CN103073447B - Synthesis method for 2-para-fluorobenzoylbut benzamide - Google Patents
Synthesis method for 2-para-fluorobenzoylbut benzamide Download PDFInfo
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- CN103073447B CN103073447B CN201310040255.6A CN201310040255A CN103073447B CN 103073447 B CN103073447 B CN 103073447B CN 201310040255 A CN201310040255 A CN 201310040255A CN 103073447 B CN103073447 B CN 103073447B
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Abstract
The invention discloses a synthesis method for 2-para-fluorobenzoylbut benzamide. The target product 2-para-fluorobenzoylbut benzamide is synthetized by taking 2-para-fluorobenzoylbut benzoic acid, phosphorus oxychloride and ammonium chloride as raw materials under the action that catalyst anhydrous lewis acid is neutralized by a dichloroethane solvent. The synthesis method for the 2-para-fluorobenzoylbut benzamide has the advantages that operating steps are simple; the reaction condition is mild; the energy consumption is low; the producing cost is reduced; the production cycle is short; the product yield is at least 95.5 percent; the product purity is at least 99 percent; and quality requirements of markets on the 2-para-fluorobenzoylbut benzamide are met.
Description
Technical field
The invention belongs to fine chemical technology field, relate to a kind of synthetic method of pharmaceutical chemicals intermediate, be specifically related to the synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide.
Background technology
2-is the fluoro-phenyl of important intermediate (E)-3-[2-cyclopropyl-4-(4-of synthetic pharmaceutical chemicals Pitavastatin Calcium to fluorobenzoyl yl-benzamide)-3-quinolyl] critical materials of propenal; in pharmaceutical chemicals is synthetic, play an important role, there are wide market outlook.
At present, preparation 2-to fluorobenzoyl yl-benzamide be taking 2-to fluorobenzoyl yl benzoic acid as raw material, first, with sulfur oxychloride chlorination, then in chlorizate, pass into ammonia, add water washing, filter 2-to fluorobenzoyl yl-benzamide.In above-mentioned synthetic method, its deficiency is: the wayward ammonia amount that passes into, easily cause the waste of ammonia, and strengthen manufacturing cost; Add that while generating product, ammonia is difficult for being absorbed, cause product yield low.Therefore select one relatively cheap, safe synthesis technique simple to operate will have very large economic worth.
Summary of the invention
For the deficiencies in the prior art; the invention provides the synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; solved in prior art production cost high, operate the problem wayward, product yield is low, operation steps of the present invention is simple, reaction conditions gentleness; energy consumption is low; with short production cycle, product yield and purity are high, and yield is more than 95.5%; purity more than 99%, meet market to 2-the specification of quality to fluorobenzoyl yl-benzamide.
The synthetic method of a kind of 2-provided by the invention to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation; synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
The synthetic method of 2-to fluorobenzoyl yl-benzamide, concrete steps comprise:
(1) 2-is joined in ethylene dichloride solvent fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride, then add the anhydrous Lewis acid of catalyzer, be heated to 77-90 DEG C, carry out insulation reaction;
(2) after having reacted, be cooled to room temperature, reaction solution is poured in frozen water, then adopt separating funnel separatory, take off a layer organic phase, washing, filtration, oven dry;
(3) material after drying in step (2) is washed, filters, dried, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide.
2-of the present invention purchases in Jiangxi Ai Feimu pharmaceutcal corporation, Ltd fluorobenzoyl yl benzoic acid, and other raw materials are commercially available prod.
Wherein the described insulation reaction of step (1) adopts electric mantle heating, reaction conditions gentleness, and temperature of reaction is 77-90 DEG C, in reaction process, solvent refluxing can be controlled the rising of temperature, forms like this reflux state reaction is more easily carried out.
Described 2-is to fluorobenzoyl yl benzoic acid: ammonium chloride: phosphorus oxychloride: the mol ratio of catalyzer is 1:1-1.5:0.2-1:1-2.
Described 2-is to fluorobenzoyl yl benzoic acid: ammonium chloride: phosphorus oxychloride: the mol ratio of catalyzer is 1:1.10-1.20:0.55:1.5-1.7.
Wherein 2-generates intermediate state 2-to fluoro benzoyl Benzoyl chloride to fluorobenzoyl yl benzoic acid and phosphorus oxychloride with specific molar ratio reaction, improve reactive behavior, reaction is more easily carried out, and then reacted generation product 2-with ammonium chloride to fluorobenzoyl yl-benzamide; Described 2-to fluorobenzoyl yl benzoic acid and catalyzer in certain molar ratio range; catalyzer is brought into play maximum catalytic effect on the one hand; the yield of product is reached more than 95.5%; water in reaction solution can be removed completely on the one hand; reaction is carried out the direction of fluorobenzoyl yl-benzamide to product 2-, the purity of product is reached more than 99%.
In described step (1), the temperature rise rate of temperature-rise period is 3.5-4.5 DEG C/min, can in temperature-rise period, reduce like this generation of impurity, has ensured the quality of product 2-to fluorobenzoyl yl-benzamide.
The time of insulation reaction is 1.5-3 hour in described step (1), if the time is too short, reacts not composition, and the quality of product can not ensure, if overlong time, the production cycle long, increase production cost.
The anhydrous Lewis acid of described catalyzer is one or more in zinc chloride, aluminum chloride, iron(ic) chloride, boron trifluoride, columbium pentachloride.
The present invention's catalyzer used is anhydrous Lewis acid; can improve the reactive behavior of ammonium chloride as electrophilic reagent; not only reaction is played the effect of catalysis; and water in reaction solution and anhydrous Lewis acid form hydrate; thereby the water in solution is removed; so described 2-is to fluorobenzoyl yl benzoic acid and catalyzer in certain molar ratio range, catalyzer could be removed the water in reaction solution completely, and reaction is carried out the direction of fluorobenzoyl yl-benzamide to product 2-.If the add-on of catalyzer is too much, in reaction process, can generate more salt, such as zinc salt, aluminium salt etc., thereby affect the quality of product; If catalyzer add-on is very few, reaction is difficult for carrying out.Adopt so anhydrous lewis acid catalyst catalysis 2-to fluorobenzoyl yl benzoic acid, ammonium chloride and phosphorus oxychloride, generate 2-to fluorobenzoyl yl-benzamide, yield and purity all improve greatly, and yield is more than 95.5%, and purity is more than 99%.
The hydrogen chloride gas producing in reaction process in step (1), by alkali liquor absorption, is transferred to pH after 6-8, can be used as electrolytic solution and uses, and has reduced so on the one hand the pollution of environment, and recycle efficient resource, has reduced production cost on the other hand.
After described step (1) has been reacted, be cooled to room temperature, reaction solution is poured in frozen water, phosphorus oxychloride reaction complete unreacted is fallen, adopt again separating funnel separatory, be divided into upper strata water and lower floor's organic phase, the hydrate that catalyzer and water form is stayed in water, takes off the further separating-purifying of layer organic phase.
Filtrate in step (2) is contained a large amount of ethylene dichloride and a small amount of water, after adopting anhydrous magnesium sulfate to process, can directly apply mechanically after reclaiming.
Baking needed temperature described in step (2) is 50-90 DEG C; time is 3-5 hour; if excess Temperature or overlong time; 2-can decompose fluorobenzoyl yl-benzamide; the quality of the finished product can not be guaranteed; if temperature is too low or the time is too short, the moisture that can contain is too many, and follow-up washing is difficult for carrying out.
The solvent adopting in washing process described in step (3) is toluene or methylene dichloride, these two kinds of solvents all do not have solvability to product, its objective is and remove the organic impurity generating in reaction process, make product 2-higher to the purity of fluorobenzoyl yl-benzamide; Because toluene is good to the solvability of organic impurity, so the solvent adopting in the washing process described in step (3) is preferably toluene.
Baking needed temperature described in step (3) is 50-90 DEG C, time is 3-5 hour, if excess Temperature or overlong time, product can decompose, and the quality of product can not be guaranteed, if temperature is too low or the time is too short, the moisture that product contains is too many, the requirement that does not reach product water content, does not meet product requirement, and the quality of same product etc. are less than guarantee.
The synthetic method of 2-of the present invention to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide.
Beneficial effect of the present invention has:
(1) operation steps is simple, reaction conditions gentleness, energy consumption is low, with short production cycle, product yield and purity are high, yield more than 95.5%, purity more than 99%, meet market to 2-the specification of quality to fluorobenzoyl yl-benzamide;
(2) 2-reacts and generates intermediate state 2-to fluoro benzoyl Benzoyl chloride with specific mol ratio with phosphorus oxychloride fluorobenzoyl yl benzoic acid, improve reactive behavior, reaction is more easily carried out, and then reacted generation product 2-with ammonium chloride to fluorobenzoyl yl-benzamide;
(3) certain speed temperature of reaction that is rapidly heated can reduce the generation of impurity like this in temperature-rise period, has ensured the quality of product 2-to fluorobenzoyl yl-benzamide;
(4) catalyzer used is anhydrous Lewis acid, can improve the reactive behavior of ammonium chloride as electrophilic reagent, not only reaction is played the effect of catalysis, make the yield of product more than 95.5%, and water in reaction solution and anhydrous Lewis acid form hydrate, thereby the water in solution can be removed completely, reaction is carried out the direction of fluorobenzoyl yl-benzamide to product 2-, make the purity of product more than 99%;
(5) hydrogen chloride gas producing in reaction process, by alkali liquor absorption, is transferred to pH after 6-8, can be used as electrolytic solution and uses, and has reduced so on the one hand the pollution of environment, and recycle efficient resource, has reduced production cost on the other hand;
(6) reaction solvent used in reaction process, can directly apply mechanically after recovery, has reduced so on the one hand the pollution of environment, and recycle efficient resource, has reduced production cost on the other hand;
In sum, the present invention greatly reduces production cost under the prerequisite that ensures product yield and quality.
Embodiment
Embodiment 1
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 120mL ethylene dichloride solvent fluorobenzoyl yl benzoic acid 12.21g, phosphorus oxychloride 4.22g and ammonium chloride 2.94g, stir, add again catalyzer zinc chloride 11.59g, be heated to 77 DEG C with the speed of 3.5 DEG C/min, carry out insulation reaction 3 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 50 DEG C, dry 5 hours; adopt toluene wash, filtration again, at 50 DEG C, dry 5 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 11.3g; yield 96.42%, purity is 99.3%.
Embodiment 2
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 1L ethylene dichloride solvent fluorobenzoyl yl benzoic acid 122.1g, phosphorus oxychloride 42.2g and ammonium chloride 32.1g, stir, add again catalyzer aluminum chloride 100.0g, be heated to 90 DEG C with the speed of 4.5 DEG C/min, carry out insulation reaction 1.5 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 90 DEG C, dry 3 hours; adopt toluene wash, filtration again, at 50 DEG C, dry 5 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 110.9g; yield 97.53%, purity is 99.5%.
Embodiment 3
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 1L ethylene dichloride solvent fluorobenzoyl yl benzoic acid 244.2g, phosphorus oxychloride 84.3g and ammonium chloride 61.5g, stir, add again catalyzer iron(ic) chloride 216.2g, be heated to 80 DEG C with the speed of 4.0 DEG C/min, carry out insulation reaction 2 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 70 DEG C, dry 4 hours; adopt toluene wash, filtration again, at 90 DEG C, dry 3 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 228.9g; yield 97.13%, purity is 99.5%.
Embodiment 4
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 10L ethylene dichloride solvent fluorobenzoyl yl benzoic acid 2442g, phosphorus oxychloride 843.3g and ammonium chloride 620.5g, stir, add again catalyzer boron fluoride 1051.0g, be heated to 85 DEG C with the speed of 3.8 DEG C/min, carry out insulation reaction 2.5 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 60 DEG C, dry 4.5 hours; adopt toluene wash, filtration again, at 70 DEG C, dry 4 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 2313.8g; yield 97.58%, purity is 99.3%.
Embodiment 5
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 10L ethylene dichloride solvent fluorobenzoyl yl benzoic acid 2442g, phosphorus oxychloride 1533g and ammonium chloride 534.9g, stir, add again catalyzer columbium pentachloride 2701.7g, be heated to 82 DEG C with the speed of 4.2 DEG C/min, carry out insulation reaction 1.5 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 80 DEG C, dry 3.5 hours; adopt washed with dichloromethane, filtration again, at 60 DEG C, dry 4.5 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 2346.7g; yield 95.51%, purity is 99.1%.
Embodiment 6
The synthetic method of a kind of 2-to fluorobenzoyl yl-benzamide; taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation, synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
。
Concrete steps comprise:
(1) 2-is joined in 1L ethylene dichloride solvent fluorobenzoyl yl benzoic acid 244.2g, phosphorus oxychloride 30.7g and ammonium chloride 80.2g, stir, add again catalyzer zinc chloride 272.6g, be heated to 88 DEG C with the speed of 4.5 DEG C/min, carry out insulation reaction 2 hours;
(2) after having reacted; be cooled to room temperature; reaction solution is poured in frozen water, then adopted separating funnel separatory, take off a layer organic phase; wash, filter, at 85 DEG C, dry 4.5 hours; adopt washed with dichloromethane, filtration again, at 70 DEG C, dry 5 hours, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide 233.4g; yield 95.97%, purity is 99.0%.
Can find out from embodiment 1-6; adopt the synthetic 2-of the present invention to fluorobenzoyl yl-benzamide; operation steps is simple; reaction conditions gentleness; product yield and purity are high; product 2-to the yield of fluorobenzoyl yl-benzamide more than 95.5%, purity more than 99%, meet market to 2-the specification of quality to fluorobenzoyl yl-benzamide.
Claims (7)
1. the 2-synthetic method to fluorobenzoyl yl-benzamide; it is characterized in that: taking 2-to fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride as raw material; under the anhydrous Lewis acid effect of ethylene dichloride solvent catalyst neutralisation; synthetic target product 2-is to fluorobenzoyl yl-benzamide, and reaction equation is as follows:
Concrete steps comprise:
(1) 2-is joined in ethylene dichloride solvent fluorobenzoyl yl benzoic acid, phosphorus oxychloride and ammonium chloride, stir, then add the anhydrous Lewis acid of catalyzer, be heated to 77-90 DEG C, carry out insulation reaction;
(2) after having reacted, be cooled to room temperature, reaction solution is poured in frozen water, then adopt separating funnel separatory, take off a layer organic phase, washing, filtration, oven dry;
(3) material after drying in step (2) is washed, filters, dried, obtain white powder, target product 2-is to fluorobenzoyl yl-benzamide;
Described 2-is to fluorobenzoyl yl benzoic acid: ammonium chloride: phosphorus oxychloride: the mol ratio of catalyzer is 1:1-1.5:0.2-1:1-2;
The anhydrous Lewis acid of described catalyzer is one or more in zinc chloride, aluminum chloride, iron(ic) chloride, boron trifluoride, columbium pentachloride.
2. the synthetic method of a kind of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: described 2-is to fluorobenzoyl yl benzoic acid: ammonium chloride: phosphorus oxychloride: the mol ratio of catalyzer is 1:1.1-1.2:0.55:1.5-1.7.
3. the synthetic method of a kind of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: in described step (1), the temperature rise rate of temperature-rise period is 3.5-4.5 DEG C/min.
4. the synthetic method of a kind of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: in described step (1), the time of insulation reaction is 1.5-3 hour.
5. the synthetic method of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: the solvent adopting in the washing process described in step (3) is toluene or methylene dichloride.
6. the synthetic method of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: the baking needed temperature described in step (2) is 50-90 DEG C, and the time is 3-5 hour.
7. the synthetic method of 2-according to claim 1 to fluorobenzoyl yl-benzamide, is characterized in that: the baking needed temperature described in step (3) is 50-90 DEG C, and the time is 3-5 hour.
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| CN109355676A (en) * | 2018-11-29 | 2019-02-19 | 福建医科大学 | A method of electro-catalysis synthesizes benzamide compound under room temperature in water phase |
| CN111320550A (en) * | 2020-03-27 | 2020-06-23 | 吉林化工学院 | Synthetic method for preparing amide compound through co-catalysis of niobium pentachloride and ionic liquid |
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| CA2320730A1 (en) * | 1998-12-23 | 2000-07-06 | Renhua Li | Thrombin or factor xa inhibitors |
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