CN105732514A - Synthetic method of 4,6-dichloropyrimidine - Google Patents
Synthetic method of 4,6-dichloropyrimidine Download PDFInfo
- Publication number
- CN105732514A CN105732514A CN201610151172.8A CN201610151172A CN105732514A CN 105732514 A CN105732514 A CN 105732514A CN 201610151172 A CN201610151172 A CN 201610151172A CN 105732514 A CN105732514 A CN 105732514A
- Authority
- CN
- China
- Prior art keywords
- pyrimidine
- synthetic method
- dichloro pyrimidine
- dihydroxy
- phosphorus oxychloride
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides a synthetic method of 4,6-dichloropyrimidine, comprising the following steps: 1), mixing 4,6-dihydroxypyrimidine with phosphorus oxychloride, and adding one of, or a combination of any of, phosgene, diphosgene and triphosgene for the purpose of reacting; 2), separating and purifying a reaction liquid obtained in step 1) to obtain phosphorus oxychloride and 4,6-dichloropyrimidine, and subjecting the recycled phosphorus oxychloride as material of step 1) to 4,6-dichloropyrimidine synthetic reaction.The complex process of organic base recycling and reutilization is avoided, no expensive catalyst is used, resource waste and product loss are avoided, the method is environment-friendly, no extra solid waste is produced, no mass phosphorus-containing waste liquid and residue are produced, product yield is high, product purity is good, a product may be commercially available without secondary purification, and the method is useful in large-scale industrial production.
Description
Technical field
The present invention relates to technical field of organic chemistry, particularly relate to a kind of 4, the synthetic method of 6-dichloro pyrimidine.
Background technology
The active molecular structure of pyrimidines, is much medicine, the intermediate of pesticide, because it is in pesticide and the world of medicine
Important function, causes the attention of numerous scholars.During as medicine intermediate, it is mainly used in the production of sulfonamides, such as sulphur
Amine dimethyl pyrimidine, ayerlucil, sulfamonomethoxine, sulfamonomethoxine etc..4,6-dichloro pyrimidine is also synthesis sulphur
Amine drug and the important intermediate of antibacterial Fluoxastrobin.
About its preparation method, existing a lot of reports in document.The most most commonly seen method is: by 4,6-dihydroxy-pyrimidine and three
The tertiary amines such as ethamine, pyridine, DMA and phosphorus oxychloride are reacted at a certain temperature, reduce pressure gained reactant mixture
Distillation, after reclaiming the phosphorus oxychloride of excess, is poured in frozen water, with organic solvent extraction, drying and dehydrating, reclaims organic solvent,
I.e. obtain 4,6-dichloro pyrimidine；Or by reactant mixture hydro-oxidation sodium solution at low temperatures neutralize, then with vapor distillation,
It is centrifuged, washs, is dried to obtain product (Yang Guiqiu, Peng Ligang, Tian Jin, Han Yan, 4, the synthesising process research of 6-dichloro pyrimidine, Shen
Sun chemical engineering institute journal, 2009,23 (2), 118-120；Peng Jun, Liu Weidong, Lan Zhili, Du Shenghua, 4,6-dichloro is phonetic
The study on the synthesis of pyridine, fine-chemical intermediate, 2009,39 (6), 14-17；US5723612；US6018045；CN102746237).
Although the method can prepare 4,6-dichloro pyrimidine, but need to use substantial amounts of organic base in preparation process, need flower
Taking huge fund to be recycled, the process operation of consequent waste water and waste residue is the most loaded down with trivial details and cost high.
The main purpose using alkali is so that reaction is thoroughly carried out with the dichloro-phosphoric acid complexation of generation in course of reaction, and by reducing alkali
Consumption improve known method and can be greatly reduced the yield of 4,6-dichloro pyrimidine.
For solving an above difficult problem, the Chinese patent of Publication No. CN1147508 discloses a kind of 4, the preparation method of 6-dichloro pyrimidine,
The method does not use any organic base, but (with 4,6-dihydroxy is phonetic to add the Phosphorous chloride. of excess and chlorine in course of reaction
The hydroxyl meter of pyridine) so that reaction is thoroughly, phosphorus oxychloride and Phosphorous chloride. are reclaimed in reaction after terminating, decompression distillation obtains product.
