CN103951567B - The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine - Google Patents
The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine Download PDFInfo
- Publication number
- CN103951567B CN103951567B CN201410014655.4A CN201410014655A CN103951567B CN 103951567 B CN103951567 B CN 103951567B CN 201410014655 A CN201410014655 A CN 201410014655A CN 103951567 B CN103951567 B CN 103951567B
- Authority
- CN
- China
- Prior art keywords
- reaction
- amine
- trimethylammonium
- heptane
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of N-substituted-phenyl-1,7, the preparation method of 7-trimethylammonium two ring [2.2.1] heptane-2-amine, organic solvent, 3 is added in reaction vessel, 5-xylidine and camphor, add proper catalyst again, put it in the microwave reactor with air set pipe and reflux condensate device, be adjusted to suitable microwave output power, under agitation condition, react 10-30 minute, after cooling, add appropriate sodium borohydride, reaction 20-40 minute, repeat above-mentioned steps, TLC point board monitoring reaction process, till reaction raw materials no longer reduces.After reaction terminates, decompression precipitation, under optimal temperature, slowly adds suitable quantity of water in above-mentioned system, stirs 1-2 hour, adds organic solvent C, and extraction, obtains final product secondary amine.Catalyzer of the present invention is cheap and easy to get, and the reaction times shortens greatly, and reaction yield improves, and reduces intermediate reaction step, cost-saving, environmental friendliness.
Description
Technical field
The present invention relates to a kind of preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, particularly a kind of N-(3,5-3,5-dimethylphenyl) preparation method of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine.
Background technology
N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine is the important intermediate of He Cheng spirooxazine photochromic compound.Spirooxazine photochromic compound is the important organic photochromic material of a class, it has good optical Response, fading rate and preferably light stability faster, have a wide range of applications in organic photochromic resin lens, data logging, optical information storage, optical filter, the field such as false proof.
Preparation method at present for N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine studies less, mainly due to the chemical structure of camphor own singularity caused by.Due to steric effect, the carbonyl position of camphor is caused to be difficult to be activated, thus difficult and aniline generation nucleophilic addition.The preparation method of disclosed similar structures compound is as described below: the people such as CHANYOU-PING in international patent application WO9708573 (A1) with aniline and 2-norbornane ketone for raw material, benzotriazole is catalyzer, back flow reaction 16 hours under hot conditions, again by system precipitation, add sodium borohydride and prepare corresponding secondary amine.Aforesaid method is also applicable to the synthesis of this product, empirical tests, and this synthetic route reaction times is 90 hours, and product total recovery is 35%.The raw material that this synthetic method uses is easy to get, and step is less, but reaction conditions is comparatively harsh, and temperature of reaction is very high, and the reaction times is longer, needs a point water in reaction, and the total yield of this route is also lower.
Summary of the invention
The object of the present invention is to provide a kind of novel method for synthesizing of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, reaction times 3-5 hour, realizes product yield about 90%.Can be illustrated by following reaction equation according to method of the present invention:
Object of the present invention is achieved through the following technical solutions:
A kind of preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, described secondary amine is N-(3,5-3,5-dimethylphenyl)-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, its structural formula is as follows:
Preparation method comprises the steps:
Organic solvent A and 3,5-xylidine, camphor drop in reaction vessel by step 1. successively, add proper catalyst B under agitation condition;
The microwave reactor that air set pipe and reflux condensate device are housed put into by reaction vessel by step 2., is adjusted to suitable microwave power, microwave reaction 10-30 minute, and described microwave power is 240W ~ 640W;
Step 3. stopped reaction, is cooled to suitable temp, preferred room temperature, adds appropriate sodium borohydride, after stirring reaction, then is adjusted to abovementioned steps microwave power, continues reaction;
Step 4. repeats above-mentioned reactions steps 2 and step 3, and the board monitoring of TLC point is reacted, and till reaction raw materials no longer reduces, reaction terminates;
Step 5. is by above-mentioned reaction system decompression precipitation, and as under ice-water bath condition under cold condition, slowly add suitable quantity of water, add organic solvent C after stirring, stir, extraction, get organic layer precipitation, column chromatography for separation obtains final product;
Above-mentioned N-substituted-phenyl-1,7, the synthetic method of 7-trimethylammonium two ring [2.2.1] heptane-2-amine, in step 1, described organic solvent A is a kind of in benzene,toluene,xylene, DMF or ethylene glycol, preferred DMF, because adopt microwave reactor to heat in the present invention's reaction, temperature of reaction is high, adopts DMF to be more conducive to the dissolving of product.
The preparation method of above-mentioned naphtho-pyrans compounds, in step 1,3,5-described xylidines are 1:1 ~ 1:3 with the ratio of the amount of substance of camphor.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in step 1, the ratio of the amount of substance of described catalyst B and 3,5-xylidine is 1:1 ~ 1:10.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in step 1, described catalyst B is a kind of in Guanidinium hydrochloride, sodium hydroxide, potassium hydroxide, aluminum chloride or benzotriazole.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in step 2, described microwave power is 240W ~ 640W, preferred 450W or 500W.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in step 3, the described stirring reaction time is 20-40 minute.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in steps of 5, the described stirring reaction time is 1-2 hour.
