CN109384671A - A kind of preparation method of bromomalonic acid diester - Google Patents
A kind of preparation method of bromomalonic acid diester Download PDFInfo
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- CN109384671A CN109384671A CN201710673441.1A CN201710673441A CN109384671A CN 109384671 A CN109384671 A CN 109384671A CN 201710673441 A CN201710673441 A CN 201710673441A CN 109384671 A CN109384671 A CN 109384671A
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- diester
- preparation
- sodium chlorite
- acid
- bromomalonic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemosynthesis technical fields, more particularly to a kind of preparation method of bromomalonic acid diester, it is mainly in hydrobromic acid and methylene chloride, diester malonate two-phase system, sodium chlorite, which was reacted with hydrobromic acid moment, when by the way that sodium chlorite solution is added dropwise releases high activity atom bromine and reacts with diester malonate, and direct synthetic bromide is for diester malonate.The raw materials such as environmental-friendly hydrobromic acid, sodium chlorite are selected in this case, avoid the use of big, volatile, high price the bromine of toxicity.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of preparation method of bromomalonic acid diester.
Background technique
Dimethyl malenate is a kind of important industrial chemicals and medicine intermediate, active due to containing in molecular structural formula
Methylene is easy to be replaced by other groups, therefore can be hydrolyzed, Michael reaction, amidation, hydroxyalkylation and alkylation etc.
A variety of substitution reactions have obtained very universal application in the industry such as dyestuff, medicine and pesticide.
Existing to mostly use bromine to diester malonate progress bromo-reaction, bromine has stronger toxicity, and bromine vapor is
Can also burn mucous membrane when keeping concentration very low, the symptoms such as appearance is coughed, mucosal secretion increases, nosebleed, dizziness.Liquid bromine is to skin
Skin has strong corrosivity, will form the scar for being difficult to heal.
Summary of the invention
Invention broadly provides a kind of preparation method of bromomalonic acid diester, environmental-friendly hydrogen bromine is selected in this case
The raw materials such as acid, sodium chlorite avoid the use of big, volatile, high price the bromine of toxicity.Its technical solution is as follows:
A kind of preparation method of bromomalonic acid diester is specifically, in hydrobromic acid and methylene chloride, diester malonate two
In phase system, sodium chlorite solution is added dropwise, direct synthetic bromide is for diester malonate.
Preferably, hydrobromic acid, methylene chloride, diester malonate molar ratio be (1.0-1.1): (3-4): 1.
Preferably, be added dropwise sodium chlorite solution when sodium chlorite reacted with hydrobromic acid moment release high activity atom bromine and
Diester malonate is reacted, and the molar ratio of sodium chlorite and diester malonate is (1.0-1.1): 1.
Preferably, the method and step of preparation is as follows:
(1) in the reaction vessel, the diester malonate and methylene chloride of formula ratio is added, it is 20% that concentration, which is then added,
Hydrobromic acid solution；
(2) it stirs evenly, the sodium chlorite solution that concentration is 10% is added, wherein the mole of chlorine element is 1.0-
1.1mol；
(3) first insulation reaction 1-2h under the conditions of 25 ± 3 DEG C, then 35 ± 3 DEG C are warming up to, carry out reaction 0.5-1.5h；
(4) split-phase is stood, organic phase is washed respectively, sodium bicarbonate is washed, is washed, until reaching neutral；
(5) the dry, precipitation by neutral inorganic phase, obtains bromomalonic acid diester crude product；
(6) by crude product rectification process, fine work is obtained.
Using the above scheme, the invention has the following advantages that
This case avoids big, volatile, high price the bromine of toxicity using raw materials such as environmental-friendly sodium chlorite, hydrobromic acids
The use of element, brominated reagent are generated as sodium chlorite is added dropwise, and reaction mitigation is easily-controllable, and selectivity is good.After completion of the reaction, product exists
Can natural layering, post-processing is simple, and toluene can recycle after washing.
Specific embodiment
Experimental method in following embodiment is conventional method unless otherwise required, related experiment reagent and material
Material is conventional biochemical reagent and material unless otherwise required.
Embodiment 1
A kind of preparation method of bromomalonic acid diester comprising following steps:
(1) in the reaction vessel, the methylene chloride that the diester malonate and 200ml density that 1mol is added are 1.325g/mL,
Then the hydrobromic acid solution that concentration is 20% is added, the mole of hydrobromic acid is 1.03mol；
(2) it stirs evenly, the sodium chlorite solution that concentration is 10% is added, wherein the mole of chlorine element is 1.03mol；
(3) first insulation reaction 2h under the conditions of 25 ± 3 DEG C, then 35 ± 3 DEG C are warming up to, carry out reaction 1h；
(4) split-phase is stood, organic phase is washed respectively, 5% sodium bicarbonate is washed, washed, until reaching neutral；
(5) the dry, precipitation by neutral inorganic phase, obtains bromomalonic acid diester crude product, content 97%；
(6) by crude product rectification process, bromomalonic acid diester fine work, content 99.3%, yield 94.5% are obtained.
Embodiment 2
A kind of preparation method of bromomalonic acid diester comprising following steps:
(1) in the reaction vessel, the methylene chloride that the diester malonate and 300ml density that 1mol is added are 1.325g/mL,
Then the hydrobromic acid solution that concentration is 20% is added, the mole of hydrobromic acid is 1.1mol；
(2) it stirs evenly, the sodium chlorite solution that concentration is 10% is added, wherein the mole of chlorine element is 1.1mol；
(3) first insulation reaction 1h under the conditions of 25 ± 3 DEG C, then 35 ± 3 DEG C are warming up to, carry out reaction 1.5h；
(4) split-phase is stood, organic phase is washed respectively, 5% sodium bicarbonate is washed, washed, until reaching neutral；
(5) the dry, precipitation by neutral inorganic phase, obtains bromomalonic acid diester crude product, content 97%；
(6) by crude product rectification process, bromomalonic acid diester fine work, content 99.4%, yield 94.8% are obtained.
Embodiment 3
A kind of preparation method of bromomalonic acid diester comprising following steps:
(1) in the reaction vessel, the methylene chloride that the diester malonate and 250ml density that 1mol is added are 1.325g/mL,
Then the hydrobromic acid solution that concentration is 20% is added, the mole of hydrobromic acid is 1.05mol；
(2) it stirs evenly, the sodium chlorite solution that concentration is 10% is added, wherein the mole of chlorine element is 1.03mol；
(3) first insulation reaction 1h under the conditions of 25 ± 3 DEG C, then 35 ± 3 DEG C are warming up to, carry out reaction 1.5h；
(4) split-phase is stood, organic phase is washed respectively, 5% sodium bicarbonate is washed, washed, until reaching neutral；
(5) the dry, precipitation by neutral inorganic phase, obtains bromomalonic acid diester crude product, content 97%；
(6) by crude product rectification process, bromomalonic acid diester fine work, content 99.2%, yield 94% are obtained.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (4)
1. a kind of preparation method of bromomalonic acid diester, it is characterised in that: in hydrobromic acid and methylene chloride, diester malonate two
In phase system, sodium chlorite solution is added dropwise, direct synthetic bromide is for diester malonate.
2. the preparation method of bromomalonic acid diester according to claim 1, it is characterised in that: hydrobromic acid, methylene chloride,
The molar ratio of diester malonate is (1.0-1.1): (3-4): 1.
3. the preparation method of bromomalonic acid diester according to claim 1, it is characterised in that: sodium chlorite solution is added dropwise
When sodium chlorite reacted with hydrobromic acid moment and release high activity atom bromine and reacted with diester malonate, sodium chlorite and third
The molar ratio of two acid diesters is (1.0-1.1): 1.
4. the preparation method of bromomalonic acid diester according to claim 1, it is characterised in that: the method and step of preparation is such as
Under:
(1) in the reaction vessel, the diester malonate and methylene chloride of formula ratio is added, the hydrogen bromine that concentration is 20% is then added
Acid solution；
(2) it stirs evenly, the sodium chlorite solution that concentration is 10% is added, wherein the mole of chlorine element is 1.0-1.1mol；
(3) first insulation reaction 1-2h under the conditions of 25 ± 3 DEG C, then 35 ± 3 DEG C are warming up to, carry out reaction 0.5-1.5h；
(4) split-phase is stood, organic phase is washed respectively, sodium bicarbonate is washed, is washed, until reaching neutral；
(5) the dry, precipitation by neutral inorganic phase, obtains bromomalonic acid diester crude product；
(6) by crude product rectification process, fine work is obtained.
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| CN201710673441.1A CN109384671A (en) | 2017-08-09 | 2017-08-09 | A kind of preparation method of bromomalonic acid diester |
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| CN201710673441.1A CN109384671A (en) | 2017-08-09 | 2017-08-09 | A kind of preparation method of bromomalonic acid diester |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119211A (en) * | 2014-08-01 | 2014-10-29 | 黄山学院 | Method for preparing alpha-monobrominated ketone and alpha, alpha-dibrominated ketone compounds by selectively brominating ketone compounds |
| CN105461496A (en) * | 2015-12-14 | 2016-04-06 | 江苏强盛功能化学股份有限公司 | Preparation method for 2-halogenated-1,3-dicarbonyl derivative |
| CN105669364A (en) * | 2016-02-19 | 2016-06-15 | 国药集团化学试剂有限公司 | Method for synthesizing bromotoluene |
| CN105801348A (en) * | 2016-04-20 | 2016-07-27 | 江苏中能化学科技股份有限公司 | 3-bromobenzotrifluoride and preparation method thereof |
| WO2017100985A1 (en) * | 2015-12-14 | 2017-06-22 | 苏州大学张家港工业技术研究院 | Preparation method for 2,2-dihalo-1,3-dicarbonyl derivatives |
-
2017
- 2017-08-09 CN CN201710673441.1A patent/CN109384671A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119211A (en) * | 2014-08-01 | 2014-10-29 | 黄山学院 | Method for preparing alpha-monobrominated ketone and alpha, alpha-dibrominated ketone compounds by selectively brominating ketone compounds |
| CN105461496A (en) * | 2015-12-14 | 2016-04-06 | 江苏强盛功能化学股份有限公司 | Preparation method for 2-halogenated-1,3-dicarbonyl derivative |
| WO2017100985A1 (en) * | 2015-12-14 | 2017-06-22 | 苏州大学张家港工业技术研究院 | Preparation method for 2,2-dihalo-1,3-dicarbonyl derivatives |
| CN105669364A (en) * | 2016-02-19 | 2016-06-15 | 国药集团化学试剂有限公司 | Method for synthesizing bromotoluene |
| CN105801348A (en) * | 2016-04-20 | 2016-07-27 | 江苏中能化学科技股份有限公司 | 3-bromobenzotrifluoride and preparation method thereof |
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