Although the method solves the problem that alkali consumption is big, but needs to add at a higher temperature chlorine, control extremely difficult, and
Spilling chlorine pollutes the environment.
US5750694 discloses a kind of 4, the synthetic method of 6-dichloro pyrimidine, 4,6-dihydroxy-pyrimidines and phosgene certain alkali (as
DMA, 4-(N, N dimethylamine base) pyridine etc.) in the presence of occur chlorination reaction to obtain 4,6-dichloro pyrimidine, 4,6-bis-
Hydroxy pyrimidine is 1:0.8-2.5:2.5-3.6 with the ratio of alkali and phosgene, and the hydrogen chloride that in course of reaction, alkali and phosgene discharge generates
Quaternary ammonium salt, if this quaternary ammonium salt does not reclaims, production cost is high, and removal process consumes substantial amounts of sodium hydroxide and produces substantial amounts of containing
Salt waste water.
For solving an above-mentioned difficult problem, US6160117 discloses one 4, the synthetic method of 6-dichloro pyrimidine, 4,6-dihydroxy-pyrimidines and light
Gas occurs chlorination reaction to obtain 4 under triaryl phosphine oxide or TRPO are catalyzed, 6-dichloro pyrimidine, and phosgene is severe toxicity gas,
Security control difficulty in actual use is big, and the method is not required to add organic base, but need to add more catalyst
(8%mol), catalyst amount is big, cost is high.
The patent of invention of Application No. 2013104377680 discloses a kind of 4, the preparation method of 6-dichloro pyrimidine, with 4, and 6-dihydroxy
Yl pyrimidines, phosphorus oxychloride, phosphorus pentachloride are that raw material prepares 4, and 6-dichloro pyrimidine, phosphorus pentachloride is solid and easily moisture absorption hydrolysis change
, in actual production process, when adding phosphorus pentachloride, there is the problem such as inconvenient operation, operation site environment difference, urgently in matter
To be modified.It addition, the molecular weight of phosphorus pentachloride is 2.1 times of phosgene, produce the 4 of equal in quality, the pentachloro-that 6-dichloro pyrimidine consumes
The quality changing phosphorus is 2.1 times of phosgene, and the large usage quantity of phosphorus pentachloride is relatively costly.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of 4, the synthetic method of 6-dichloro pyrimidine,
For solving, the recycling and reuse process of organic base in prior art is loaded down with trivial details, the consumption of catalyst is big and high in cost of production problem.
For achieving the above object and other relevant purposes, the present invention provides a kind of 4, and the synthetic method of 6-dichloro pyrimidine, including as follows
Step:
1) by 4,6-dihydroxy-pyrimidine mixes with phosphorus oxychloride, and adds one or more groups in phosgene, surpalite, triphosgene
Conjunction is reacted；
2) to step 1) the reactant liquor separating-purifying of gained prepares phosphorus oxychloride and 4,6-dichloro pyrimidine, and the phosphorus oxychloride of recovery is made
For step 1) raw material for 4,6-dichloro pyrimidine synthetic reaction.
Preferably, step 1) in be individually added into phosgene or surpalite is reacted.Phosgene or surpalite are liquid, easy to operate,
Need not additionally add solvent react, production cost is lower, and production efficiency is higher.
Further, step 1) described in phosphorus oxychloride and 4, the weight ratio of 6-dihydroxy-pyrimidine is 1-50:1.
Further, step 1) in when adding phosgene reaction, phosgene and 4, the mol ratio of 6-dihydroxy-pyrimidine is 2-4:1.
Further, step 1) in when adding surpalite reaction, surpalite and 4, the mol ratio of 6-dihydroxy-pyrimidine is 1-2:1.
Further, step 1) in when adding triphosgene reaction, triphosgene and 4, the mol ratio of 6-dihydroxy-pyrimidine is 0.67-1.35:1.
Further, step 1) in reaction temperature be 40-120 DEG C.
Further, step 1) in, reaction can be carried out in the absence of a solvent, it is also possible to enters under conditions of having solvent
OK.
Further, step 1) in, when reaction is carried out in the presence of a solvent, described solvent selected from aromatic solvents,
One or more combination in halogenated hydrocarbon solvent, polyether solvent.Aromatic agent include but not limited to toluene, dimethylbenzene, three
Toluene, chlorobenzene, Nitrobenzol etc.；Chlorohydrocarbon includes but not limited to dichloroethanes, sym-tetrachloroethane etc.；Polyethers includes Polyethylene Glycol
Dimethyl ether etc., triphosgene is solid to use solvent mainly to consider, adds after solvent dissolves and conveniently feeds intake, uses phosgene or double light
During gas, solubilizer effect is not more preferable, and separation is simple, energy consumption is low.
Further, step 1) in reaction in reaction system 4, the knot when percentage contents of 6-dihydroxy-pyrimidine is less than 1%
Bundle.Herein during 1% finger liquid chromatography middle control analysis, the DHP's (4,6-dihydroxy-pyrimidine) that employing area normalization method calculates
Percentage contents, when DHP accounting is 1%, raw material fundamental reaction is complete, adds phosgene and continues to react the most uneconomical, meeting
Improve production cost, reduce production efficiency.The calculating of above-mentioned percentage ratio does not comprise solvent, when reaction system comprises solvent,
Solvent not integration, terminates reaction when DHP accounting is less than 1%.
Further, step 2) in process for separation and purification be rectification, recrystallization or steam distillation.
Further, step 2) described in rectification for directly using rectification under vacuum method to obtain trichlorine oxygen successively by boiling point difference
Phosphorus, solvent and 4,6-dichloro pyrimidine finished product.
Further, step 2) described in recrystallization method be first to reclaim phosphorus oxychloride, then recovery section solvent, colder
But crystallization obtains 4,6-dichloro pyrimidine finished product.
Further, step 2) described in water vapour method time, first reclaim phosphorus oxychloride, then the temperature of 100-111 DEG C
Under be passed through steam, then cool down, filter, be dried to obtain 4,6-dichloro pyrimidine finished product.
The beneficial effects of the present invention is: the present invention proposes a kind of 4, the synthetic method of 6-dichloro pyrimidine, it is to avoid organic base returns
Receive and the complicated processes of recycling, the most do not use the catalyst of costliness, it is to avoid the waste of resource and product loss, environmental friendliness,
Extra solid waste will not be produced, also will not produce substantial amounts of containing phosphorus waste liquid with waste residue；And product yield is high, purity is good, is not required to two
Secondary purification can reach commercially available requirement, can be used for large-scale industrial production.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
(following involved content is mass content to embodiment 1, and DCP is 4, the abbreviation of 6-dichloro pyrimidine, and DHP is 4,6-
The abbreviation of dihydroxy-pyrimidine)
In the device equipped with reflux condenser, thermometer, agitator and constant pressure funnel, add 4,6-dihydroxy-pyrimidine
(114.3g, content 98%, 1mol), phosphorus oxychloride (1140g, 99%) are uniformly mixed, and are warming up to 95-100 DEG C,
And be slowly added to phosgene (220g, 99%, 2.2mol) and react, sampling after 8h, HPLC analyzes 4, and 6-dihydroxy-pyrimidine contains
Amount is 0.9%, 4, and 6-dichloro pyrimidine content is 98.3%, and reaction terminates, rectification under vacuum reactant mixture (oil bath temperature 95 DEG C,
Vacuum-0.095MPa), obtain phosphorus oxychloride 1082g (content 99%)；4,6-dichloro pyrimidine 142.8g (content 99.0%),
Yield 94.9% (with 4,6-dihydroxy-pyrimidine meter),Wherein, W (DCP) refers to
The quality of DCP, W (DHP) refers to the quality of DHP, and content refers to the mass content of DCP, and 112 is the molecule of DHP
Amount, 149 is the molecular weight of DCP.
Embodiment 2
In the device equipped with reflux condenser, thermometer, agitator and constant pressure funnel, add 4,6-dihydroxy-pyrimidine
(114.3g, content 98%, 1mol), phosphorus oxychloride (600g, 99%) and Nitrobenzol 1000mL, be uniformly mixed,
Being warming up to 95-100 DEG C, and be slowly added to phosgene (220g, 99%, 2.2mol) and react, sample after 7h, HPLC divides
Analysis 4,6-dihydroxy-pyrimidine content is 0.65%, 4, and 6-dichloro pyrimidine content is 97.8%, and reaction terminates, rectification under vacuum reaction mixing
Thing (oil bath temperature 95 DEG C, vacuum-0.095MPa), obtains phosphorus oxychloride 565g (content 99%)；4,6-dichloro pyrimidine
140.0g (content 99.5%), yield 93.5% (with 4,6-dihydroxy-pyrimidine meter).
