CN105801371B - Purposes of the oxidant in bromo-reaction - Google Patents
Purposes of the oxidant in bromo-reaction Download PDFInfo
- Publication number
- CN105801371B CN105801371B CN201410839939.7A CN201410839939A CN105801371B CN 105801371 B CN105801371 B CN 105801371B CN 201410839939 A CN201410839939 A CN 201410839939A CN 105801371 B CN105801371 B CN 105801371B
- Authority
- CN
- China
- Prior art keywords
- concentration
- hours
- reaction
- added
- hydrobromic acid
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The purposes that the present invention relates to oxidants in bromo-reaction.Purposes of the oxidant provided by the invention in bromo-reaction, improves the yield of two bromine reactants, can obtain average yield 50% or more, reaction product of the average purity 80% or more is with obvious effects to be better than the prior art.
Description
Technical field
The present invention relates to chemical drugs fields, and in particular to purposes of the oxidant in bromo-reaction.
Background technology
Mitolactol is also known as dibromo galactitol, is the isomers of dibromannitol, although being typically considered alkanisation
Agent, but its effect cannot be explained with alkanisation theory completely inhibits DNA synthesis to inhibit strong compared with RNA synthesis, it is in vivo
Main metabolites are di-epoxide, are cell cycle nonspecific agent (CCNSA).The LD50 of rat is：Oral 1400mg/kg, abdomen
Chamber injects 470mg/kg.Effect is similar to dibromannitol, is converted to the dianhydrogalactitol with diethyl epoxy construction in vivo
Afterwards, alkanisation is played.
Synthesis about mitolactol, it has been disclosed that following preparation method：
" synthesis of anticancer agent Dibromoducitol "《Jiangxi Medical College's journal》Preparation method is disclosed in the second phase in 1984：
Be under normal pressure 90 DEG C (± 1 DEG C) suitable heating time from melampyrin synthesis Dibromoducitol optimum temperature it is 9 hours；Hydrobromic acid
Concentration should be not less than 69-70%, and otherwise yield substantially reduces；Recrystallization solution boiling point cannot be too high, and heating time cannot be too long,
Otherwise yield can all be significantly reduced.Use the recrystallization mitolactol highest yield that this method obtains be 40% (with mole
Meter).
" stability of Dibromoducitol indicates high pressure liquid chromatography in aqueous solution "《External medicine synthetic drug Biochemical Drugs
Preparation fascicle》The 4th phase of volume 10 in 1989, also refer to the preparation method of mitolactol：Galactitol 400mg is placed in cold
Freeze glass reaction kettle and be dissolved in dense HBr 1.2ml, the closed container, is heated 12 hours in 70 water-baths, mixed liquor is poured into
In 3g ice, DBD is crystallized immediately, and after ice all dissolving, filtration, filter residue is dissolved in hot methanol, is recrystallized." this method gained two
The yield of bromine dulcitol is not open, and dense HBr refers to the acetum of HBr.
Since dissolubility is all very poor in most solvent for dulcitol, the narrow range for making bromating agent can be selected, to anti-
Condition is answered to require harsh, and method made above is suitable only for laboratory lab scale, because experimental raw is all made of analysis rank, sample
All conditions can disregard cost and accomplish most preferably when trial-production, when mass production, in order to reduce production cost, generally use industry
Grade raw material, condition can not possibly have that yield is low, purity is low such as the mitolactol that laboratory lab scale obtains, and uncomfortable
It is combined to for industry more than feather weight.
Mitolactol technology is prepared by existing, in addition to hydrobromic acid, if using remaining bromating agent, usage amount is mostly winged euonymus
10 times or more of alcohol weight could react completely, cause waste of solvent and environmental pollution.When selection hydrobromic acid is bromating agent, if
Obtain the higher mitolactol of purity, must also select the solvent of high-purity, such as a concentration of 69% hydrobromic acid solution with
On, the mitolactol of 70% or so purity could be obtained, if use low concentration hydrobromic acid solution yield usually 10% with
Under.The maximum concentration hydrobromic acid being commercially available in the market is 62%, is more than this concentration, it is necessary to which oneself is prepared, complex process, behaviour
Make process danger close, and differs and be surely successfully prepared.
