat temperature raising, makes interior temperature at 60-66 DEG C of stirring reaction 1h, cooling, recrystallization, filtration under diminished pressure, washing, obtain promethazine hydrochloride crude product;
(6), promethazine hydrochloride crude product is joined in reaction vessel, at room temperature stir after adding toluene, water wherein, then regulate PH=12, oil bath heat temperature raising, be incubated 34-38 DEG C of stirring reaction 4h, reaction terminates the vibration of rear reaction solution, separatory, toluene layer, after washing, concentrating under reduced pressure, underpressure distillation, obtains distillation episome, adds hydrochloric acid and makes salt, filter, obtain refining promethazine hydrochloride.
In described step (1), the mass ratio of diethylamide, propylene oxide and water is 1: 0.78-0.79: 0.016-0.017.
The mass ratio of the mixed solution of the sulfur oxychloride in described step (2) reaction, toluene and 1-diethylamino-2-propyl alcohol and toluene is 1: 1.45-1.5: 2.15-2.2; Sodium hydroxide solution in described step (2) selects mass percent to be 20% sodium hydroxide solution; The mass ratio of the water dripped after described step (2) reaction, toluene, 20% sodium hydroxide solution and the diatomite added and 1-diethylamino-2-propyl alcohol is 1.9-2: 1.45-2::4.1-4.2: 1.
The mass ratio of thiodiphenylamine, toluene, potassium hydroxide and the 1-diethylamino-2 cbloropropane isopropyl chloride in described step (3) back flow reaction is 0.09-0.1: 0.8-0.85: 0.25-0.3: 1; Sodium hydroxide solution in described step (3) selects mass percent to be 24% sodium hydroxide solution; Sulfamic acid solution in described step (3) selects mass percent to be 16.7% sulfamic acid solution; The mass ratio of the first part's water after described step (3) back flow reaction, 16.7% sulfamic acid solution, second section water, 24% sodium hydroxide solution and 1-diethylamino-2 cbloropropane isopropyl chloride is 0.7-0.75: 1.4-1.5: 0.7-0.75: 0.45-0.5.
In described step (5), the concrete steps of recrystallization add crystal seed under making interior temperature 30-35 DEG C condition, then keeps 25-35 DEG C to stir 3h, then continue to be cooled to 15-20 DEG C, stir 1h under this condition.
In described step (6), the mass ratio of promethazine hydrochloride crude product, toluene and water is 1: 3-3.1: 2.9-3.1.
Advantage of the present invention:
Promethazine hydrochloride quality prepared by the present invention is good, and yield is high, and preparation method is simple, and less energy consumption, cost is low.
Embodiment
A preparation method for promethazine hydrochloride, comprises the steps:
(1), 89g diethylamide and 70g propylene oxide are joined in reaction vessel and stirs, then 1.43g water is added, heat temperature raising, make stirring reaction 46h between temperature maintenance 40-50 DEG C, again reaction solution is heated after 46h, its temperature is made to keep 50-60 DEG C of reaction 21h, after again heat up, make maintenance 60-70 DEG C of stirring reaction 6h, temperature is made to heat up after 70-80 DEG C of stirring reaction 6h afterwards more again, make at 80-100 DEG C of stirring reaction 6h, to be allowed to condition at after 100-128 DEG C of stirring reaction 12h stirring reaction 2.5h between 128-130 DEG C more again, reaction solution is made to naturally cool to less than 50 DEG C after end, by reaction solution underpressure distillation, collect main distillate fraction 1-diethylamino-2-propyl alcohol,
(2), 16.7g sulfur oxychloride and 24.3g toluene are put in reaction vessel and stirs, then by mixed to the 1-diethylamino-2-propyl alcohol of 16.7g and 14.3g toluene be incorporated in be less than 20 DEG C of conditions under be added dropwise in reaction vessel, dropwise, be warming up to 80-90 DEG C of stirring reaction 2h, cool after reaction terminates, 32g water is being dripped when being cooled to 15-20 DEG C, dropwise, after keeping 10-20 DEG C to stir 30min, layering, water layer is after washing, pour 25g toluene wherein into, ice bath is cooled to less than 5 DEG C, drip 69g 20% sodium hydroxide solution wherein, dropwise, insulation leaves standstill, layering, water layer toluene wash, combining methylbenzene layer, then at room temperature in toluene layer, 4.7g diatomite is added, stir 15min, filter, 2.7g Anhydrous potassium carbonate is added in filtrate, stir 15min, filter, 1-diethylamino-2 cbloropropane isopropyl chloride is obtained after concentrated,
(3), by 15g thiodiphenylamine, 43.5g toluene is put in reaction vessel and is stirred, then 14.1g potassium hydroxide is poured into wherein, heating makes it backflow, after backflow 2h, 52.5g 1-diethylamino-2 cbloropropane isopropyl chloride is dripped wherein under maintenance reflux state, dropwise and continue backflow 1h, cooling down to 30 DEG C, add the vibration of 37.5g water, layering, then dripping 75g mass percent to toluene layer is 16.7% sulfamic acid solution, after dropwising, stirring at normal temperature, layering, toluene layer washes with water, combining water layer, 37.5g water is added in water layer, control temperature is less than 20 DEG C, dripping 25g mass percent is wherein 24% sodium hydroxide solution, dropwise rear stirring 10min, then water layer toluene wash, combining methylbenzene layer, wash three times with water, gained toluene layer concentrating under reduced pressure removes toluene, obtain the thick episome of promethazine,
