CN105801364A - Preparation method of brominated hexanehexol - Google Patents
Preparation method of brominated hexanehexol Download PDFInfo
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- CN105801364A CN105801364A CN201410839711.8A CN201410839711A CN105801364A CN 105801364 A CN105801364 A CN 105801364A CN 201410839711 A CN201410839711 A CN 201410839711A CN 105801364 A CN105801364 A CN 105801364A
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- dulcitol
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Abstract
The invention relates to a preparation method of brominated hexanehexol. The preparation method of brominated hexanehexol is used, and the reaction product whose average yield is 50% or above and average purity is 80% or above is obtained; and compared with the prior art, the effect is obviously better.
Description
Technical field
The present invention relates to chemical drugs field, the preparation method being specifically related to a kind of bromo hexanhexol.
Background technology
Mitolactol is also known as dibromo galactitol, isomer for mitobronitol, although being typically considered alkylating agent, but its effect can not be explained by alkanisation theory completely, DNA synthesis is suppressed relatively RNA synthesis to suppress strong by it, its main metabolites in vivo is di-epoxide, for cell cycle nonspecific agent (CCNSA).The LD50 of rat is: oral 1400mg/kg, lumbar injection 470mg/kg.Act on similar to mitobronitol, after changing into the dianhydrodulcitol with diethyl epoxy construction in vivo, play alkanisation.
Synthesis about mitolactol, it has been disclosed that following preparation method:
Preparation method disclosed in " synthesis of anticarcinogen Dibromoducitol " " Jiangxi Medical College's journal " second phase in 1984 is: synthesizing Dibromoducitol optimum temperature from melampyrin at ambient pressure be 90 DEG C (± 1 DEG C) suitable heat time heating time is 9 hours；Hydrobromic acid concentration should be not less than 69-70%, and otherwise yield is substantially reduced；Recrystallization solution boiling point can not be too high, and heat time heating time can not be oversize, otherwise all can significantly reduce productivity.Adopting the recrystallization the highest yield of mitolactol that the method obtains was 40% (in mol).
" in aqueous solution the stability instruction high pressure liquid chromatography of Dibromoducitol " " medicine abroad. synthetic drug. Biochemical Drugs. preparation fascicle " the 10th volume the 4th phase in 1989, also the preparation method that refer to mitolactol: galactitol 400mg is placed in refrigeration glass reactor and is dissolved in dense HBr1.2ml, this container airtight, heating 12 hours in 70 DEG C of water-baths, poured into by mixed liquor in 3g ice, DBD is crystallization immediately, after ice all dissolves, filtering, filtering residue is dissolved in hot methanol, recrystallization." yield of the method gained mitolactol is open, and dense HBr refers to the acetum of HBr.
Owing to dulcitol dissolubility in most solvent is all very poor, can select that the narrow range making bromating agent, reaction condition is required harshness, and method made above is suitable only for laboratory lab scale, because experimental raw all adopts analysis rank, during sample trial-production, all conditions can be disregarded cost and accomplishes the best, during production in enormous quantities, in order to reduce production cost, generally adopt industrial raw material, can not all there is the problem that yield is low, purity is low by mitolactol as laboratory lab scale obtains in condition, and be not suitable for the industrialization synthesis of more than feather weight.
By existing mitolactol technology of preparing, outside dehydrogenation bromic acid, if using remaining bromating agent, making consumption mostly be more than 10 times ability complete reactions of dulcitol weight, causing waste of solvent and environmental pollution.When selection hydrobromic acid is bromating agent, if obtaining the mitolactol that purity is higher, also must select highly purified solvent, as more than hydrobromic acid solution that concentration is 69%, the mitolactol of about 70% purity could be obtained, if adopting low concentration hydrobromic acid solution yield generally below 10%.The maximum concentration hydrobromic acid being commercially available on market is 62%, exceedes this concentration, it is necessary to oneself preparation, complex process, operating process danger close, and differs and be successfully prepared surely.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of bromo hexanhexol.
The preparation method of bromo hexanhexol of the present invention includes bromination step, it is characterised in that comprise the steps:
Take dulcitol and put in reaction vessel, addition dulcitol weight 1-10 times, concentration are the hydrobromic acid organic acid soln of 5-60%, simultaneously, oxidant is added by the 1-15% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.1-1.0Mpa, heat to 30-55 DEG C, continuously stirred reaction 10-30 hour.
Preferably, described oxidant is perchloric acid, potassium hyperchlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide.
Preferably, described stirring reaction is 10-28 hour.
Preferably, described stirring reaction is 20-25 hour.
Preferably, temperature during described reaction is 40-50 DEG C.
Preferably, described hydrobromic acid organic acid soln is hydrobromic acid glacial acetic acid solution or hydrobromic acid formic acid solution or hydrobromic acid propionic acid solution or hydrobromic acid butanoic acid solution.
Preferably, described hydrobromic acid organic acid soln concentration is 30-60%.
Preferably, described hydrobromic acid organic acid soln is prepared by the following method and is obtained: lower than, at-5 DEG C of temperature, hydrogen bromide gas being passed in organic acid, obtaining the hydrobromic acid organic acid soln that concentration is 30-60%.
Preferably, described organic acid is glacial acetic acid, formic acid, propanoic acid or butanoic acid.
The preparation method of bromo hexanhexol of the present invention, comprises the steps:
1) take dulcitol and put in reaction vessel, addition dulcitol weight 1-10 times, concentration are the hydrobromic acid organic acid soln of 5-60%, simultaneously, oxidant is added by the 1-15% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.1-1.0Mpa, keep temperature to 30-55 DEG C, continuously stirred reaction 10-30 hour；
2) purified water adding dulcitol weight 1-10 times stirs 2-3 hour, supernatant is pumped after standing at least 12 hours, add dulcitol weight 0.1-2 times, concentration is 70-95% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70-95% washing with alcohol by dulcitol weight 1-5 times, concentration, the solid collected is dried 24-48 hour at 25-35 DEG C, obtains mitolactol.
In dulcitol and hydrobromic acid organic acid reaction process, dominant response material is dulcitol and hydrogen bromide, and hydrogen bromide is dissolved in organic acid soln, and when solution concentration drops to certain proportion, hydrogen bromide precipitates out extremely difficult, causes that sluggish maybe can not be further continued for carrying out.Reaction solution adds oxidant, it is possible to promote bromine slowly to precipitate out from the hydrobromic acid organic acid soln of low concentration, be oxidized to simple substance bromine, while increasing the yield of mitolactol, reduce the addition of hydrobromic acid organic acid soln, save cost, alleviate environmental pollution.
Pass into HBr gas in reaction whole process, keep bromine to maintain saturation in the reaction, it is possible to improve the yield of reaction rate and mitolactol always.
The preparation method of a kind of bromo hexanhexol provided by the invention has the advantage that
1, mitolactol purity is high: the obtained mitolactol product purity of prior art, all below 70%, adopts the mitolactol that the present invention is prepared from, and purity reaches more than 80%.
2, adopt the present invention to be applied to industrialization and produce yield height during mitolactol: prior art is appropriate only for laboratory lab scale, large-scale production mitolactol yield below 40% (in mol), present invention process safe and reasonable, prepared mitolactol average yield is more than 50%.
3, low concentration hydrobromic acid solution is readily available, and reduces in big production the injury of operator ' s health and minimizing environmental pollution.
4, mitolactol preparation method disclosed in prior art all have employed high concentration of hydrogen bromic acid, high temperature, in the short time reaction and obtain.Because the reagent operation of high concentration is dangerous big, and high-temperature operation is difficult to control to the precise procedural of reaction.The present invention adopts relatively low temperature conditioned response, not only that equipment requirements is not high, and easily controllable, it is possible to adjust at any time, although the response time is longer than prior art, but the yield of gained reactant of the present invention and purity are above prior art products obtained therefrom.
