CN1193034C - Process for preparing ferriporphyrin sodium salt - Google Patents
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- CN1193034C CN1193034C CNB011322039A CN01132203A CN1193034C CN 1193034 C CN1193034 C CN 1193034C CN B011322039 A CNB011322039 A CN B011322039A CN 01132203 A CN01132203 A CN 01132203A CN 1193034 C CN1193034 C CN 1193034C
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- sodium salt
- ferriporphyrin
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- sodium
- iron
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- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 iron porphyrin sodium salt Chemical compound 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- GPRXGEKBQVXWAQ-UHFFFAOYSA-L disodium;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethyl-22,23-dihydroporphyrin-2-yl]propanoate Chemical compound [Na+].[Na+].N1C(C=C2C(=C(C)C(=CC=3C(C)=C(CCC([O-])=O)C(N=3)=C3)N2)C=C)=C(C)C(C=C)=C1C=C1C(C)=C(CCC([O-])=O)C3=N1 GPRXGEKBQVXWAQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- OGMQNMUHVLRDRT-UHFFFAOYSA-J disodium;3-[20-(carboxylatomethyl)-18-(dioxidomethylidene)-8-ethenyl-13-ethyl-3,7,12,17-tetramethyl-2,3-dihydroporphyrin-23-id-2-yl]propanoate;hydron;iron(2+) Chemical compound [H+].[Na+].[Na+].[Fe+2].C1=C([N-]2)C(CC)=C(C)C2=CC(C(=C2C)C=C)=NC2=CC(C(C2CCC([O-])=O)C)=NC2=C(CC([O-])=O)C2=NC1=C(C)C2=C([O-])[O-] OGMQNMUHVLRDRT-UHFFFAOYSA-J 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005899 aromatization reaction Methods 0.000 claims description 2
- 229940125773 compound 10 Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 2
- AWJZMUKFUBQPRP-UHFFFAOYSA-N quinoline;sodium Chemical compound [Na].[Na].N1=CC=CC2=CC=CC=C21 AWJZMUKFUBQPRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 abstract description 6
- 229950003776 protoporphyrin Drugs 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229930002875 chlorophyll Natural products 0.000 abstract description 3
- 235000019804 chlorophyll Nutrition 0.000 abstract description 3
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 abstract description 3
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 abstract 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 208000007502 anemia Diseases 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010836 blood and blood product Substances 0.000 description 2
- 229940125691 blood product Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention discloses a method for preparing iron porphyrin sodium salt from chlorophyll iron sodium salt. The method is characterized in that deferrization is carried out to chlorophyll iron sodium salt through diluted sulfuric acid; then, aromatizing reaction is carried out for removing isoamyl rings for forming 1, 3, 5, 8-tetramethyl-2-vinyl-4-ethyl-6, 7 sodium dipropionate porphyrin in a large pi bonding structure; protoporphyrin generates complexation with iron ions for generating iron porphyrin; than, water-soluble sodium salt is prepared. The present invention has the advantages of simple and reliable production technology, low cost and high yield and can be used for industrialization production with certain scales.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound, relate in particular to a kind of preparation method of ferriporphyrin sodium salt.
Background technology
1996, we invented the method for producing iron porphyrin from chlorophyll, and 1998, we invented the production technique of metalloporphyrin again.In order to satisfy the needs of medicine industry, we have developed the industrialized preparing process of ferriporphyrin sodium salt again with great concentration.Ferriporphyrin sodium salt is the water-soluble sodium salt of iron porphyrin, it be generally acknowledge in the world prevent and treat the most effective medicine of hypoferric anemia, because of its iron-holder height (9.03%), and with its molecular form directly be absorbed by the body, the utilization ratio height, absorb fast, can reach the function of enriching blood fast, thereby be considered to substitute the update medicine that traditional in the market inorganic salts is mended chalybeate.In addition, also can be used for foodstuff additive, add the functional foodstuff of making the treatment hypoferric anemia in beverage, cake, candy, biscuit, the chocolate etc.
The ferriporphyrin sodium salt compound is not all seen the report that suitability for industrialized production is arranged at home and abroad, thereby does not have commodity yet, and some scholars, expert attempt to be unrealized with the synthetic method both at home and abroad, but because of processing condition require harshly, complicated, cost is too high and can not implement.Also attempt from the blood of animal, to extract, as ox blood, pig blood, sheep blood etc., but also preserve and be subjected to strict restriction because of the transportation of blood products, the extraction and separation process complexity, cost consumption is too big, thereby does not form scale production, and its purity also is restricted, over more than 100 year, domestic and international scientist's way that never achieves a solution.
Summary of the invention
Purpose of the present invention is exactly for a kind of preparation method with ferriporphyrin sodium salt of the hypoferric anemia of preventing and treating is provided, and this method technology is simple, cost is lower.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of ferriporphyrin sodium salt, and the structural formula of this ferriporphyrin sodium salt is as follows:
It is characterized in that the preparation method of described ferriporphyrin sodium salt comprises following processing step: the first step with sodium-iron-chlorophyllin dilute sulphuric acid deferrization, generates CHLOROPHYLLINE; Second step, with the CHLOROPHYLLINE that obtains in the ethylene glycol solution of 20～50% (weight) potassium hydroxide, aromatization under reflux temperature, generate 1,3,5,8-tetramethyl--2-vinyl-4-ethyl-6,7-dipropionic acid porphyrin generates sodium salt with this porphyrin and sodium hydroxide effect again, and centrifugal spray drying makes protoporphyrin disodium salt; The 3rd step, the prophyll quinoline disodium salt that makes and ferrous ion compound 10～70 ℃ of following complexings 3～5 hours, are neutralized to PH=4 with protonic acid again and separate out crystallization, filter, washing, add sodium hydroxide and generate ferriporphyrin sodium salt solution, centrifugal spray drying makes the ferriporphyrin sodium salt product.
Described CHLOROPHYLLINE is reacted in the ethylene glycol solution of 30～40% (weight) potassium hydroxide, and the ratio of CHLOROPHYLLINE and this solution is 1: 4～6 (weight).
Described reflux temperature is 190～210 ℃, and the reaction times is 2～24 hours.
Described ferrous ion compound is selected from a kind of in ferrous sulfate, the iron protochloride.
Described protonic acid is selected from a kind of in sulfuric acid, the hydrochloric acid.
Advantage of the present invention is tangible: technology is simple, the yield height, and the chemical structure of purpose compound is consistent substantially with protoheme, and iron-holder height, ferro element account for 9% of ferriporphyrin sodium salt, exceed 6 times of pig blood products.The present invention is raw material with the sodium-iron-chlorophyllin, and the production technique Nonpoisonous, non-environmental-pollution produces, and quality product is safe and reliable.
Ferriporphyrin sodium salt shows that through the bioavailability evaluation it is a good benefit chalybeate of preventing and treating hypoferric anemia.Prove that through toxicity test to mice lavage, observe a week with the dosage of 10g/Kg, not seeing has the acute poisoning symptom and the phenomena of mortality, belong to nontoxic level.Simultaneously negative through its result of Salmonella reversion test, therefore, the method for the ferriporphyrin sodium salt of producing from sodium-iron-chlorophyllin for the suitability for industrialized production of the medicine of effectively preventing and treating hypoferric anemia, has been opened up an approach with very high realistic meaning and practical value.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of ferriporphyrin sodium salt, the structural formula of this ferriporphyrin sodium salt is as follows:
The preparation method of described ferriporphyrin sodium salt comprises following technological process:
1. the sulfuric acid that in the deferrization still of band stirring and thermometer, adds 57% (weight), under agitation add the 2Kg sodium-iron-chlorophyllin in batches, at ambient temperature, reacted 2～3 hours, after finishing, reaction is neutralized to PH=7 with sodium hydroxide, washing, filtration, drying obtain 1800 gram deferrization CHLOROPHYLLINE, and yield is 90%.
2. in the reactor of band stirring, thermometer and air reflux exchanger, add the ethylene glycol of 2200ml and 8 kilograms potassium hydroxide, under agitation slowly add 2Kg deferrization CHLOROPHYLLINE, being warming up to temperature of reaction gradually is 198～205 ℃, reaction is 3 hours under refluxing, and reaction solution is reddened gradually by green, after reaction is finished, be cooled to room temperature, be neutralized to PH=4 with dilute sulphuric acid then, precipitation, washing, acquisition protoporphyrin add 240 gram NaOH and make it become protoporphyrin disodium salt.Wherein, described protoporphyrin disodium salt content is about 2Kg, and yield is 98%.
3. in above-mentioned solution, add sulfuric acid and make into the protoporphyrin dicarboxylic acid, in the complexing still, add 1500 gram ferrous sulfate and the complexings of protoporphyrin dicarboxylic acid then, under agitation controlled temperature is 70 ℃, reacted 3～5 hours, and made into PH=4 after reaction is finished and separate out crystallization, filter washing, add 240 gram sodium hydroxide and make into sodium salt, carry out centrifugal drying with spray-drier, must be as the ferriporphyrin sodium salt of above-mentioned structural formula, yield is 95%.
Embodiment 2
Repeat the process of embodiment 1, but do not adopt the dilute sulphuric acid neutralization in the step 2, separate out crystallization, filter, wash, add 240 gram sodium hydroxide and make into protoporphyrin disodium salt but after reaction is finished, be neutralized to PH=4 with hydrochloric acid, centrifugal spray drying gets the finished product protoporphyrin disodium salt.Add hydrochloric acid and make into protoporphyrin, add iron protochloride 1000 grams then, temperature control to 70 ℃ under agitation, time is 5 hours, make PH=4 after complex reaction is finished, separate out crystallization, filter washing, add sodium hydroxide and form sodium salt, dewatering with centrifugal spray-dryer forms ferriporphyrin sodium salt as embodiment 1 structural formula.
Embodiment 3
Repeat the process of embodiment 1, but in the process of step 3, described protoporphyrin dicarboxylic acid and ionic metal salt such as water soluble salt complexings such as zinc, copper, nickel, chromium, cobalt, tin, can make the corresponding metal porphyrin sodium salt as embodiment 1 structural formula.
Claims (5)
1. the preparation method of a ferriporphyrin sodium salt, the structural formula of this ferriporphyrin sodium salt is as follows:
It is characterized in that the preparation method of described ferriporphyrin sodium salt comprises following processing step: the first step with sodium-iron-chlorophyllin dilute sulphuric acid deferrization, generates CHLOROPHYLLINE; Second step, is in the ethylene glycol solution of 20～50% potassium hydroxide with the CHLOROPHYLLINE that obtains in weight ratio, aromatization under reflux temperature, generate 1,3,5,8-tetramethyl--2-vinyl-4-ethyl-6,7-dipropionic acid porphyrin generates sodium salt with this porphyrin and sodium hydroxide effect again, and centrifugal spray drying makes protoporphyrin disodium salt; The 3rd step, the prophyll quinoline disodium salt that makes and ferrous ion compound 10～70 ℃ of following complexings 3～5 hours, are neutralized to PH=4 with protonic acid again and separate out crystallization, filter, washing, add sodium hydroxide and generate ferriporphyrin sodium salt solution, centrifugal spray drying makes the ferriporphyrin sodium salt product.
2. preparation method according to claim 1 is characterized in that, described CHLOROPHYLLINE is reacted in weight ratio is the ethylene glycol solution of 30～40% potassium hydroxide, and the part by weight of CHLOROPHYLLINE and this solution is 1: 4～6.
3. preparation method according to claim 1 and 2 is characterized in that, described reflux temperature is 190～210 ℃, and the reaction times is 2～24 hours.
4. preparation method according to claim 1 is characterized in that, described ferrous ion compound is selected from a kind of in ferrous sulfate, the iron protochloride.
5. preparation method according to claim 1 is characterized in that, described protonic acid is selected from a kind of in sulfuric acid, the hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011322039A CN1193034C (en) | 2001-11-14 | 2001-11-14 | Process for preparing ferriporphyrin sodium salt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011322039A CN1193034C (en) | 2001-11-14 | 2001-11-14 | Process for preparing ferriporphyrin sodium salt |
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|---|---|
| CN1418885A CN1418885A (en) | 2003-05-21 |
| CN1193034C true CN1193034C (en) | 2005-03-16 |
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| CNB011322039A Expired - Fee Related CN1193034C (en) | 2001-11-14 | 2001-11-14 | Process for preparing ferriporphyrin sodium salt |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2914302A1 (en) * | 2007-03-30 | 2008-10-03 | Sanofi Pasteur Sa | PROCESS FOR PREPARING PORPHYRIN DERIVATIVES, SUCH AS PROTOPORPHYRIN (IX) AND INTERMEDIATE SYNTHESIS |
| CN102617581B (en) * | 2012-03-15 | 2013-11-06 | 中国药科大学 | 58Fe hemin, its preparation and its application in pharmacokinetic research |
| CN102967649B (en) * | 2012-05-24 | 2015-03-04 | 新疆科丽生物技术有限公司 | Application of inductively coupled plasma mass spectrometry in drug testing of hemin |
| CN103193782B (en) * | 2012-05-28 | 2015-10-28 | 复旦大学附属金山医院 | Photosensitizers CHLOROPHYLLINE sodium salt derivative and its production and use |
| KR101894575B1 (en) * | 2017-01-03 | 2018-09-04 | 주식회사 인트론바이오테크놀로지 | The chemical production method of heme-iron which is not derived from porcine blood |
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