CN106045917A - Synthetic process for preparing 4,6-dichloropyrimidine through one-step method - Google Patents
Synthetic process for preparing 4,6-dichloropyrimidine through one-step method Download PDFInfo
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- CN106045917A CN106045917A CN201610571181.2A CN201610571181A CN106045917A CN 106045917 A CN106045917 A CN 106045917A CN 201610571181 A CN201610571181 A CN 201610571181A CN 106045917 A CN106045917 A CN 106045917A
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- China
- Prior art keywords
- tower reactor
- phosgene
- step method
- synthesis technique
- dichloro pyrimidine
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- 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
Abstract
The invention discloses a synthetic process for preparing 4,6-dichloropyrimidine through a one-step method. The synthetic process comprises the following steps: (1) phosgenation reaction; (2) waste gas treatment, trichloromethane and pyridine material recycle, and 4,6-dichloropyrimidine product refining. According to the synthetic process, through the arrangement of a phosgene distributor in a reactor, the effective utilization ratio of phosgene can be greatly improved, and the unit consumption of phosgene is reduced from 1.8 percentage points to 1.2 percentage points; through the arrangement of an alkali liquor spraying system above a gathering tank, hydrogen chloride and phosgene can be effectively absorbed, and leakage of toxic gases can be avoided; meanwhile, through the arrangement of a draught fan, mixed gas can upwards enter the spraying system to be absorbed; through the setting of different rectification temperatures to recycle the materials, the cost is reduced, and the recycle of resources can be realized.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to one-step method and prepare 4, the synthesis technique of 6-dichloro pyrimidine.
Background technology
Pyrimidines is the heterocycle compound that a class contains nitrogen element, because they special structures, therefore has
Having specific character, pyrimidines has certain antifungal and the effect of regulation promotion plant growing, thus can be extensive
For preparing the chemicals such as herbicide, insecticide and antibacterial.Pyrimidines and metal ion can form coordination compound, can
To improve the persistence of former medicine, extend the expiration date growth and half-life, and can effectively reduce the toxicity that animal is produced.
4,6-dichloro pyrimidines are the heterocycle compounds of a kind of Nitrogen element, are the important centres of synthesis pyrimidines
One of body, is widely used in medical product, the synthesis of pesticide miazines product, sulfamonomethoxine, sulfamonomethoxine etc.
Sulfa drugs, 4,6-dichloro pyrimidines are the representatives of typical case's intermediate therein.From 4,6-dichloro pyrimidine at the weight of every field
Acting on it can be seen that market is to 4 in the short time, 6-dichloro pyrimidine and raw material 4 thereof, the demand of 6-dihydroxy-pyrimidine can constantly increase
Adding, the industrialized production of 4,6-dichloro pyrimidines also can grow steadily.
According to pertinent literature, synthesizing 4, the method for 6-dichloro pyrimidine mainly has two kinds of methods:
(1) phosphorus oxychloride chloridising: with 4,6-dihydroxy-pyrimidine makees raw material, uses phosphorus oxychloride in the presence of anhydrous triethylamine
Chlorination synthesis 4,6-dichloro pyrimidine；
(2) solid phosgene chloridising: with 4,6-dihydroxy-pyrimidine makees raw material, replaces phosphorus oxychloride synthesis 4 with solid phosgene,
6-dichloro pyrimidine.
First method needs to use substantial amounts of solvent so that the recovery of solvent is more complicated, and in the reaction, by hydroxyl
Hydrion is transferred on triethylamine with triethylamine effect by the phosphorus oxychloride of one chlorine of displacement, adds water tune in last handling process
Joint pH, operation complexity, and course of reaction easily occurs three kinds of by-products, bad control.And about solid phosgene chlorination legal system
Standby 4, the report of the concrete synthetic method of 6-dichloro pyrimidine is little, but the product yield that obtains of conventional solid phosgene chloridising and pure
Degree does not all have the height of first method.
Summary of the invention:
The present invention is in order to overcome the deficiencies in the prior art, it is provided that one-step method prepares 4, the synthesis technique of 6-dichloro pyrimidine.
The present invention can be achieved through the following technical solutions:
One-step method prepares 4, the synthesis technique of 6-dichloro pyrimidine, it is characterised in that synthesis technique comprises the following steps:
(1) in tower reactor, 1 weight portion 4 is put into, 6-dihydroxy-pyrimidine and the chloroform of 3 weight portions, open
Agitator is stirred, and continuously adds the pyridine catalyst of 0.5 weight portion, is then turned on jacket steam and makes temperature in tower reactor
Being increased to 50 DEG C, be passed through 1-3 weight portion phosgene bottom tower reactor, phosgene first passes around the gas distribution of inside reactor
Device, is entered inside tower reactor by the aperture of even compact on gas distributor, and then reacts with material；
(2) after reaction terminates, being caught up with gas by being filled with nitrogen bottom tower reactor, mixed gas is via tower reactor top
Gas outlet, enters capture tank；Again the product in tower reactor is transferred in rectifying column, be successively respectively provided with rectification temperature
Degree, for 55-70 DEG C, 105-125 DEG C and 170-180 DEG C, collects the fraction under relevant temperature respectively, and the most recyclable chloroform is molten
Agent and pyridine catalyst, be to wash after the cooling of 170-180 DEG C of fraction, be dried temperature, i.e. can get 4,6-dichloro pyrimidine.
Further, the gas distributor described in step 1 is that triangular shape is placed on tower reactor.
Further, the capture tank described in step 2 is arranged over alkali liquor spray system, and the bottom of capture tank is provided with wind
Machine.
Further, described alkali liquor is any one in sodium hydroxide solution, ammonia.
The invention have the benefit that 1) by arranging phosgene distributor in the reactor, phosgene can be increased substantially
Effective rate of utilization so that the unit consumption of phosgene is dropped to 1.2 percentage points by 1.8 percentage points；2) by the top of capture tank
Alkali liquor spray system is set, can effectively absorbing hydrogen chloride and phosgene, it is to avoid leaking of toxic gas, the setting of blower fan can simultaneously
So that mixed gas is upwardly into spray system and is absorbed；3) by arranging different rectification temperatures, material is reclaimed,
Cost can be reduced, it is achieved the recycling of resource.
Detailed description of the invention:
By embodiment, the detailed description of the invention of the present invention is made an explanation below.
Embodiment
One-step method prepares 4, and the synthesis technique of 6-dichloro pyrimidine, its synthesis technique comprises the following steps: (1) is to tower reaction
Putting into the 4 of 1 weight portion in device, 6-dihydroxy-pyrimidine and the chloroform of 3 weight portions, turn on agitator is stirred, and continues to add
Enter the pyridine catalyst of 0.5 weight portion, be then turned on temperature in jacket steam makes tower reactor and be increased to 50 DEG C, from tower reaction
Being passed through 1 weight portion phosgene bottom device, phosgene first passes around the gas distributor of inside reactor, and gas distributor is that triangular shape is put
Putting bottom tower reactor, gas distributor has the aperture of a lot of even compact, phosgene is entered tower reactor by aperture
Inside, and then react with material；(2), after reaction terminates, gas, mixed gas warp are caught up with by being filled with nitrogen bottom tower reactor
Being exported by tower reactor top gas, enter capture tank, capture tank is arranged over ammonia spray system, the bottom peace of capture tank
Equipped with blower fan, in gas enters capture tank, blower fan feed gas into ammonia spray system, thus avoid phosgene and hydrogen chloride
The leakage of gas；Transferring in rectifying column by the product in tower reactor again, being successively respectively provided with rectification temperature is 55-70
DEG C, 105-125 DEG C and 170-180 DEG C, collect the fraction under relevant temperature respectively, the most recyclable chloroform solvent and pyridine are urged
Agent, is to wash after the cooling of 170-180 DEG C of fraction, be dried temperature, i.e. can get 4,6-dichloro pyrimidine.
The invention have the benefit that 1) by arranging phosgene distributor in the reactor, phosgene can be increased substantially
Effective rate of utilization so that the unit consumption of phosgene is dropped to 1.2 percentage points by 1.8 percentage points；2) by the top of capture tank
Alkali liquor spray system is set, can effectively absorbing hydrogen chloride and phosgene, it is to avoid leaking of toxic gas, the setting of blower fan can simultaneously
So that mixed gas is upwardly into spray system and is absorbed；3) by arranging different rectification temperatures, material is reclaimed,
Cost can be reduced, it is achieved the recycling of resource.
Claims (4)
1. one-step method prepares 4, the synthesis technique of 6-dichloro pyrimidine, it is characterised in that synthesis technique comprises the following steps:
(1) in tower reactor, 1 weight portion 4 is put into, 6-dihydroxy-pyrimidine and the chloroform of 3 weight portions, open stirring
Device is stirred, and continuously adds the pyridine catalyst of 0.5 weight portion, is then turned on temperature in jacket steam makes tower reactor and raises
To 50 DEG C, being passed through 1-3 weight portion phosgene bottom tower reactor, phosgene first passes around the gas distributor of inside reactor,
Entered inside tower reactor by the aperture of even compact on gas distributor, and then react with material；
(2) after reaction terminates, being caught up with gas by being filled with nitrogen bottom tower reactor, mixed gas is via tower reactor top gas
Outlet, enters capture tank；Transferring in rectifying column by the product in tower reactor again, being successively respectively provided with rectification temperature is
55-70 DEG C, 105-125 DEG C and 170-180 DEG C, collect the fraction under relevant temperature respectively, the most recyclable chloroform solvent and
Pyridine catalyst, is to wash after the cooling of 170-180 DEG C of fraction, be dried temperature, i.e. can get 4,6-dichloro pyrimidine.
One-step method the most according to claim 1 prepares 4, the synthesis technique of 6-dichloro pyrimidine, it is characterised in that in step 1
Described gas distributor is that triangular shape is placed on tower reactor.
One-step method the most according to claim 1 prepares 4, the synthesis technique of 6-dichloro pyrimidine, it is characterised in that in step 2
Described capture tank is arranged over alkali liquor spray system, and the bottom of capture tank is provided with blower fan.
One-step method the most according to claim 3 prepares 4, the synthesis technique of 6-dichloro pyrimidine, it is characterised in that described alkali
Liquid is any one in sodium hydroxide solution, ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610571181.2A CN106045917A (en) | 2016-07-19 | 2016-07-19 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
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| CN201610571181.2A CN106045917A (en) | 2016-07-19 | 2016-07-19 | Synthetic process for preparing 4,6-dichloropyrimidine through one-step method |
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| CN106045917A true CN106045917A (en) | 2016-10-26 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146766A (en) * | 1994-04-26 | 1997-04-02 | 曾尼卡有限公司 | Process for the preparation of 4,6-dichloropyrimidine |
| CN1206408A (en) * | 1995-01-30 | 1999-01-27 | 曾尼卡有限公司 | Process for preparing 4,6-dichloro-pyrimidine |
| US6160117A (en) * | 1997-11-06 | 2000-12-12 | Zeneca Limited | Chemical process |
| CN1687036A (en) * | 2005-06-20 | 2005-10-26 | 江苏省激素研究所有限公司 | Method for preparing 4,6 dichloropyridine |
| CN101519377A (en) * | 2009-04-10 | 2009-09-02 | 江苏常隆化工有限公司 | Method for producing substituted dichloropyrimidine |
| CN105195080A (en) * | 2015-10-10 | 2015-12-30 | 开封华瑞化工新材料股份有限公司 | Synthesis device and method for xylylene diisocynate |
| CN105732514A (en) * | 2016-03-16 | 2016-07-06 | 重庆紫光国际化工有限责任公司 | Synthetic method of 4,6-dichloropyrimidine |
-
2016
- 2016-07-19 CN CN201610571181.2A patent/CN106045917A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146766A (en) * | 1994-04-26 | 1997-04-02 | 曾尼卡有限公司 | Process for the preparation of 4,6-dichloropyrimidine |
| CN1206408A (en) * | 1995-01-30 | 1999-01-27 | 曾尼卡有限公司 | Process for preparing 4,6-dichloro-pyrimidine |
| US6160117A (en) * | 1997-11-06 | 2000-12-12 | Zeneca Limited | Chemical process |
| CN1687036A (en) * | 2005-06-20 | 2005-10-26 | 江苏省激素研究所有限公司 | Method for preparing 4,6 dichloropyridine |
| CN101519377A (en) * | 2009-04-10 | 2009-09-02 | 江苏常隆化工有限公司 | Method for producing substituted dichloropyrimidine |
| CN105195080A (en) * | 2015-10-10 | 2015-12-30 | 开封华瑞化工新材料股份有限公司 | Synthesis device and method for xylylene diisocynate |
| CN105732514A (en) * | 2016-03-16 | 2016-07-06 | 重庆紫光国际化工有限责任公司 | Synthetic method of 4,6-dichloropyrimidine |
Non-Patent Citations (2)
| Title |
|---|
| 彭志海: "嘧菌酯关键中间体CMB的合成工艺研究及CMP的回收利用", 《湘潭大学硕士学位论文》 * |
| 韩玉墀，等: "《化工工人岗位培训读本》", 31 December 1989, 化学工业出版社 * |
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Application publication date: 20161026 |