Embodiment 3
212g triphosgene (99%, 2.1mol) is dissolved in 500mL Nitrobenzol stand-by；Equipped with reflux condenser, temperature
In the device of meter, agitator and constant pressure funnel, addition 4,6-dihydroxy-pyrimidine (114.3g, content 98%, 1mol),
Phosphorus oxychloride (600g, 99%), is uniformly mixed, is warming up to 90-95 DEG C, the nitrobenzene solution of dropping triphosgene, reaction
Sample analysis after 6 hours, HPLC analyzes 4, and 6-dihydroxy-pyrimidine content is 0.45%, 4, and 6-dichloro pyrimidine content is 97.1%, instead
Should terminate, rectification under vacuum reactant mixture (oil bath temperature 95 DEG C, vacuum-0.095MPa), obtain phosphorus oxychloride 565g and (contain
Amount 99%)；4,6-dichloro pyrimidine 140.8g (content 99.7%), yield 94.2% (with 4,6-dihydroxy-pyrimidine meter).
Comparative example 1 (being not added with phosgene)
Equipped with reflux condenser, thermometer, agitator device in, add 4,6-dihydroxy-pyrimidine (114.3g, content 98%,
1mol), phosphorus oxychloride (1140g, 99%) be uniformly mixed, be warming up to 95-100 DEG C, 8h reactor still has a large amount of 4,6-
Dihydroxy-pyrimidine exists, sampling, and HPLC analyzes 4, and 6-dichloro pyrimidine content is less than 1.0%, and reaction can not be carried out.
Comparative example 2 (being not added with phosphorus oxychloride)
In the device equipped with reflux condenser, thermometer, agitator and constant pressure funnel, add 4,6-dihydroxy-pyrimidine
(114.3g, content 98%, 1mol), Nitrobenzol 1000mL, be uniformly mixed, and slow under conditions of temperature control 95-100 DEG C
Slowly adding phosgene (220g, 99%, 2.2mol), sample after 8 hours, HPLC analyzes without 4, and 6-dichloro pyrimidine generates, and continues
Being warming up to 120 DEG C, reaction 5h, HPLC analyze still without 4, and 6-dichloro pyrimidine generates.
Comparative example 3 (adding DMA, with reference to US5750694)
In the device equipped with reflux condenser, thermometer, agitator and constant pressure funnel, add 4,6-dihydroxy-pyrimidine
(20.5g, content 98%, 0.18mol), DMA (40.4g, 99%, 0.33mol) dichloromethane 400mL
And 56g phosgene (0.57mol), airtight, heating reflux reaction 17h, the phosgene nitrogen blow-off of excess, it is subsequently adding 400mL
Water, split-phase, aqueous phase dichloromethane extracts (2*100mL), merges organic facies, and anhydrous sodium sulfate is dried, and filters, and reclaims
Dichloromethane obtains light yellow crystal 28g, content 78.3%, yield 81.7%, and yield is significantly lower than the present invention.
(the catalyst triphenylphosphinc oxide adding 25%, wherein, 25% refers to triphenylphosphinc oxide and 4 to comparative example 4, and 6-dihydroxy is phonetic
The amount percentage ratio of the material of pyridine, with reference to US6160117)
In the device equipped with reflux condenser, thermometer, agitator and constant pressure funnel, add 4,6-dihydroxy-pyrimidine
(51.8g, content 98%, 0.45mol), triphenylphosphine oxide (31.3g, content 98%, 0.11mol), Nitrobenzol 1000mL
It is heated to 60 DEG C, adds 180g phosgene (content 99%, 1.8mol), be warming up to 105 DEG C, react to 4,6-dihydroxy-pyrimidine
Content in reaction system be less than 1%, excess phosgene nitrogen blow-off, be subsequently adding 1000mL water, split-phase, organic facies
It is 5.93% that weight 1130g, HPLC analyze wherein DCP content, rectification under vacuum reactant mixture (oil bath temperature 95 DEG C, vacuum
Degree-0.095MPa), obtain 4,6-dichloro pyrimidine 61.8g (content 98.5%), yield 90.8% (with 4,6-dihydroxy-pyrimidine meter).
It can thus be seen that the 4 of this comparative example, 6-dichloro pyrimidine yield is slightly below the present invention, but because adds substantial amounts of catalyst
Triphenylphosphine oxide, its cost is apparently higher than the present invention.
In sum, present invention effectively prevents the complicated processes that in traditional method, organic base recycles, it also avoid and make
By the expensive catalyst of triphenylphosphinc oxide etc, hence it is evident that reduce production cost, improve production efficiency.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this skill
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of art.Therefore, such as
All that in art, tool usually intellectual is completed under without departing from disclosed spirit and technological thought etc.
Effect is modified or changes, and must be contained by the claim of the present invention.
Claims (10)
1. one kind 4, the synthetic method of 6-dichloro pyrimidine, it is characterised in that comprise the steps:
1) by 4,6-dihydroxy-pyrimidine mixes with phosphorus oxychloride, and adds the one in phosgene, surpalite, triphosgene or several
Plant combination to react；
2) to step 1) the reactant liquor separating-purifying of gained prepares phosphorus oxychloride and 4,6-dichloro pyrimidine, the phosphorus oxychloride of recovery
As step 1) raw material for 4,6-dichloro pyrimidine synthetic reaction.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) described in phosphorus oxychloride
It is 1-50:1 with the weight ratio of 4,6-dihydroxy-pyrimidine.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) middle addition phosgene reaction
Time, phosgene and 4, the mol ratio of 6-dihydroxy-pyrimidine is 2-4:1.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) in add surpalite anti-
At once, surpalite and 4, the mol ratio of 6-dihydroxy-pyrimidine is 1-2:1.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) in add triphosgene anti-
At once, triphosgene and 4, the mol ratio of 6-dihydroxy-pyrimidine is 0.67-1.35:1.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) in reaction temperature be
40-120℃。
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) in, reaction is at solvent
When carrying out under conditions of existence, described solvent one or several in aromatic solvents, halogenated hydrocarbon solvent, polyether solvent
Plant combination.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 1) in reaction to reactant
In system, the percentage contents of 4,6-dihydroxy-pyrimidine terminates when being less than 1%.
The synthetic method of the most according to claim 14,6-dichloro pyrimidine, it is characterised in that: step 2) in process for separation and purification
For rectification, recrystallization or steam distillation.
The synthetic method of the most according to claim 94,6-dichloro pyrimidine, it is characterised in that: step 2) middle employing water steaming
During vapour method separating-purifying reactant liquor, first reclaim phosphorus oxychloride, at a temperature of 100-111 DEG C, be then passed through steam, colder
But, filter, be dried to obtain 4,6-dichloro pyrimidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610151172.8A CN105732514A (en) | 2016-03-16 | 2016-03-16 | Synthetic method of 4,6-dichloropyrimidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610151172.8A CN105732514A (en) | 2016-03-16 | 2016-03-16 | Synthetic method of 4,6-dichloropyrimidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105732514A true CN105732514A (en) | 2016-07-06 |
Family
ID=56250707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610151172.8A Pending CN105732514A (en) | 2016-03-16 | 2016-03-16 | Synthetic method of 4,6-dichloropyrimidine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732514A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045917A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
| CN106187913A (en) * | 2016-07-19 | 2016-12-07 | 安徽广信农化股份有限公司 | A kind of production technology of 4,6 dichloro pyrimidines after improvement |