Invention content
The object of the present invention is to provide oxidant increase 6-7 carbon two bromo reaction yield of polyalcohol in purposes,
It is characterized in that the oxidability of the oxidant is higher than bromine simple substance.
Preferably, the oxidant is perchloric acid, potassium hyperchlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide.
Preferably, the polyalcohol of the 6-7 carbon is hexitol and volemitol.
Purposes of the oxidant of the present invention in the two bromo reaction yield of polyalcohol for increasing 6-7 carbon, it is characterised in that bromine
Generation reaction includes the following steps：
1) it takes the polyalcohol of 6-7 carbon to set in reaction vessel, the hydrogen of 1-10 times of polyol weight, a concentration of 5-60% is added
Bromic acid organic acid soln stirs 0.5-5 hours at room temperature；
2) the addition oxidant for pressing the 1-15% of polyol quality, is heated to 30-55 DEG C, it is small to be persistently stirred to react 5-30
When.
Preferably, it is 10-28 hours that the step 2), which is stirred to react,.
Preferably, it is 20-25 hours that the step 2), which is stirred to react,.
Preferably, temperature when step 2) reaction is 40-50 DEG C.
Preferably, primary every sampling in 0.5-3 hours during the reaction after oxidant is added in the step 2), it measures
If being less than 20% hydrobromic acid organic acid soln is added, until hydrogen bromide in reaction solution in the concentration of hydrogen bromide in reaction solution
Concentration is 30% or more.
Preferably, the hydrobromic acid organic acid soln is hydrobromic acid glacial acetic acid solution or hydrobromic acid formic acid solution or hydrogen bromine
Sour propionic acid solution or hydrobromic acid butyric acid solution.
Preferably, a concentration of 34-60% of hydrobromic acid organic acid soln.
Preferably, the hydrobromic acid organic acid soln concentration being added after the step 2) sampling is 40% or more.
Purposes of the oxidant of the present invention in the two bromo reaction yield of polyalcohol for increasing 6-7 carbon, includes the following steps：
1) polyalcohol of 6-7 carbon is taken to set in reaction vessel, be added 1-10 times of dulcitol weight, a concentration of 5-60% hydrogen
Bromic acid organic acid soln stirs 0.5-5 hours at room temperature；
2) oxidant is added in the 1-15% for pressing polyol quality, is heated to 30-55 DEG C, is persistently stirred to react 5-30 hours,
It is primary every sampling in 0.5-3 hours during the reaction, the concentration of hydrogen bromide in reaction solution is measured, if it is less than 20%, plus
Enter hydrobromic acid organic acid soln, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 1-10 times of polyol weight is added stirs 2-3 hour, and supernatant is pumped after standing at least 12 hours
Liquid adds 0.1-2 times of polyol weight, a concentration of 70-95% ethyl alcohol, stirs evenly, filtering, filter residue with purified water rinse to
After neutrality, washed with 1-5 times of polyol weight, a concentration of 70-95% ethyl alcohol, the solid being collected into is dry at 25-35 DEG C
24-48 hours, obtain dibromo polyalcohol.
During the polyalcohol and hydrobromic acid organic acid reaction of 6-7 carbon, key reaction substance is the polyalcohol of 6-7 carbon
And hydrogen bromide, hydrogen bromide are dissolved in organic acid soln, when solution concentration drops to certain proportion, hydrogen bromide is precipitated very tired
Difficulty leads to reaction slowly or cannot be further continued for carrying out.Oxidant is added in reaction solution, hydrogen of the bromine from low concentration can be promoted
It is slowly precipitated in bromic acid organic acid soln, is oxidized to simple substance bromine, while increasing dibromo polyalcohol yield, reducing hydrobromic acid has
The addition of machine acid solution, it is cost-effective, mitigate environmental pollution.
The concentration for monitoring hydrogen bromide in reaction solution by sampling during the reaction, it is molten to be replenished in time hydrobromic acid organic acid
Liquid, makes the concentration of hydrogen bromide maintain sufficient concentration, and reaction can keep saturation state, improve reaction rate and dibromo be more
The yield of first alcohol.
Purposes of the oxidant provided by the invention in the two bromo reaction yield of polyalcohol for increasing 6-7 carbon has following
Advantage：
1, dibromo polyalcohol purity is high：The obtained dibromo polyol product purity of the prior art 70% hereinafter, using
The dibromo polyalcohol that the present invention is prepared, purity reach 80% or more.