Detailed description of the invention
Further illustrate the present invention by the examples below.It should be understood that embodiments of the invention are an illustration for the present invention rather than limitation of the present invention.The simple modifications that the present invention is carried out by the essence according to the present invention broadly falls into the scope of protection of present invention.Except as otherwise noted, the percent of the amount of alcohol in the present invention is percentage by volume, and v/v represents the volume ratio of solution.
Embodiment 1: prepare hydrobromic acid ice organic acid soln
At-5 DEG C of temperature, hydrogen bromide gas is passed in organic acid, obtain the hydrobromic acid organic acid soln that concentration is 30%.
Embodiment 2: prepare hydrobromic acid organic acid soln
At-10 DEG C of temperature, hydrogen bromide gas is passed in organic acid, obtain the hydrobromic acid organic acid soln that concentration is 60%.
Embodiment 3:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 4 times, concentration is 45% hydrobromic acid glacial acetic acid solution, simultaneously, hydrogen peroxide is added by the 7% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.6Mpa, keep temperature to 45 DEG C, continuously stirred 20 hours.
2) purified water adding dulcitol weight 10 times stirs 2 hours, supernatant is pumped after standing 12 hours, add dulcitol weight 0.1 times, concentration is 70% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70% washing with alcohol by dulcitol weight 1 times, concentration, the solid collected is dried 36 hours at 27 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 60.5%, average purity 89.8%
Embodiment 4:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 2 times, concentration is 50% hydrobromic acid butanoic acid solution, simultaneously, potassium hyperchlorate is added by the 5% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.4Mpa, keep temperature to 35 DEG C, continuously stirred 10 hours.
2) purified water adding dulcitol weight 8 times stirs 2 hours, supernatant is pumped after standing 15 hours, add dulcitol weight 0.5 times, concentration is 75% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 75% washing with alcohol by dulcitol weight 2 times, concentration, the solid collected is dried 48 hours at 25 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 56.2%, average purity 88.4%
Embodiment 5:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 6 times, concentration is 30% hydrobromic acid propionic acid solution, simultaneously, potassium permanganate is added by the 1% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.2Mpa, keep temperature to 40 DEG C, continuously stirred 25 hours.
2) purified water adding dulcitol weight 6 times stirs 3 hours, supernatant is pumped after standing 18 hours, add dulcitol weight 1 times, concentration is 95% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 95% washing with alcohol by dulcitol weight 3 times, concentration, the solid collected is dried 48 hours at 28 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 58.1%, average purity 88.6%
Embodiment 6:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 1 times, concentration is 60% hydrobromic acid formic acid solution, simultaneously, perchloric acid is added by the 3% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.1Mpa, keep temperature to 30 DEG C, continuously stirred 18 hours.
2) purified water adding dulcitol weight 5 times stirs 2.5 hours, supernatant is pumped after standing 16 hours, add dulcitol weight 1 times, concentration is 80% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 80% washing with alcohol by dulcitol weight 5 times, concentration, the solid collected is dried 24 hours at 32 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 53.7%, average purity 87.2%
Embodiment 7:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 8 times, concentration is 20% hydrobromic acid glacial acetic acid solution, simultaneously, hydrogen peroxide is added by the 12% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.8Mpa, keep temperature to 55 DEG C, continuously stirred 28 hours.
2) purified water adding dulcitol weight 4 times stirs 3 hours, supernatant is pumped after standing 20 hours, add dulcitol weight 1.5 times, concentration is 90% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 90% washing with alcohol by dulcitol weight 3 times, concentration, the solid collected is dried 36 hours at 34 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 57.3%, average purity 86.5%
Embodiment 8:
1) take 5.0kg dulcitol and put in reactor, add dulcitol weight 10 times, concentration is 5% hydrobromic acid glacial acetic acid solution, simultaneously, hydrogen peroxide is added by the 15% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 1.0Mpa, keep temperature to 50 DEG C, continuously stirred 30 hours.
2) purified water adding dulcitol weight 2 times stirs 2.5 hours, supernatant is pumped after standing 24 hours, add dulcitol weight 2 times, concentration is 85% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 85% washing with alcohol by dulcitol weight 1 times, concentration, the solid collected is dried 48 hours at 30 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 54.0%, average purity 85.3%
Comparative example 1: with reference to the embodiment of the present invention 3, anaerobic agent, does not pass into hydrogen bromide gas
1) taking 5.0kg dulcitol and put in reactor, addition dulcitol weight 4 times, concentration are 45% hydrobromic acid glacial acetic acid solution, keep temperature to 45 DEG C, continuously stirred reaction 20 hours.
2) purified water adding dulcitol weight 10 times stirs 2 hours, supernatant is pumped after standing 12 hours, add dulcitol weight 0.1 times, concentration is 70% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70% washing with alcohol by dulcitol weight 1 times, concentration, the solid collected is dried 36 hours at 27 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 34.0%, average purity 64.5%
Comparative example 2: with reference to the embodiment of the present invention 3, anaerobic agent
1) taking 5.0kg dulcitol and put in reactor, addition dulcitol weight 4 times, concentration are 45% hydrobromic acid glacial acetic acid solution, after adding all reaction raw materials, closed reaction vessel, by hydrogen bromide gas, pressure remains between 0.6Mpa, keep temperature to 45 DEG C, continuously stirred 20 hours.
2) purified water adding dulcitol weight 10 times stirs 2 hours, supernatant is pumped after standing 12 hours, add dulcitol weight 0.1 times, concentration is 70% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70% washing with alcohol by dulcitol weight 1 times, concentration, the solid collected is dried 36 hours at 27 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 35.8%, average purity 66.7%
Comparative example 3: with reference to the embodiment of the present invention 3, do not pass into hydrogen bromide gas
1) taking 5.0kg dulcitol and put in reactor, addition dulcitol weight 4 times, concentration are 45% hydrobromic acid glacial acetic acid solution, meanwhile, add hydrogen peroxide by the 7% of dulcitol quality, keep temperature to 45 DEG C, continuously stirred 20 hours.
2) purified water adding dulcitol weight 10 times stirs 2 hours, supernatant is pumped after standing 12 hours, add dulcitol weight 0.1 times, concentration is 70% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70% washing with alcohol by dulcitol weight 1 times, concentration, the solid collected is dried 36 hours at 27 DEG C of temperature, obtains mitolactol.
Experimental result: mitolactol average yield 38.1%, average purity 68.3%
Process ration is tested:
Experimental technique: according to reaction conditions such as reaction pressure disclosed by the invention, reaction temperatures, prepares embodiment 1-8 sample；On embodiment preparation method basis, not oxidizer, do not pass into hydrogen bromide gas, prepare comparative example 1-4 sample respectively；Result is in Table 1.
Yield computational methods:
Method for detecting purity: method for detecting purity: according to high effective liquid chromatography for measuring, by external standard method with calculated by peak area, to obtain final product.Reference substance is laboratory self-control, and purity is 98.57%.
Table 1: dulcitol bromination reaction experimental result
Table 1 result shows: comparative example has deducted oxidant, do not passed into hydrogen bromide gas, and reaction result shows that the yield of so operation acquisition mitolactol reactant and purity are unsatisfactory.Midway adds together with adding in time starting, and its result has significant difference.
Test result indicate that: by response parameter provided by the invention, it is possible to obtain being substantially better than prior art and prepare the effect of gained mitolactol.
Although, above use generality explanation, detailed description of the invention and test, the present invention is described in detail, but on basis of the present invention, it is possible to it is made some modifications or improvements, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (10)
1. a preparation method for bromo hexanhexol, including bromination step, it is characterised in that: comprise the steps:
Take dulcitol and put in reaction vessel, addition dulcitol weight 1-10 times, concentration are the hydrobromic acid organic acid soln of 5-60%, simultaneously, oxidant is added by the 1-15% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.1-1.0Mpa, keep temperature to 30-55 DEG C, continuously stirred reaction 10-30 hour.
2. the method for claim 1, it is characterised in that described oxidant is perchloric acid, potassium hyperchlorate, potassium permanganate, sodium hypochlorite, hydrogen peroxide.
3. the method for claim 1, it is characterised in that described stirring reaction is 10-28 hour.
4. method as claimed in claim 3, it is characterised in that described stirring reaction is 20-25 hour.
5. the method for claim 1, it is characterised in that temperature during described reaction is 40-50 DEG C.
6. the method for claim 1, it is characterised in that described hydrobromic acid organic acid soln is hydrobromic acid glacial acetic acid solution or hydrobromic acid formic acid solution or hydrobromic acid propionic acid solution or hydrobromic acid butanoic acid solution.
7. the method for claim 1, it is characterised in that described hydrobromic acid organic acid soln concentration is 30-60%.
8. method as claimed in claim 7, it is characterised in that described hydrobromic acid organic acid soln is prepared by the following method and obtained: lower than, at-5 DEG C of temperature, hydrogen bromide gas being passed in organic acid, obtaining the hydrobromic acid organic acid soln that concentration is 30-60%.
9. method as claimed in claim 8, it is characterised in that described organic acid is glacial acetic acid, formic acid, propanoic acid or butanoic acid.
10. the method for claim 1, it is characterised in that comprise the steps:
1) take dulcitol and put in reaction vessel, addition dulcitol weight 1-10 times, concentration are the hydrobromic acid organic acid soln of 5-60%, simultaneously, oxidant is added by the 1-15% of dulcitol quality, closed reaction vessel, passes into hydrogen bromide gas, and pressure remains between 0.1-1.0Mpa, keep temperature to 30-55 DEG C, continuously stirred reaction 10-30 hour；
2) purified water adding dulcitol weight 1-10 times stirs 2-3 hour, supernatant is pumped after standing at least 12 hours, add dulcitol weight 0.1-2 times, concentration is 70-95% ethanol, stir, filtering, filtering residue purified water is rinsed to neutrality, is 70-95% washing with alcohol by dulcitol weight 1-5 times, concentration, the solid collected is dried 24-48 hour at 25-35 DEG C, obtains mitolactol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU195227B (en) * | 1986-02-28 | 1988-04-28 | Chinoin Gyogyszer Es Vegyeszet | New process for preparing 1,6-dibromo-dideoxy-d-mannitol and 1,6-dibromo-dideoxy-dulcitol |
| CN101070268A (en) * | 2007-06-14 | 2007-11-14 | 大连理工大学 | Process for preparing 2,7-2-bromofluorene |
| WO2012024368A2 (en) * | 2010-08-18 | 2012-02-23 | Del Mar Pharmaceuticals | Method of synthesis of substituted hexitols such as dianhydrogalactitol |
| CN103923039A (en) * | 2014-01-30 | 2014-07-16 | 天津中津药业股份有限公司 | Method for preparing dianhydrogalactitol |
-
2014
- 2014-12-30 CN CN201410839711.8A patent/CN105801364B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU195227B (en) * | 1986-02-28 | 1988-04-28 | Chinoin Gyogyszer Es Vegyeszet | New process for preparing 1,6-dibromo-dideoxy-d-mannitol and 1,6-dibromo-dideoxy-dulcitol |
| CN101070268A (en) * | 2007-06-14 | 2007-11-14 | 大连理工大学 | Process for preparing 2,7-2-bromofluorene |
| WO2012024368A2 (en) * | 2010-08-18 | 2012-02-23 | Del Mar Pharmaceuticals | Method of synthesis of substituted hexitols such as dianhydrogalactitol |
| CN103923039A (en) * | 2014-01-30 | 2014-07-16 | 天津中津药业股份有限公司 | Method for preparing dianhydrogalactitol |
Non-Patent Citations (2)
| Title |
|---|
| 刘铭勋等: "抗癌剂二溴卫茅醇的合成", 《江西医学院学报》 * |
| 龚年华: "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", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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