(4), put in vacuum distillation apparatus by thick for 20.8g promethazine episome, nitrogen heats under bad border, underpressure distillation, collects lower than 180 DEG C of front-end volatiles 0.4g respectively, collects 180-199 DEG C of main distillate fraction 16.3g, collects higher than 200 DEG C of after cut 3.2g;
(5), 16.3g episome main distillate fraction is put in reaction vessel, then 32.5g water is added in stirring at room temperature, oil bath heating again, temperature is made to drip 16.5g15% hydrochloric acid soln wherein at 50-55 DEG C, PH is regulated to be less than 3, heat temperature raising, make interior temperature at 60-66 DEG C of stirring reaction 1h, cooling, adds crystal seed 0.1g under making interior temperature 30-35 DEG C condition, then keeps 25-35 DEG C to stir 3h, and then continue to be cooled to 15-20 DEG C, stir 1h under this condition, filtration under diminished pressure, washing, obtain promethazine hydrochloride crude product;
(6), 9.5g promethazine hydrochloride crude product is joined in reaction vessel, at room temperature stir after adding 29g toluene, 28.5g water wherein, then 28%NaOH solution is added wherein, temperature control makes it less than 30 DEG C, after dropwising, survey PH=12, oil bath heat temperature raising, be incubated 34-38 DEG C of stirring reaction 4h, separating funnel is poured into, vibration, separatory after reaction terminates, toluene layer water (30ml × 2) washes twice, concentrating under reduced pressure, except underpressure distillation after toluene, obtains distillation episome, adds hydrochloric acid and make salt, filter, obtain refining promethazine hydrochloride.
Claims (6)
1. a preparation method for promethazine hydrochloride, is characterized in that, comprises the steps:
(1), diethylamide and propylene oxide are joined in reaction vessel and stirs, then water is added, heat temperature raising, make stirring reaction 46h between temperature maintenance 40-50 DEG C, again reaction solution is heated after 46h, its temperature is made to keep 50-60 DEG C of reaction 21h, after again heat up, make maintenance 60-70 DEG C of stirring reaction 6h, temperature is made to heat up after 70-80 DEG C of stirring reaction 6h afterwards more again, make at 80-100 DEG C of stirring reaction 6h, to be allowed to condition at after 100-128 DEG C of stirring reaction 12h stirring reaction 2.5h between 128-130 DEG C more again, reaction solution is made to naturally cool to less than 50 DEG C after end, by reaction solution underpressure distillation, collect main distillate fraction 1-diethylamino-2-propyl alcohol,
(2), sulfur oxychloride and toluene are put in reaction vessel and stirs, then 1-diethylamino-2-propyl alcohol step (1) obtained and toluene by 1: 1.15-1.2 mass ratio mixed be incorporated in be less than 20 DEG C of conditions under be added dropwise in reaction vessel, dropwise, be warming up to 80-90 DEG C of stirring reaction 2h, cool after reaction terminates, water is being dripped when being cooled to 15-20 DEG C, dropwise, after keeping 10-20 DEG C to stir 30min, layering, water layer is after washing, pour toluene into wherein, ice bath is cooled to less than 5 DEG C, drip sodium hydroxide solution wherein, dropwise, insulation leaves standstill, layering, water layer toluene wash, combining methylbenzene layer, then at room temperature in toluene layer, diatomite is added, stir 15min, filter, Anhydrous potassium carbonate is added in filtrate, stir 15min, filter, 1-diethylamino-2 cbloropropane isopropyl chloride is obtained after concentrated,
(3), by thiodiphenylamine, toluene is put in reaction vessel and is stirred, then potassium hydroxide is poured into wherein, heating makes it backflow, after backflow 2h, keeping under reflux state, dripping the obtained 1-diethylamino-2 cbloropropane isopropyl chloride of step (2) wherein, dropwise and continue backflow 1h, cooling down to 30 DEG C, add first part's water vibration, layering, then sulfamic acid solution is dripped to toluene layer, after dropwising, stirring at normal temperature, layering, toluene layer washes with water, combining water layer, second section water is added in water layer, control temperature is less than 20 DEG C, drip sodium hydroxide solution wherein, dropwise rear stirring 10min, then water layer toluene wash, combining methylbenzene layer, wash three times with water, gained toluene layer concentrating under reduced pressure removes toluene, obtain the thick episome of promethazine,
(4), put in vacuum distillation apparatus by thick for promethazine episome, nitrogen heats under bad border, underpressure distillation, collects lower than 180 DEG C of front-end volatiles respectively, collects 180-199 DEG C of main distillate fraction, collects higher than 200 DEG C of after cut;
(5), episome main distillate fraction is put in reaction vessel, then water is added in stirring at room temperature, oil bath heating again, temperature is made to regulate PH to be less than 3 at 50-55 DEG C, heat temperature raising, makes interior temperature at 60-66 DEG C of stirring reaction 1h, cooling, recrystallization, filtration under diminished pressure, washing, obtain promethazine hydrochloride crude product;
(6), promethazine hydrochloride crude product is joined in reaction vessel, at room temperature stir after adding toluene, water wherein, then regulate PH=12, oil bath heat temperature raising, be incubated 34-38 DEG C of stirring reaction 4h, reaction terminates the vibration of rear reaction solution, separatory, toluene layer, after washing, concentrating under reduced pressure, underpressure distillation, obtains distillation episome, adds hydrochloric acid and makes salt, filter, obtain refining promethazine hydrochloride.
2. the preparation method of a kind of promethazine hydrochloride according to claim 1, is characterized in that: in described step (1), the mass ratio of diethylamide, propylene oxide and water is 1: 0.78-0.79: 0.016-0.017.
3. the preparation method of a kind of promethazine hydrochloride according to claim 1, is characterized in that: the mass ratio of the mixed solution of the sulfur oxychloride in described step (2) reaction, toluene and 1-diethylamino-2-propyl alcohol and toluene is 1: 1.45-1.5: 2.15-2.2; Sodium hydroxide solution in described step (2) selects mass percent to be 20% sodium hydroxide solution; The mass ratio of the water dripped after described step (2) reaction, toluene, 20% sodium hydroxide solution and the diatomite added and 1-diethylamino-2-propyl alcohol is 1.9-2: 1.45-2::4.1-4.2: 1.
4. the preparation method of a kind of promethazine hydrochloride according to claim 1, is characterized in that: the mass ratio of thiodiphenylamine, toluene, potassium hydroxide and the 1-diethylamino-2 cbloropropane isopropyl chloride in described step (3) back flow reaction is 0.09-0.1: 0.8-0.85: 0.25-0.3: 1; Sodium hydroxide solution in described step (3) selects mass percent to be 24% sodium hydroxide solution; Sulfamic acid solution in described step (3) selects mass percent to be 16.7% sulfamic acid solution; The mass ratio of the first part's water after described step (3) back flow reaction, 16.7% sulfamic acid solution, second section water, 24% sodium hydroxide solution and 1-diethylamino-2 cbloropropane isopropyl chloride is 0.7-0.75: 1.4-1.5: 0.7-0.75: 0.45-0.5.
5. the preparation method of a kind of promethazine hydrochloride according to claim 1, it is characterized in that: in described step (5), the concrete steps of recrystallization add crystal seed under making interior temperature 30-35 DEG C condition, then keep 25-35 DEG C and stir 3h, continue again to be cooled to 15-20 DEG C, under this condition, stir 1h.
6. the preparation method of a kind of promethazine hydrochloride according to claim 1, is characterized in that: in described step (6), the mass ratio of promethazine hydrochloride crude product, toluene and water is 1: 3-3.1: 2.9-3.1.
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| CN201410689269.5A CN104387338B (en) | 2014-11-26 | 2014-11-26 | Preparation method of promethazine hydrochloride |
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| CN201410689269.5A CN104387338B (en) | 2014-11-26 | 2014-11-26 | Preparation method of promethazine hydrochloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292513A (en) * | 2021-05-25 | 2021-08-24 | 常州康普药业有限公司 | Preparation method of high-purity promethazine hydrochloride |
| CN115974813A (en) * | 2022-12-20 | 2023-04-18 | 云鹏医药集团有限公司 | Synthetic method of high-purity promethazine hydrochloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2526118A (en) * | 1950-10-17 | Paul chabpentier | ||
| GB688481A (en) * | 1950-03-14 | 1953-03-11 | Wellcome Found | Improvements in or relating to diphenyl ketones of pharmaceutical value and to the preparation thereof |
-
2014
- 2014-11-26 CN CN201410689269.5A patent/CN104387338B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2526118A (en) * | 1950-10-17 | Paul chabpentier | ||
| GB688481A (en) * | 1950-03-14 | 1953-03-11 | Wellcome Found | Improvements in or relating to diphenyl ketones of pharmaceutical value and to the preparation thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292513A (en) * | 2021-05-25 | 2021-08-24 | 常州康普药业有限公司 | Preparation method of high-purity promethazine hydrochloride |
| CN113292513B (en) * | 2021-05-25 | 2022-03-25 | 常州康普药业有限公司 | Preparation method of high-purity promethazine hydrochloride |
| CN115974813A (en) * | 2022-12-20 | 2023-04-18 | 云鹏医药集团有限公司 | Synthetic method of high-purity promethazine hydrochloride |
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| CN104387338B (en) | 2017-01-18 |
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