| CN106885866A (en) * | 2017-04-21 | 2017-06-23 | 重庆紫光国际化工有限责任公司 | A kind of constituent analysis method of testing of 4,6 dihydroxy-pyrimidine reaction solutions of bipolar film process |
| CN111635367A (en) * | 2020-06-24 | 2020-09-08 | 京博农化科技有限公司 | Purification method of 4, 6-dichloropyrimidine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160117A (en) * | 1997-11-06 | 2000-12-12 | Zeneca Limited | Chemical process |
| CN103539747A (en) * | 2013-09-24 | 2014-01-29 | 重庆紫光化工股份有限公司 | Preparation method of 4,6-dichloropyrimidine |
| CN105061330A (en) * | 2015-08-27 | 2015-11-18 | 重庆紫光化工股份有限公司 | Preparing method for 4, 6-dichloropyrimidine |
-
2016
- 2016-03-16 CN CN201610151172.8A patent/CN105732514A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160117A (en) * | 1997-11-06 | 2000-12-12 | Zeneca Limited | Chemical process |
| CN103539747A (en) * | 2013-09-24 | 2014-01-29 | 重庆紫光化工股份有限公司 | Preparation method of 4,6-dichloropyrimidine |
| CN105061330A (en) * | 2015-08-27 | 2015-11-18 | 重庆紫光化工股份有限公司 | Preparing method for 4, 6-dichloropyrimidine |
Non-Patent Citations (1)
| Title |
|---|
| 俞铁铭等: "《精细有机单元反应与工艺》", 31 January 2015 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045917A (en) * | 2016-07-19 | 2016-10-26 | 安徽广信农化股份有限公司 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
| CN106187913A (en) * | 2016-07-19 | 2016-12-07 | 安徽广信农化股份有限公司 | A kind of production technology of 4,6 dichloro pyrimidines after improvement |
| CN106885866A (en) * | 2017-04-21 | 2017-06-23 | 重庆紫光国际化工有限责任公司 | A kind of constituent analysis method of testing of 4,6 dihydroxy-pyrimidine reaction solutions of bipolar film process |
| CN111635367A (en) * | 2020-06-24 | 2020-09-08 | 京博农化科技有限公司 | Purification method of 4, 6-dichloropyrimidine |
| CN111635367B (en) * | 2020-06-24 | 2023-05-30 | 山东京博农化科技股份有限公司 | Purification method of 4, 6-dichloropyrimidine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732514A (en) | Synthetic method of 4,6-dichloropyrimidine | |
| CN102311392B (en) | Synthetic method of azoxystrobin and special intermediate for synthesis | |
| CN101654229A (en) | Method for preparing fluorine-containing sulphonyl (phosphoryl) imine and alkali metal salt thereof | |
| CN108602781A (en) | The method for preparing 2- [4- (4- chlorophenoxies) -2- (trifluoromethyl) phenyl] -1- (1,2,4- triazol-1-yls) propan-2-ol | |
| KR20190136060A (en) | Process for producing high purity fluoro ethylene carbonate | |
| CN102627582B (en) | A kind of method of synthesizing HDI | |
| TWI739871B (en) | New compound and process | |
| CN103539747B (en) | The preparation method of 4,6-dichloro pyrimidine | |
| CN105408293B (en) | The manufacture method of methyl fluoride | |
| CN108341784A (en) | The synthetic method of 4,6- dichloro pyrimidines | |
| CN108178749A (en) | One kind 4,6- dichloro pyrimidine production technologies | |
| CN109824551A (en) | A method of trimethyl fluoride sulfonyl fluorine is prepared by trimethyl fluoride sulfonyl chlorine | |
| CN112479165B (en) | Method for synthesizing lithium difluorosulfimide by one-step method | |
| CN103787894A (en) | Method for recovering TDA (Toluene Diamine) from residues and wastes formed in preparation process of TDI (Toluene Diisocyanate) | |
| CN105061330B (en) | The preparation method of 4,6 dichloro pyrimidines | |
| CN104529779A (en) | Synthesis method of D-dibenzoyl tartaric acid | |
| CN101624379B (en) | Method for preparing 2-chlorine-4, 6-dimethoxy-1, 3, 5-triazine | |
| CN105417556A (en) | Preparation method of ammonium bifluoride | |
| CN107188805A (en) | A kind of continuous preparation technology of the carbonate of dimethyl two | |
| CN105960409A (en) | Solid forms of tenofovir | |
| CN109180416A (en) | The synthetic method of naphthalene system fluoro-containing intermediate 1- fluoronaphthalene | |
| CN101891657B (en) | Manufacturing method of chlorosulfonyl isocyanate | |
| CN105130989B (en) | A kind of 2 fluoroadenine synthetic methods | |
| CN105693510A (en) | Preparation method of ethyl 6,8-dichlorocaprylate | |
| CN103664713B (en) | A kind of method and device preparing fluorine sulfimidic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160706 |