The preparation method of above-mentioned N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, in steps of 5, described organic solvent C is a kind of in methylene dichloride, toluene, ethyl acetate or tetrahydrofuran (THF).
Compared with prior art, its remarkable advantage is in the present invention: the synthetic route step that (1) the present invention selects is few, and by product is few, and yield is high, reaches about 90%; (2) heating means that the present invention adopts microwave reactor to heat substantially reduce the reaction times, foreshorten to a few hours, raise the efficiency, and save the energy; (3) in the present invention's reaction, sodium borohydride is not the completely rear disposable last hydrogenating reduction step all having added synthetic route of question response, but limit coronite adds, and repeats, and promotes that balanced reaction is carried out to product direction, improves productive rate; (4) catalyzer selected of the present invention is cheap, and easily prepare, and devise most suitable add-on, catalytic efficiency is high; (5) all reaction conditionss of the present invention are gentle, without harsh reaction conditionss such as high pressure-temperatures, are applicable to suitability for industrialized production; (6) the easy separating-purifying of products obtained therefrom of the present invention, good economy performance.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the inventive method;
Fig. 2 is embodiment of the present invention gained N-(3,5-3,5-dimethylphenyl) the nucleus magnetic hydrogen spectrum figure of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine;
Fig. 3 is embodiment of the present invention gained N-(3,5-3,5-dimethylphenyl) infrared spectrogram of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine.
Embodiment
(embodiment 1)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 9.9g, yield 88%.
(embodiment 2)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 18.9g(123.78mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 10.1g, yield 89.8%.
(embodiment 3)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer benzotriazole 0.5g(4.19mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate tetrahydrofuran (THF), stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 8.9g, yield 79.18%.
(embodiment 4)
In 150mL single port flask, add ethylene glycol 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add hydrochloric guanidine 3.94g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 9g, yield 80%.
(embodiment 5)
In 150mL single port flask, add DMF20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add q. s. methylene chloride, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 8.9g, yield 79.18%.
(embodiment 6)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 240W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add q. s. toluene, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 7.5g, yield 66.7%.
(embodiment 7)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer potassium hydroxide 4.6g(82.52mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 7.8g, yield 69.39%.
(embodiment 8)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer sodium hydroxide 0.83g(20.63mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 20 minutes.Cool to room temperature, adds sodium borohydride 0.3g(8mmol), stir 40 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 2 hours, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 7g, yield 62.3%.
(embodiment 9)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 6.3g(41.26mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 640W, reacts 10 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 40 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 2 hours, add q. s. toluene, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 10.2g, yield 90.7%.
(embodiment 10)
In 150mL single port flask, add dimethylbenzene 20mL, 3,5-xylidine 5g(41.26mmol), camphor 9.4g(61.89mmol), under stirring, add catalyzer benzotriazole 4.9g(41.26mmol).Above-mentioned single port flask is put into the microwave reactor with air set pipe and reflux condensate device, and under agitation condition, adjustment microwave output power is 400W, reacts 30 minutes.Cool to room temperature, adds sodium borohydride 0.15g(3.96mmol), stir 30 minutes.Repeat above-mentioned steps, the board monitoring of TLC point is reacted, until raw material no longer reduces, reaction terminates.Decompression precipitation, under ice-water bath condition, slowly joins water in above-mentioned system, stirs 1 hour, add appropriate ethyl acetate, stir, extraction, extract organic layer decompression precipitation, column chromatography obtains pale yellow oil matter, is product secondary amine through nucleus magnetic hydrogen spectrum, infrared spectrum.Product gross weight 9.3g, yield 82.74%.
Claims (8)
1. prepare the method for following structure and N-(3,5-3,5-dimethylphenyl)-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine for one kind,
Described preparation method is characterized in that: comprise the steps:
Organic solvent A and 3,5-xylidine, camphor drop in reaction vessel by step 1. successively, add proper catalyst B under agitation condition;
The microwave reactor that air set pipe and reflux condensate device are housed put into by reaction vessel by step 2., is adjusted to suitable microwave power, microwave reaction 10-30 minute, and described microwave power is 240W ~ 640W;
Step 3. stopped reaction, is cooled to suitable temp, adds appropriate sodium borohydride, stirring reaction 20-40 minute, then is adjusted to microwave power described in step 2, continues reaction;
Step 4. repeats reactions steps in above-mentioned steps 2 and step 3, and the board monitoring of TLC point is reacted, and till reaction raw materials no longer reduces, reaction terminates;
Step 5. is by above-mentioned reaction system decompression precipitation, and under cold condition, slowly add suitable quantity of water, stir 1-2 hour, add organic solvent C, stir, extraction, get organic layer precipitation, column chromatography for separation obtains final product.
2. N-according to claim 1 (3,5-3,5-dimethylphenyl)-1,7, the preparation method of 7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: in step 1,3,5-described xylidines are 1:1 ~ 1:3 with the ratio of the amount of substance of camphor.
3. N-(3 according to claim 1,5-3,5-dimethylphenyl) preparation method of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: the ratio of the amount of substance of described catalyst B and 3,5-xylidine is 1:1 ~ 1:10.
4. N-(3 according to claim 1,5-3,5-dimethylphenyl) preparation method of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: in step 1, described organic solvent A is a kind of in benzene,toluene,xylene, DMF or ethylene glycol.
5. N-(3 according to claim 1,5-3,5-dimethylphenyl)-1,7, the preparation method of 7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: in step 1, described catalyst B is a kind of in Guanidinium hydrochloride, sodium hydroxide, potassium hydroxide, aluminum chloride or benzotriazole.
6. the preparation method of N-according to claim 1 (3,5-3,5-dimethylphenyl)-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, is characterized in that: in step 3, described add sodium borohydride after churning time be 20-40 minute.
7. the preparation method of N-according to claim 1 (3,5-3,5-dimethylphenyl)-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: in steps of 5, described churning time is 1-2 hour.
8. N-(3 according to claim 1,5-3,5-dimethylphenyl) preparation method of-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine, it is characterized in that: in steps of 5, described organic solvent C is a kind of in methylene dichloride, toluene, ethyl acetate or tetrahydrofuran (THF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410014655.4A CN103951567B (en) | 2014-01-13 | 2014-01-13 | The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410014655.4A CN103951567B (en) | 2014-01-13 | 2014-01-13 | The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951567A CN103951567A (en) | 2014-07-30 |
| CN103951567B true CN103951567B (en) | 2016-01-20 |
Family
ID=51328955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410014655.4A Active CN103951567B (en) | 2014-01-13 | 2014-01-13 | The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951567B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194037A (en) * | 1995-08-30 | 1998-09-23 | 康宁股份有限公司 | Photochromic spiroxazines, compositions and articles containing them |
-
2014
- 2014-01-13 CN CN201410014655.4A patent/CN103951567B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194037A (en) * | 1995-08-30 | 1998-09-23 | 康宁股份有限公司 | Photochromic spiroxazines, compositions and articles containing them |
Non-Patent Citations (1)
| Title |
|---|
| 胺的合成方法及研究进展;张惠欣等;《安徽农业科学》;20091231;第37卷(第35期);第17310页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951567A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105418483A (en) | Preparation method of crystalline nintedanib esylate | |
| CN103012362A (en) | Preparation method of diamidodibenzo-18-crown ether-6 bonded silica gel stationary phase and intermediate thereof | |
| CN103342649B (en) | 3-amino-2,4,6-trinitro-diphenylethylene compounds and preparation method thereof | |
| CN101735023B (en) | Method for preparing 3-bromo-5-chlorophenol | |
| CN108276414B (en) | A kind of preparation method of citric acid tropsch imatinib | |
| CN103951567B (en) | The preparation method of N-substituted-phenyl-1,7,7-trimethylammonium two ring [2.2.1] heptane-2-amine | |
| CN104031652A (en) | Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof | |
| CN103772278A (en) | Important tetrahydroisoquinoline derivative midbody and synthesis method thereof | |
| CN105541637A (en) | Preparation method of 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl | |
| CN103232397B (en) | The synthetic method of 5-amino-N-substituted benzimidazole ketone | |
| CN104628626A (en) | Preparation method of 2,2,6,6-tetramethyl-4-piperidinol | |
| CN104030978A (en) | High-stability bromine-bond liquid crystal and preparation method thereof | |
| CN104447391A (en) | Methylenebisamide derivative and preparation method thereof | |
| CN103275034A (en) | Preparation method of micromolecule cathepsin D inhibitor | |
| CN105348285A (en) | Low-cost and high-yield adenine preparation method | |
| CN109970582A (en) | A method of preparing the chloro- 3- methyl benzoic acid of 2- amino -5- | |
| CN108084067B (en) | A kind of preparation method of Li Tasite intermediate | |
| CN104774183A (en) | Preparation method of formoxyl rosuvastatin calcium intermediate | |
| CN106632077B (en) | A kind of preparation method of 2- amino -4- Bromopyrimidine | |
| CN103864693B (en) | Method for preparing low-sensitivity high-energy explosive 1-amino-2,4-dinitroimidazole | |
| CN104447534A (en) | 6-[(7-chloroquinoline-4-oxyl) phenolic ether]-2-naphthamide derivative as well as preparation method and application thereof | |
| CN109384683A (en) | A kind of preparation method of 2- amino-5-fluorine acetophenone | |
| CN113929582B (en) | Synthesis method of 2- (5-fluoro-2-nitrophenoxy) acetate | |
| CN103360323A (en) | Preparation method of triclabendazole | |
| CN103408435B (en) | Method for synthesizing TATB (triamino trinitrobenzene) by normal pressure phase-transfer catalysis and amination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |