CN102807584B - A kind of preparation method of metabolic improver Butaphosphan - Google Patents
A kind of preparation method of metabolic improver Butaphosphan Download PDFInfo
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- CN102807584B CN102807584B CN201210290311.7A CN201210290311A CN102807584B CN 102807584 B CN102807584 B CN 102807584B CN 201210290311 A CN201210290311 A CN 201210290311A CN 102807584 B CN102807584 B CN 102807584B
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- Prior art keywords
- acetone
- phosphorous acid
- ortho phosphorous
- butyl amine
- hours
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YHLWPOLSPCBOPC-UHFFFAOYSA-O butyl(2-phosphopropan-2-yl)azanium Chemical compound CCCCNC(C)(C)[P+](O)=O YHLWPOLSPCBOPC-UHFFFAOYSA-O 0.000 title claims abstract 7
- 230000002503 metabolic effect Effects 0.000 title abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 86
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 13
- -1 amine salt Chemical class 0.000 claims description 12
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 150000002466 imines Chemical class 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- WCXWARPXYQCRPP-UHFFFAOYSA-N chembl1979022 Chemical compound CCCCNC(C)(C)P(O)=O WCXWARPXYQCRPP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 208000030852 Parasitic disease Diseases 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960002134 butafosfan Drugs 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 208000017580 chronic wasting disease Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000011720 vitamin B Chemical class 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
Abstract
The present invention relates to technical field of animal remedy preparation, provide a kind of preparation method of novel metabolic improver Butaphosphan, present method is with n-Butyl Amine 99, acetone, Hypophosporous Acid, 50 for raw material, and n-Butyl Amine 99 and condensation of acetone generate imines, obtains by Hypophosporous Acid, 50 reduction.Its step comprises: add in reactor by n-Butyl Amine 99, acetone, stirring at room temperature, drips the acetone soln of Hypophosporous Acid, 50, controls temperature of reaction and is no more than 40 DEG C.After back flow reaction terminates, cold filtration, centrifugal crude product.Crude product joins in crystallization kettle, adds acetone/methanol solution, and reflux, cooling, centrifugal, drying obtain finished product.The inventive method raw materials cost is low, step is short, operability is high, it is little to pollute, yield is high, and target compound total recovery is about 90%.
Description
Technical field
The invention belongs to technical field of animal remedy preparation, relate generally to a kind of preparation method of metabolic improver Butaphosphan.
Background technology
Butaphosphan is by German Bayer company through developing the aminopropan phosphorus compound gone on the market in approval in 1958 for many years, and chemical name is 1-(butyl is amino)-1-methylethyl]-phosphonic acids, English Butafosfan by name; (1-Butylamino-1-methyl-ethyl)-phosphinic acid; Molecular formula is C
7h
18nO
2p; Molecular weight is: 179.20
Structural formula is:
The object developing this compound is at that time the comprehensive de-synchronization state such as calcium magnesium Metabolic disorder, immunity of organisms decline, physical function disorder caused due to nutritional imbalance and various stress reaction to solve large animal.Through the market application of 20 years, not only find this compound and vitamins B
12mixed preparation can be good achieve the above object, and the animal body caused for various disease is weak, recover slowly also have good effect after being ill.Also can be used in the assisting therapy of parasitosis, transmissible disease and other chronic wasting diseases simultaneously.This compound is in more than 70 countries and regions listings such as Germany, France, Italy, Spain and the European Community at present.Bayer company also obtains Ministry of Agriculture's license listing in June, 2002 in China.
Also specifically do not report the document of Butaphosphan synthesis both at home and abroad, one section of document is only had to be general preparative methods (Kreutzkamp about alpha-substitution phosphoramidic acid series compound, 1967), namely replacing amine and Hypophosporous Acid, 50 with acetone, alkyl is raw material, one-step synthesis method target compound.The method is easy and simple to handle.But the concrete synthetic method of Butaphosphan is not mentioned in this article.Butaphosphan price prepared by prior art is very expensive, and the synthetic method therefore studying the high Butaphosphan of a kind of yield with low cost is significant.
Summary of the invention
The object of the invention is the deficiency for existing synthetic technology and provide that a kind of starting material are easy to get, the preparation method of Butaphosphan that the high and low pollution of operability, high yield, suitability for industrialized are produced.
The present invention adopts one-step synthesis method target compound, and synthetic route is as follows:
Preparation method of the present invention, step is as follows:
1) in reactor, add n-Butyl Amine 99, acetone, mix and blend, be then under agitation slowly added in said mixture by ortho phosphorous acid acetone soln, wherein, n-Butyl Amine 99, mol ratio between Hypophosporous Acid, 50 and acetone are 1:1 ~ 1.8:8 ~ 12.
2) above-mentioned reaction system reflux is reacted for more than 4 hours.
3) after reaction terminates, cool, separate out solid, filter and obtain solid.
4) gained solid adds the methyl alcohol of 5 ~ 7 times (W/V), heating for dissolving, then drip solid 1 ~ 2 times (W/V) acetone, dropwise, after solid all dissolves, cooling, separate out solid, through centrifugal, obtain its phosphorus of solid cloth.
Preferably, step is as follows:
1) in reactor, add n-Butyl Amine 99, acetone, mix and blend, be then under agitation slowly added in said mixture by ortho phosphorous acid acetone soln, wherein, n-Butyl Amine 99, mol ratio between Hypophosporous Acid, 50 and acetone are 1:1.5:10.
2) above-mentioned reaction system reflux 4 hours.
3) after reaction terminates, cool, separate out solid, filter and obtain solid.
4) gained solid adds the methyl alcohol of 6 times (W/V), heating for dissolving, then drip solid 1.5 times (W/V) acetone, dropwise, after solid all dissolves, cooling, separate out solid, through centrifugal, obtain its phosphorus of solid cloth.
Wherein, described ortho phosphorous acid acetone soln is the saturated solution under normal temperature, and the ortho phosphorous acid being generally 140-160kg is dissolved in 50 liters of acetone and obtains.
Within wherein said more than 4 hours, comprise 4 hours, 5 hours, 6 hours, preferably 4 hours.
Single stage method of the present invention obtains Butaphosphan.Avoid the generation of unstable group with imine moiety, technique simplifies more, and total recovery can reach about 90-95%, and production cost can be controlled in less than 200 yuan/kilogram.Improve the operability of reaction, product postprocessing is very convenient, namely obtains thick product, be easy to suitability for industrialized production after cold filtration.Gained Butaphosphan quality of finished product good, stability is high, and content can reach more than 98.9%.
Embodiment
By the following examples technical scheme is specifically described, but the present invention is not limited to embodiment:
Embodiment 1
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 300l, be separately dissolved in 50l acetone by 144kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 225kg after cooling in crystallization kettle, centrifugal, drying.
Embodiment 2
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 300l, be separately dissolved in 50l acetone by 155kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 230kg after cooling in crystallization kettle, centrifugal, drying.
Embodiment 3
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 300l, be separately dissolved in 50l acetone by 165kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 235kg after cooling in crystallization kettle, centrifugal, drying.
Embodiment 4
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 350l, be separately dissolved in 50l acetone by 144kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 230kg after cooling in crystallization kettle, centrifugal, drying.
Embodiment 5
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 350l, be separately dissolved in 50l acetone by 154kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 233kg after cooling in crystallization kettle, centrifugal, drying.
Embodiment 6
Dropped in reactor by 108kg n-Butyl Amine 99, add acetone 350l, be separately dissolved in 50l acetone by 164kg98% ortho phosphorous acid, be then added in the solution of n-Butyl Amine 99 by ortho phosphorous acid acetone soln, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out.After being refluxed 4 hours by system heating in water bath, terminate reaction.System is put into cooling tank, placement of spending the night, product is separated out, and filters, centrifugally obtains crude product, then with the methanol acetone mixed system recrystallization by 4 times amount, is incubated 1 hour, obtains product 238kg after cooling in crystallization kettle, centrifugal, drying.
Claims (5)
1. a preparation method for Butaphosphan, is characterized in that, step is as follows:
1) in reactor, add n-Butyl Amine 99, acetone, mix and blend, be then under agitation slowly added in said mixture by ortho phosphorous acid acetone soln, wherein, n-Butyl Amine 99, mol ratio between Hypophosporous Acid, 50 and acetone are 1:1.5:10,
2) above-mentioned reaction system reflux 4 hours,
3) after reaction terminates, cool, separate out solid, filter and obtain solid,
4) gained solid adds the methyl alcohol of 6 times, heating for dissolving, then drips the acetone of solid 1.5 times, dropwises, and after solid all dissolves, cooling, separates out solid, through centrifugal, obtain its phosphorus of solid cloth.
2. a preparation method for Butaphosphan, is characterized in that, step is as follows:
108kg n-Butyl Amine 99 is dropped in reactor, add acetone 300L, separately 144kg 98% ortho phosphorous acid is dissolved in 50L acetone, then ortho phosphorous acid acetone soln is added in the solution of n-Butyl Amine 99, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out, and after being refluxed 4 hours by system heating in water bath, terminates reaction, system is put into cooling tank, spend the night placement, product is separated out, and filters, centrifugally obtain crude product, then use the methanol acetone mixed system recrystallization of 4 times amount, be incubated 1 hour, cool in crystallization kettle, obtain product 225kg after centrifugal, drying.
3. a preparation method for Butaphosphan, is characterized in that, step is as follows:
108kg n-Butyl Amine 99 is dropped in reactor, add acetone 300L, separately 155kg 98% ortho phosphorous acid is dissolved in 50L acetone, then ortho phosphorous acid acetone soln is added in the solution of n-Butyl Amine 99, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out, and after being refluxed 4 hours by system heating in water bath, terminates reaction, system is put into cooling tank, spend the night placement, product is separated out, and filters, centrifugally obtain crude product, then use the methanol acetone mixed system recrystallization of 4 times amount, be incubated 1 hour, cool in crystallization kettle, obtain product 230kg after centrifugal, drying.
4. a preparation method for Butaphosphan, is characterized in that, step is as follows:
108kg n-Butyl Amine 99 is dropped in reactor, add acetone 300L, separately 165kg98% ortho phosphorous acid is dissolved in 50L acetone, then ortho phosphorous acid acetone soln is added in the solution of n-Butyl Amine 99, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out, and after being refluxed 4 hours by system heating in water bath, terminates reaction, system is put into cooling tank, spend the night placement, product is separated out, and filters, centrifugally obtain crude product, then with the methanol acetone mixed system recrystallization of 4 times amount, be incubated 1 hour, after cooling in crystallization kettle, centrifugal, drying, obtain product 235kg.
5. a preparation method for Butaphosphan, is characterized in that, step is as follows:
108kg n-Butyl Amine 99 is dropped in reactor, add acetone 350L, separately 144kg98% ortho phosphorous acid is dissolved in 50L acetone, then ortho phosphorous acid acetone soln is added in the solution of n-Butyl Amine 99, stir 3 hours, the amine salt that system has ortho phosphorous acid is separated out, and after being refluxed 4 hours by system heating in water bath, terminates reaction, system is put into cooling tank, spend the night placement, product is separated out, and filters, centrifugally obtain crude product, then use the methanol acetone mixed system recrystallization of 4 times amount, be incubated 1 hour, cool in crystallization kettle, obtain product 230kg after centrifugal, drying.
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| CN101914112A (en) * | 2010-08-25 | 2010-12-15 | 杭州福斯特药业有限公司 | Method for preparing butafosfan |
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