High income when 2, using the present invention applied to industrialization production dibromo polyalcohol：The prior art is appropriate only for laboratory
Lab scale, large-scale production dibromo polyalcohol yield below 40% (in mol), present invention process safe and reasonable, obtained two
Bromine polyalcohol average yield is 50% or more.
3, low concentration hydrobromic acid solution is easy to get, and reduce the injury in big production to operator's health and
It reduces environmental pollution.
4, dibromo polyols preparation method disclosed in the prior art has been all made of high concentration of hydrogen bromic acid, in high temperature, short time
It is interior reaction and obtain.Because the reagent operation of high concentration is dangerous big, and high-temperature operation is difficult to control the precise procedural of reaction.This
Invention is not only high to equipment requirement and easily controllable using compared with low temperature conditioned response, can adjust at any time, although reaction
Time is longer than the prior art, but the yield of gained reactant of the present invention and purity are above prior art products obtained therefrom.
Specific implementation mode
It is further illustrated the present invention below by embodiment.It should be understood that the embodiment of the present invention is for illustrating
The present invention is rather than limiting the invention.The simple modifications that essence according to the present invention carries out the present invention belong to the present invention
Claimed range.Unless otherwise indicated, the percentage of the amount of alcohol in the present invention is percentage by volume, and v/v indicates solution
Volume ratio.
Embodiment 1：Prepare hydrobromic acid organic acid soln
At a temperature of -5 DEG C, bromination hydrogen is passed through in organic acid, obtains a concentration of 34% hydrobromic acid organic acid soln.
Embodiment 2：Prepare hydrobromic acid organic acid soln
At a temperature of -10 DEG C, bromination hydrogen is passed through in organic acid, obtain a concentration of 40% hydrobromic acid organic acid it is molten
Liquid.
Embodiment 3：
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 3 times of dulcitol weight, a concentration of 50% hydrobromic acid glacial acetic acid
Solution stirs 1.5 hours at room temperature；
2) hydrogen peroxide is added in press dulcitol quality 8%, is heated to 40 DEG C, persistently stirs 25 hours, in reaction process
In it is primary every sampling in 1.5 hours, measure the concentration of hydrogen bromide in reaction solution, if being less than 20%, hydrobromic acid ice vinegar be added
Acid solution, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 10 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 12 hours, adds and defend
0.1 times of lance alcohol weight, a concentration of 70% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
1 times of weight, the washing of a concentration of 70% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 27 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 56.7%, average purity 88.8.
Embodiment 4：
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 1 times of dulcitol weight, a concentration of 45% hydrobromic acid propionic acid it is molten
Liquid stirs 2 hours at room temperature；
2) perchloric acid is added in press dulcitol quality 4%, is heated to 30 DEG C, persistently stirring 18 hours, during the reaction
It is primary every sampling in 1 hour, the concentration of hydrogen bromide in reaction solution is measured, if being less than 20%, hydrobromic acid propionic acid solution is added,
To hydrogen bromide in reaction solution concentration 30% or more；
3) purified water that 8 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 15 hours, adds and defend
0.5 times of lance alcohol weight, a concentration of 75% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
2 times of weight, the washing of a concentration of 75% ethyl alcohol, the solid being collected into is 48 hours dry at a temperature of 25 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 54.2%, average purity 87.4.
Embodiment 5：
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 7 times of dulcitol weight, a concentration of 34% hydrobromic acid glacial acetic acid
Solution stirs 1 hour at room temperature；
2) potassium hyperchlorate is added in press dulcitol quality 12%, is heated to 35 DEG C, persistently stirs 20 hours, in reaction process
In it is primary every sampling in 1 hour, measure the concentration of hydrogen bromide in reaction solution, if being less than 20%, hydrobromic acid glacial acetic acid be added
Solution, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 6 times of dulcitol weight is added stirs 3 hours, pumps supernatant after standing 18 hours, adds and defend
1 times of lance alcohol weight, a concentration of 95% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, with dulcitol weight
3 times of amount, the washing of a concentration of 95% ethyl alcohol, the solid being collected into is 48 hours dry at a temperature of 28 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 55.1%, average purity 86.9.
Embodiment 6：
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 5 times of dulcitol weight, a concentration of 60% hydrobromic acid butyric acid it is molten
Liquid stirs 3 hours at room temperature；
2) potassium permanganate is added in press dulcitol quality 6%, is heated to 34 DEG C, persistently stirs 28 hours, in reaction process
In it is primary every sampling in 2 hours, measure the concentration of hydrogen bromide in reaction solution, if being less than 20%, it is molten that hydrobromic acid butyric acid be added
Liquid, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 5 times of dulcitol weight is added stirs 2.5 hours, pumps supernatant after standing 16 hours, adds
1 times of dulcitol weight, a concentration of 80% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
5 times of weight, the washing of a concentration of 80% ethyl alcohol, the solid being collected into is 24 hours dry at a temperature of 32 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 53.7%, average purity 85.3.
Embodiment 7：
1) 5.0kg volemitols is taken to set in reaction kettle, be added 8 times of volemitol weight, a concentration of 20% hydrobromic acid formic acid it is molten
Liquid stirs 0.5 hour at room temperature；
2) hydrogen peroxide is added in press volemitol quality 2%, is heated to 50 DEG C, persistently stirs 10 hours, in reaction process
In it is primary every sampling in 0.5 hour, measure the concentration of hydrogen bromide in reaction solution, if being less than 20%, hydrobromic acid formic acid be added
Solution, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 4 times of volemitol weight is added stirs 3 hours, pumps supernatant after standing 20 hours, adds heptan
Seven 1.5 times of alcohol weight, a concentration of 90% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses volemitol
3 times of weight, the washing of a concentration of 90% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 34 DEG C, obtain dibromo volemitol.
Experimental result：Dibromo volemitol average yield 55.3%, average purity 86.4.
Embodiment 8：
1) 5.0kg volemitols is taken to set in reaction kettle, be added 10 times of volemitol weight, a concentration of 5% hydrobromic acid glacial acetic acid
Solution stirs 2.5 hours at room temperature；
2) sodium hypochlorite is added in press volemitol quality 15%, is heated to 55 DEG C, persistently stirs 30 hours, in reaction process
In it is primary every sampling in 3 hours, measure the concentration of hydrogen bromide in reaction solution, if being less than 20%, hydrobromic acid glacial acetic acid be added
Solution, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 2 times of volemitol weight is added stirs 2.5 hours, pumps supernatant after standing 24 hours, adds
2 times of volemitol weight, a concentration of 85% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses volemitol
1 times of weight, the washing of a concentration of 85% ethyl alcohol, the solid being collected into is 48 hours dry at a temperature of 30 DEG C, obtain dibromo volemitol.
Experimental result：Dibromo volemitol average yield 54.5%, average purity 85.6.
Comparative example 1：With reference to the embodiment of the present invention 3, anaerobic agent is added without hydrobromic acid organic acid halfway
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 3 times of dulcitol weight, a concentration of 55% hydrobromic acid glacial acetic acid
Solution stirs 1.5 hours, is heated to 40 DEG C at room temperature, persistently stirs 25 hours.
2) purified water that 10 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 12 hours, adds and defend
0.1 times of lance alcohol weight, a concentration of 70% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
1 times of weight, the washing of a concentration of 70% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 27 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 33.2%, average purity 64.5.
Comparative example 2：With reference to the embodiment of the present invention 3, anaerobic agent
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 3 times of dulcitol weight, a concentration of 55% hydrobromic acid glacial acetic acid
Solution stirs 1.5 hours, is heated to 40 DEG C at room temperature, persistently stirs 25 hours, was sampled during the reaction every 1.5 hours
Once, the concentration of hydrogen bromide in reaction solution is measured, if being less than 20%, hydrobromic acid glacial acetic acid solution is added, until reaction solution
The concentration of middle hydrogen bromide is 30% or more；
2) purified water that 10 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 12 hours, adds and defend
0.1 times of lance alcohol weight, a concentration of 70% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
1 times of weight, the washing of a concentration of 70% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 27 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 34.6%, average purity 65.7.
Comparative example 3：With reference to the embodiment of the present invention 3, it is added without hydrobromic acid organic acid halfway
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 3 times of dulcitol weight, a concentration of 55% hydrobromic acid glacial acetic acid
Solution stirs 1.5 hours at room temperature；Hydrogen peroxide is added by the 8% of dulcitol quality, is heated to 40 DEG C, it is small persistently to stir 25
When.
2) purified water that 10 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 12 hours, adds and defend
0.1 times of lance alcohol weight, a concentration of 70% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
1 times of weight, the washing of a concentration of 70% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 27 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 35.1%, average purity 65.3.
Comparative example 4：With reference to the embodiment of the present invention 3, it is added without hydrobromic acid organic acid halfway, improves addition when starting reaction
Amount
1) 5.0kg dulcitols is taken to set in reaction kettle, be added 4 times of dulcitol weight, a concentration of 55% hydrobromic acid glacial acetic acid
Solution stirs 1.5 hours at room temperature；Hydrogen peroxide is added by the 8% of dulcitol quality, is heated to 40 DEG C, it is small persistently to stir 25
When,
2) purified water that 10 times of dulcitol weight is added stirs 2 hours, pumps supernatant after standing 12 hours, adds and defend
0.1 times of lance alcohol weight, a concentration of 70% ethyl alcohol, stir evenly, and filtering, filter residue is rinsed with purified water to neutrality, uses dulcitol
1 times of weight, the washing of a concentration of 70% ethyl alcohol, the solid being collected into is 36 hours dry at a temperature of 27 DEG C, obtain mitolactol.
Experimental result：Mitolactol average yield 38.4%, average purity 67.0.
Process ration is tested：
Experimental method：Disclosed reaction pressure, reaction temperature etc. according to the present invention prepare embodiment 1-8 samples；In reality
On the basis of applying a preparation method, not oxidizer, subtract midway be added hydrobromic acid organic acid reaction condition, prepare comparison respectively
Example sample；It the results are shown in Table 1.
Table 1：Bromination reaction experimental result
1 result of table is shown：The hydrobromic acid organic acid content that comparative example has subtracted oxidant or has been added when midway is monitored, adds
To start reaction when simultaneously be added, reaction result show in this way operate acquisition dibromo polyol reactant yield and purity not
It is ideal.Midway addition is added together with when starting, as a result, significant difference.
The experimental results showed that：By response parameter provided by the invention, it may be significantly and prepared better than prior art
The effect of gained dibromo polyalcohol.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (8)
1. purposes of the oxidant in the two bromo reaction yield of polyalcohol for increasing 6-7 carbon, which is characterized in that the bromo
Reaction includes the following steps：
1) it takes the polyalcohol of 6-7 carbon to set in reaction vessel, 1-10 times of polyol weight, a concentration of 5-60% is added
Hydrobromic acid organic acid soln stirs 0.5-5 hours at room temperature；
2) the addition oxidant for pressing the 1-15% of polyol quality, is heated to 30-55 DEG C, it is small to be persistently stirred to react 5-30
When；
It is primary every sampling in 0.5-3 hours during the reaction after oxidant is added in the step 2), measure reaction solution
If being less than 20% hydrobromic acid organic acid soln is added, until the concentration of hydrogen bromide exists in reaction solution in the concentration of middle hydrogen bromide
30% or more；
The oxidant is perchloric acid, potassium hyperchlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide；The 6-7 carbon it is more
First alcohol is hexitol and volemitol.
2. the method as described in claim 1, which is characterized in that it is 10-28 hours that the step 2), which is stirred to react,.
3. the method as described in claim 2, which is characterized in that it is 20-25 hours that the step 2), which is stirred to react,.
4. the method as described in claim 1, which is characterized in that temperature when step 2) reaction is 40-50 DEG C.
5. the method as described in claim 1, which is characterized in that the hydrobromic acid organic acid soln is that hydrobromic acid glacial acetic acid is molten
Liquid or hydrobromic acid formic acid solution or hydrobromic acid propionic acid solution or hydrobromic acid butyric acid solution.
6. the method as described in claim 1, which is characterized in that a concentration of 34-60% of hydrobromic acid organic acid soln.
7. the method as described in claim 1, which is characterized in that the hydrobromic acid organic acid being added after the step 2) sampling
Solution concentration is 40% or more.
8. the method as described in claim 1, which is characterized in that include the following steps：
1) it takes the polyalcohol of 6-7 carbon to set in reaction vessel, 1-10 times of the polyol weight, a concentration of 5- is added
60% hydrobromic acid organic acid soln stirs 0.5-5 hours at room temperature；
2) oxidant is added in the 1-15% for pressing polyol quality, is heated to 30-55 DEG C, is persistently stirred to react 5-30 hours,
It is primary every sampling in 0.5-3 hours during the reaction, the concentration of hydrogen bromide in reaction solution is measured, if being less than 20%,
Hydrobromic acid organic acid soln is added, until the concentration of hydrogen bromide is 30% or more in reaction solution；
3) purified water that 1-10 times of polyol weight is added stirs 2-3 hour, is pumped after standing at least 12 hours
Clear liquid adds 0.1-2 times of polyol weight, a concentration of 70-95% ethyl alcohol, stirs evenly, filtering, filter residue purified water
It rinses to neutrality, is washed with 1-5 times of polyol weight, a concentration of 70-95% ethyl alcohol, by the solid being collected into 25-
It is dry at 35 DEG C
24-48 hours, obtain dibromo polyalcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410839939.7A CN105801371B (en) | 2014-12-30 | 2014-12-30 | Purposes of the oxidant in bromo-reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410839939.7A CN105801371B (en) | 2014-12-30 | 2014-12-30 | Purposes of the oxidant in bromo-reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801371A CN105801371A (en) | 2016-07-27 |
| CN105801371B true CN105801371B (en) | 2018-09-28 |
Family
ID=56980151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410839939.7A Active CN105801371B (en) | 2014-12-30 | 2014-12-30 | Purposes of the oxidant in bromo-reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801371B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8921585B2 (en) * | 2010-08-18 | 2014-12-30 | Del Mar Pharmaceuticals | Method of synthesis of substituted hexitols such as dianhydrogalactitol |
-
2014
- 2014-12-30 CN CN201410839939.7A patent/CN105801371B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 氢溴酸/双氧水溴代体系的应用及4-甲基二苯甲酮衍生物的合成;龚年华;《中国优秀硕士学位论文全文数据库-工程科技I辑》;20100515(第5期);第一章第1页第3段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801371A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105837563B (en) | The production method of flumioxazin | |
| CN105218610B (en) | Method for synthesizing cholesterol by using stigmasterol degradation products as raw materials | |
| CN105399791B (en) | A kind of preparation method of betamethasone intermediate | |
| CN102796035A (en) | Condensation method of m-,p-mixed di-(tert-butyl isopropyl peroxide)benzene | |
| CN103694094B (en) | A kind of preparation method of the chloro-2 pentanone of 5- | |
| CN105801371B (en) | Purposes of the oxidant in bromo-reaction | |
| CN104086466B (en) | The preparation method of the thiamphenicol benzoic acid of 2 chlorine 4 | |
| CN105801370B (en) | A method of improving two substitution dulcitol reaction product yields | |
| CN105801374B (en) | A kind of synthetic method for improving bromo hexitol reaction product yield | |
| CN105801364B (en) | A kind of preparation method of bromo hexitol | |
| CN105198728B (en) | A kind of method for preparing medicinal potassium acetate | |
| CN105801369B (en) | The method for improving mitolactol substitution reaction product yield and purity | |
| CN102992989A (en) | Synthetic method of beta-menadione | |
| CN102942574B (en) | Novel process for producing rifamycin S | |
| CN109608511B (en) | Chemical synthesis process of prednisolone valerate acetate | |
| CN110790687A (en) | Production method of 3- (cyclohexylamine) -1-propanesulfonic acid | |
| TWI762736B (en) | Method for producing dihydroxyindoles | |
| CN106496031A (en) | A kind of method for improving dimethyl malenate yield | |
| CN105801361B (en) | A kind of two replace the synthetic method of dulcitol | |
| CN106630342B (en) | Decomplexation method of N-methyl pyrrolidone metal complex in salt-containing organic waste liquid | |
| CN110256234A (en) | A kind of preparation method of calcium gluconate | |
| CN105801366B (en) | A kind of synthetic method of bromo alkylating agent | |
| CN105801360B (en) | A kind of preparation method of dibromo hexitol | |
| CN103497844A (en) | Method for electric hydrogenation of soybean oil in supercritical H2 condition | |
| CN105801358B (en) | A kind of preparation method of dulcitol bromo-reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |