CN109705094A - A kind of preparation method of pyridine quinazoline - Google Patents
A kind of preparation method of pyridine quinazoline Download PDFInfo
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- CN109705094A CN109705094A CN201910115651.8A CN201910115651A CN109705094A CN 109705094 A CN109705094 A CN 109705094A CN 201910115651 A CN201910115651 A CN 201910115651A CN 109705094 A CN109705094 A CN 109705094A
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Abstract
The invention discloses a kind of preparation methods of pyridine quinazoline; using 2- methyl -4- (perfluoropropane -2- base) carbanilate as raw material; through acetylation, chlorination, hydrazine hydrate cyclization; it finally reacts to obtain the pyridine quinazoline of content 97.5%~98.5% with 3- halogen methyl pyridine, total recovery is 59.0~63.0% (in terms of 2- methyl -4- (perfluoropropane -2- base) carbanilates).The invention avoids the dangerous techniques such as catalytic hydrogenation, shorten reaction step, provide a kind of preparation method of pyridine quinazoline at low cost and simple and safe technological operation.
Description
Technical field
The present invention relates to a kind of preparation methods of pyridine quinazoline.
Background technique
Pyridine quinazoline is a kind of novel quinazoline quinoline insecticides, and the medicament is effective to Pentatomiddae pest, more to Phytophthira, powder
Lice class, mealybug class, the effect brilliance of leafhopper class and thrips class.Molecular formula: C19H15F7N4O2, molecular weight: 464.11, molecular structure
Formula:
Its content and yield directly influence the production cost and use cost of such high-efficient low toxicity insecticide.It has been reported that at present
Method is mainly the following.
EP1097932 discloses one kind with 2- nitro -5- hepta-fluoroiso-propyl benzaldehyde, nitrile methyl formate, N, N- carbonyl two
Imidazoles, acetic anhydride, nicotinonitrile are the method that seven step of raw material reacts pyridine synthesis quinazoline.The synthesis is related to two-step catalysis
Hydrogenation reaction, a step reaction under high pressure, reaction under high pressure pressure are up to 2Mpa, it is difficult to realize industrialization.Using to the 3- that should not be saved
Pyridine carboxaldehyde and the more expensive N of price, N- carbonyl dimidazoles are unfavorable for carrying out industrialization as reaction raw materials, high production cost.
JP2001342186 discloses a kind of 2- chloromethyl -4- hepta-fluoroiso-propyl aniline, methylchloroformate, hydrazine hydrate, vinegar
Acid anhydrides, nicotinonitrile are the method that seven step of raw material reacts pyridine synthesis quinazoline.It, should although there is certain advantage on yield
Method still has two-step catalyzing hydrogenation reaction, and it is limited which applies number, also increases cost.Because using sodium hydride, to anti-
Answer the water content requirement of system stringent, in addition equally facing 3- pyridine carboxaldehyde should not save, and be not suitable for industrialized production.
WO2005123695 discloses one kind with 2-aminotoluene, hepta-fluoroiso-propyl bromine, methylchloroformate, chlorine, acetic acid
Acid anhydride, nicotinonitrile are the method that eight step of raw material reacts pyridine quinazoline.It is similar with synthetic method disclosed in JP2001342186,
This method has two-step catalyzing hydrogenation reaction, and uses sodium hydride, stringent to the water content requirement of reaction system, in addition equally faces
3- pyridine carboxaldehyde should not save, and industrialized production difficulty is larger.
Summary of the invention
The purpose of the present invention is overcoming the defect of the above-mentioned prior art, 3- halogen methyl pyridine is used to be condensed again using first acetylation
New process, reduce two-step catalysis step of hydrogenation, provide a kind of pyridine quinoline azoles at low cost and simple and safe technological operation
Quinoline preparation method.
Realize the technical scheme is that
2- methyl -4- (perfluoropropane -2- base) carbanilate reacts to obtain methyl acetyl with acetic anhydride, sodium methoxide
(2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate；
Methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate and chlorine reaction obtain methyl second
Acyl group (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) carbamate；
Methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) carbamate is obtained with 80% hydration hydrazine reaction
To 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one；
1- acetyl group -3- amino -6- (perfluoropropane -2- base) (1H) -one of -3,4- dihydroquinazoline -2 and 3- halogen methyl pyrrole
Pyridine, sodium carbonate react to obtain pyridine quinazoline raw medicine；
Pyridine quinazoline is 97.5%~98.5% raw medicine product by being recrystallized to give content, and total recovery is 59.0~63.0%
(in terms of 2- methyl -4- (perfluoropropane -2- base) carbanilate).
Reaction equation is as follows:
StepThe molar ratio of 2- methyl -4- (perfluoropropane -2- base) carbanilate and acetic anhydride, sodium methoxide
For 1:1.2:1.2, the dosage of solvent toluene is the 5~8 of 2- methyl -4- (perfluoropropane -2- base) carbanilate quality
Times, acetic anhydride time for adding was controlled at 30 minutes, was added dropwise to complete back flow reaction 4 hours, saturated aqueous sodium carbonate washing reaction
Twice, vacuum distillation solvent obtains methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate to liquid；
StepDescribed in methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate and chlorine
Molar ratio is 1:1.2, and solvent chlorobenzene dosage is methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamic acid
4~6 times of ester quality are controlled at 55~60 DEG C, are controlled logical chlorine speed and are completed in 10h, the reaction was continued 2h, saturated sodium carbonate
Aqueous solution washing, reuses washing, precipitation obtains thick methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) benzene
Base) carbamate；
StepDescribed in methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) carbamate and 80%
The molar ratio of hydrazine hydrate is 1:2.3, and the dosage of solvent methanol is methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base)
Phenyl) 3~6 times of carbamate quality, 50~55 DEG C of reaction temperature, hydrazine hydrate time for adding was controlled at 30 minutes, was added dropwise
The reaction was continued after the completion 5 hours, is extracted twice using dichloroethanes, merges oil reservoir, and oil reservoir is evaporated under reduced pressure to obtain 1- acetyl group -3-
Amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one；
StepDescribed in 1- acetyl group -3- amino -6- (perfluoropropane -2- base) (1H) -one of -3,4- dihydroquinazoline -2 with
3- halogen methyl pyridine, sodium carbonate molar ratio be 1:1.1:0.6, the dosage of solvent dichloroethanes is 1- acetyl group -3- amino -6-
3~5 times of (perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one quality, control are reacted 5 hours at 60~65 DEG C,
After the reaction was completed, it is washed to neutrality, the dry oil reservoir of anhydrous sodium sulfate, vacuum distillation obtains product, reuses methanol and tied again
Crystalline substance obtains pyridine quinazoline raw medicine.
Compared with other synthetic methods, the invention has the following advantages that
1) product content is high, and content is 97.5%~98.5%(liquid chromatogram, external standard)；
2) high income, total recovery are 59.0%~63.0% (with 2- methyl -4- (perfluoropropane -2- base) carbanilate
Meter)；
3) the use of 3- halogen methyl pyridine substitution nicotinonitrile is raw material, reduces the cost of raw material, it is anti-to avoid catalytic hydrogenation
It answers；
4) process route has been innovated, reaction step is kept to four-step reaction from six steps, reduces production cost.
Specific embodiment
Embodiment 1
By 66.9g (0.20mol) 2- methyl -4- (perfluoropropane -2- base) carbanilate, 12.9g sodium methoxide
(0.24mol), 330g toluene be added with mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, flow back 0.5 hour
Afterwards, 24.5g (0.24mol) acetic anhydride, again back flow reaction 4 hours are added, after the reaction was completed, aqueous sodium carbonate is washed till neutrality,
Branch vibration layer, oil reservoir are evaporated under reduced pressure to obtain 71.5g methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) amino first
Acid esters, content 95.5%(liquid compose external standard), yield 91%.
By 71.5g (0.182mol) methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamic acid
Ester, 285g chlorobenzene be added with mechanical stirring, condenser pipe, thermometer, air-breather 1000mL three-necked flask, control reaction temperature
Degree is passed through 15.5g (0.218mol) chlorine, control is passed through time 10h, the reaction was continued 2h at 55 DEG C, after the reaction was completed, saturated carbon
Acid sodium aqueous solution washs oil reservoir, is washed till neutrality, and oil reservoir is evaporated under reduced pressure to obtain 65.5g methyl acetyl that (2- (chloromethyl) -4- is (complete
Fluoro-propane -2- base) phenyl) carbamate, content 91% (liquid spectrum external standard), yield 80%.
By 59.6g (0.146mol) methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) amino first
Acid esters, 80% hydrazine hydrate of 20.9g (0.335mol), 180g methanol be added stirred with machinery, tri- mouthfuls of 500mL of condenser pipe, thermometer
Flask controls 50 DEG C of reaction temperature, and hydrazine hydrate time for adding is controlled in 30min, and the reaction was continued 5 hours after being added dropwise to complete, reaction
After the completion, it is extracted twice using dichloroethanes, merges oil reservoir, oil reservoir is evaporated under reduced pressure to obtain 54.1g1- acetyl group -3- amino -6-
(perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one, content 97% (liquid spectrum external standard), yield 96.5%.
By 54.06g (0.140mol) 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2
Band is added in (1H) -one, 19.6g (0.1540mol) 3- chloromethylpyridine, 8.9g (0.084mol) sodium carbonate, 160g dichloroethanes
Have mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, control reaction temperature 60 DEG C react 5 hours, reaction complete
Afterwards, it is washed to neutrality, vacuum distillation obtains crude product, reuses methanol and carry out being recrystallized to give 55.4g pyridine quinazoline raw medicine, contain
Measure 98.5% (liquid spectrum external standard), total recovery 59.0%.
Embodiment 2
By 66.9g (0.20mol) 2- methyl -4- (perfluoropropane -2- base) carbanilate, 12.9g sodium methoxide
(0.24mol), 400g toluene be added with mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, flow back 0.5 hour
Afterwards, 24.5g (0.24mol) acetic anhydride, again back flow reaction 4 hours are added, after the reaction was completed, aqueous sodium carbonate is washed till neutrality,
Branch vibration layer, oil reservoir are evaporated under reduced pressure to obtain 71.5g methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) amino first
Acid esters, content 95.8% (liquid spectrum external standard), yield 91.3%.
By 71.5g (0.183mol) methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamic acid
Ester, 285g chlorobenzene be added with mechanical stirring, condenser pipe, thermometer, air-breather 1000mL three-necked flask, control reaction temperature
Degree is passed through 15.6g (0.220mol) chlorine, control is passed through time 10h, the reaction was continued 2h at 60 DEG C, after the reaction was completed, saturated carbon
Acid sodium aqueous solution washs oil reservoir, is washed till neutrality, and oil reservoir is evaporated under reduced pressure to obtain 66.6g methyl acetyl that (2- (chloromethyl) -4- is (complete
Fluoro-propane -2- base) phenyl) carbamate, content 90% (liquid spectrum external standard), yield 80%.
By 66.6g (0.146mol) methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) amino first
Acid esters, 80% hydrazine hydrate of 21.04g (0.337mol), 180g methanol be added with machinery stir, the 500mL tri- of condenser pipe, thermometer
Mouthful flask controls 55 DEG C of reaction temperature, and hydrazine hydrate time for adding is controlled in 30min, the reaction was continued after being added dropwise to complete 5 hours, instead
It after the completion of answering, is extracted twice using dichloroethanes, merges oil reservoir, oil reservoir is evaporated under reduced pressure to obtain 54.2g1- acetyl group -3- amino -
6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one, content 97.1% (liquid spectrum external standard), yield 96.3%.
By 54.2g (0.141mol1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2
Band is added in (1H) -one, 19.8g (0.155mol) 3- chloromethylpyridine, 8.9g (0.085mol) sodium carbonate, 160g dichloroethanes
Have mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, control reaction temperature 65 DEG C react 5 hours, reaction complete
Afterwards, it is washed to neutrality, vacuum distillation obtains crude product, reuses methanol and carry out being recrystallized to give 60.0g pyridine quinazoline raw medicine, contain
Measure 97.7% (liquid spectrum external standard), total recovery 63.0%.
Embodiment 3
By 66.9g (0.20mol) 2- methyl -4- (perfluoropropane -2- base) carbanilate, 12.9g sodium methoxide
(0.24mol), 465g toluene be added with mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, flow back 0.5 hour
Afterwards, 24.5g (0.24mol) acetic anhydride, again back flow reaction 4 hours are added, after the reaction was completed, aqueous sodium carbonate is washed till neutrality,
Branch vibration layer, oil reservoir are evaporated under reduced pressure to obtain 71.5g methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) amino first
Acid esters, content 95.5% (liquid spectrum external standard), yield 91%.
By 71.5g (0.182mol) methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamic acid
Ester, 430g chlorobenzene be added with mechanical stirring, condenser pipe, thermometer, air-breather 1000mL three-necked flask, control reaction temperature
Degree is passed through 15.5g (0.218mol) chlorine, control is passed through time 10h, the reaction was continued 2h at 55 DEG C, after the reaction was completed, saturated carbon
Acid sodium aqueous solution washs oil reservoir, is washed till neutrality, and oil reservoir is evaporated under reduced pressure to obtain 65.1g methyl acetyl that (2- (chloromethyl) -4- is (complete
Fluoro-propane -2- base) phenyl) carbamate, content 91% (liquid spectrum external standard), yield 79.4%.
By 65.1g (0.145mol) methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) amino first
Acid esters, 80% hydrazine hydrate of 20.8g (0.332mol), 240g methanol be added stirred with machinery, tri- mouthfuls of 500mL of condenser pipe, thermometer
Flask controls 50 DEG C of reaction temperature, and hydrazine hydrate time for adding is controlled in 30min, and the reaction was continued 5 hours after being added dropwise to complete, reaction
After the completion, it is extracted twice using dichloroethanes, merges oil reservoir, oil reservoir is evaporated under reduced pressure to obtain 53.6g1- acetyl group -3- amino -6-
(perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one, content 97% (liquid spectrum external standard), yield 96.5%.
By 53.6g (0.139mol) 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2
Band is added in (1H) -one, 26.3g (0.153mol) 3- bromo methyl cycloheptapyridine, 8.8g (0.072mol) sodium carbonate, 270g dichloroethanes
Have mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, control reaction temperature 60 DEG C react 5 hours, reaction complete
Afterwards, it is washed to neutrality, vacuum distillation obtains crude product, reuses methanol and carry out being recrystallized to give 56.7g pyridine quinazoline raw medicine, contain
Measure 97.5% (liquid spectrum external standard), total recovery 59.75%.
Embodiment 4
By 66.9g (0.20mol) 2- methyl -4- (perfluoropropane -2- base) carbanilate, 12.9g sodium methoxide
(0.24mol), 530g toluene be added with mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, flow back 0.5 hour
Afterwards, 24.5g (0.24mol) acetic anhydride, again back flow reaction 4 hours are added, after the reaction was completed, aqueous sodium carbonate is washed till neutrality,
Branch vibration layer, oil reservoir are evaporated under reduced pressure to obtain 70.9g methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) amino first
Acid esters, content 95.8% (liquid spectrum external standard), yield 90.6%.
By 70.9g (0.181mol) methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamic acid
Ester, 430g chlorobenzene be added with mechanical stirring, condenser pipe, thermometer, air-breather 1000mL three-necked flask, control reaction temperature
Degree is passed through 15.4g (0.217mol) chlorine, control is passed through time 10h, the reaction was continued 2h at 60 DEG C, after the reaction was completed, saturated carbon
Acid sodium aqueous solution washs oil reservoir, is washed till neutrality, and oil reservoir is evaporated under reduced pressure to obtain 64.3g methyl acetyl that (2- (chloromethyl) -4- is (complete
Fluoro-propane -2- base) phenyl) carbamate, content 92.4% (liquid spectrum external standard), yield 80.1%.
By 64.3g (0.145mol) methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) amino first
Acid esters, 20.8g(0.333mol) 80% hydrazine hydrate, 240g methanol be added stirred with machinery, tri- mouthfuls of 500mL of condenser pipe, thermometer
Flask controls 55 DEG C of reaction temperature, and hydrazine hydrate time for adding is controlled in 30min, and the reaction was continued 5 hours after being added dropwise to complete, reaction
After the completion, it is extracted twice using dichloroethanes, merges oil reservoir, oil reservoir is evaporated under reduced pressure to obtain 54.0g1- acetyl group -3- amino -6-
(perfluoropropane -2- base) -3,4- dihydroquinazoline -2 (1H) -one, content 97.1% (liquid spectrum external standard), yield 96.9%.
By 54.0g (0.140mol) 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4- dihydroquinazoline -2
Band is added in (1H) -one, 26.5g (0.154mol) 3- bromo methyl cycloheptapyridine, 8.9g (0.084mol) sodium carbonate, 270g dichloroethanes
Have mechanical stirring, condenser pipe, thermometer 500mL three-necked flask, control reaction temperature 65 DEG C react 5 hours, reaction complete
Afterwards, it is washed to neutrality, vacuum distillation obtains crude product, reuses methanol and carry out being recrystallized to give 57.6g pyridine quinazoline raw medicine, contain
Measure 98.1% (liquid spectrum external standard), total recovery 61.2%.
Claims (6)
1. a kind of preparation method of pyridine quinazoline, it is characterised in that: with 2- methyl -4- (perfluoropropane -2- base) phenyl amino
Formic acid esters is raw material, through acetylization reaction, chlorination reaction, hydrazine hydrate annulation, is finally condensed four steps with 3- halogen methyl pyridine
Reaction obtains the pyridine quinazoline of content 97.5%~98.5%, and total recovery is 59.0~63.0%,
Reaction equation is as follows.
2. the preparation method of pyridine quinazoline according to claim 1, it is characterised in that second in the acetylization reaction
Acid anhydrides is acetylation reagent, 2- methyl -4- (perfluoropropane -2- base) carbanilate: acetic anhydride: sodium methoxide molar ratio is
1:1.2:1.2, solvent toluene dosage are 5~8 times of 2- methyl -4- (perfluoropropane -2- base) carbanilate quality, drop
Add the acetic anhydride time 30 minutes, then back flow reaction 4 hours, reaction solution is washed twice with saturated aqueous sodium carbonate, and organic matter subtracts
Pressure obtains methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate after being distilled to recover solvent.
3. the preparation method of pyridine quinazoline according to claim 1, it is characterised in that chlorine in the chlorination reaction
For chlorinating agent, the molar ratio of methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate and chlorine is
1:1.2, solvent chlorobenzene dosage are methyl acetyl (2- methyl -4- (perfluoropropane -2- base)-phenyl) carbamate quality
It 4~6 times, controls at 55~60 DEG C, controls logical chlorine speed and completed in 10h, the reaction was continued 2h, saturated aqueous sodium carbonate is washed
It washs, is washed with water, organic phase precipitation obtains thick methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl)
Carbamate.
4. the preparation method of pyridine quinazoline according to claim 1, it is characterised in that methyl acetyl in annulation
The molar ratio of (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) carbamate and 80% hydrazine hydrate is 1:2.3, solvent first
The dosage of alcohol is 3~6 times of methyl acetyl (2- (chloromethyl) -4- (perfluoropropane -2- base) phenyl) carbamate quality,
50~55 DEG C of reaction temperature, hydrazine hydrate time for adding was controlled at 30 minutes, and the reaction was continued 5 hours after being added dropwise to complete, and used dichloro
Ethane is extracted twice, and merges oil reservoir, and oil reservoir is evaporated under reduced pressure to obtain 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4-
Dihydroquinazoline -2 (1H) -one.
5. the preparation method of pyridine quinazoline according to claim 1, it is characterised in that 1- second described in condensation reaction
Acyl group -3- amino -6- (perfluoropropane -2- base) (1H) -one of -3,4- dihydroquinazoline -2 and 3- halogen methyl pyridine, sodium carbonate
Molar ratio is 1:1.1:0.6, and the dosage of solvent dichloroethanes is 1- acetyl group -3- amino -6- (perfluoropropane -2- base) -3,4-
3~5 times of dihydroquinazoline -2 (1H) -one quality, control are reacted 5 hours at 60~65 DEG C, after the reaction was completed, are washed to
Property, the dry oil reservoir of anhydrous sodium sulfate, vacuum distillation obtains product, reuses methanol and carry out being recrystallized to give pyridine quinazoline original
Medicine.
6. 3- halogen methyl pyridine according to claim 5 is 3- chloromethylpyridine or 3- bromo methyl cycloheptapyridine.
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Cited By (3)
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| CN110698416A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline intermediate |
| CN111533701A (en) * | 2020-07-02 | 2020-08-14 | 湖南速博生物技术有限公司 | Synthetic method of pyridine quinazoline intermediate |
| CN111704604A (en) * | 2020-08-19 | 2020-09-25 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698416A (en) * | 2019-12-16 | 2020-01-17 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline intermediate |
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| CN111533701A (en) * | 2020-07-02 | 2020-08-14 | 湖南速博生物技术有限公司 | Synthetic method of pyridine quinazoline intermediate |
| CN111533701B (en) * | 2020-07-02 | 2020-10-16 | 湖南速博生物技术有限公司 | Synthetic method of pyridine quinazoline intermediate |
| CN111704604A (en) * | 2020-08-19 | 2020-09-25 | 湖南速博生物技术有限公司 | Preparation method of pyridine quinazoline |
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