CN100393734C - Process for synthesizing tetra-substituted amino macrocyclic metal complex - Google Patents
Process for synthesizing tetra-substituted amino macrocyclic metal complex Download PDFInfo
- Publication number
- CN100393734C CN100393734C CNB2006100507204A CN200610050720A CN100393734C CN 100393734 C CN100393734 C CN 100393734C CN B2006100507204 A CNB2006100507204 A CN B2006100507204A CN 200610050720 A CN200610050720 A CN 200610050720A CN 100393734 C CN100393734 C CN 100393734C
- Authority
- CN
- China
- Prior art keywords
- diamido
- tetra
- substituted amino
- reaction
- diacid
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a method for synthesizing a tetramino-macrocyclic complex, which uses amino acid as a raw material; under the condition that an organic solvent, alkali or nitrogen exists, the amino acid reacts with diacid chloride to obtain diamido diacid, and then the diamido diacid reacts with a chlorinating agent to obtain diamido diacid chloride; finally, under the condition that the organic solvent, the alkali or the nitrogen exists, metallic ions are used as a template agent, and the metal complex of a tetramino-macrocyclic ligand is obtained through the one-step reaction of the diamido diacid chloride, diamine or the derivatives thereof and the metallic ions. The synthesis technology of the present invention has the advantages of simple process, high reaction selectivity, high reaction yield and easy industrialization.
Description
Technical field
The present invention relates to the preparation of tetra-substituted amino macrocyclic ligand metal title complex, a kind of synthetic method of tetra-substituted amino macrocyclic ligand metal title complex is provided especially.
Background technology
Tetra-substituted amino macrocyclic ligand metal title complex can be used as oxide catalyst, " green " oxygenants such as this catalyzer can activating hydrogen peroxide in acid, neutrality and alkaline aqueous solution, oxygen are applied to many fields such as textile bleaching, pulp bleaching, treatment of dyeing wastewater and organic synthesis.WO98/03263, US5298618, US6127536 relates to the various synthetic methods of tetra-substituted amino macrocyclic part in the patent documentation of US6384279 and US5853428.Wherein, method and the most approaching title complex of the present invention that provides with US6051704:
5,6-Benzo-3,8,11,13-tetraoxo-2,2,9,9,12,12-hexmethyl-1,4,7, its synthetic route of 10-tetraazacyclotridecane is as follows:
This synthetic route is complicated, is divided into four steps, as shown above.Wherein, obtain the reaction of D by chlorination, reagent such as used phosphorus trichloride, phosphorus pentachloride and sulfur oxychloride are big for environment pollution; Cyclisation obtains the reaction of E, need carry out in very rare solution, and solvent consumption is very big, and reaction yield only is 30%; The reaction needed that generates F is used n-Butyl Lithium reagent, severe reaction conditions, and the cost height makes and realizes that there is more difficulty in industrialization.
Summary of the invention
The object of the present invention is to provide a kind of improved tetra-substituted amino macrocyclic part and metal complexes synthetic method thereof.
It is synthetic that principle of the present invention was based on for three steps, and its reaction formula is:
(1) alpha amino acid+diacid chloride → diamido diacid
(2) diamido diacid+two (trichloromethyl) carbonic ether → diamido diacid chloride
(3) diamido diacid chloride+1,8-naphthylene diamine → tetra-substituted amino macrocyclic metal complex
The synthetic method of tetra-substituted amino macrocyclic title complex of the present invention is characterized in that, it may further comprise the steps:
1, the diamido diacid is synthetic
Under the condition that organic solvent, alkali and nitrogen exist, obtain the diamido diacid by amino acid and diacid chloride reaction, wherein the add-on of solvent is raw material amino acid/11～10 times weight (preferred 3～7 times), the add-on of alkali is a raw material amino acid whose 1～4 times (wt) (preferred 1.5～2 times), temperature of reaction can be-20 ℃～40 ℃ (preferred-1 () ℃～10 ℃), reacted 1～8 hour, and came the purified reaction mixture by washing, alkali cleaning, pickling then;
2, the diamido diacid chloride is synthetic
By the diamido diacid that obtains is raw material, obtain the diamido diacid chloride with chlorination reagent two (trichloromethyl) carbonate reaction, the consumption of two (trichloromethyl) carbonic ether is 1～5 times of weight (preferred 1～3 times) of raw material diamido diacid, temperature of reaction can be between 40 ℃～80 ℃, reaction times is 2～4 hours, with the method for underpressure distillation, purification diamido diacid chloride from reaction mixture;
3, tetra-substituted amino macrocyclic ligand metal title complex is synthetic
Diamido diethyl acyl chlorides with acquisition is a raw material, under the condition that organic solvent, alkali and nitrogen exist, obtain tetra-substituted amino macrocyclic ligand metal title complex with diamines, metal ion single step reaction, the add-on of organic solvent is 2～8 times of weight of diamido diethyl acyl chlorides (preferred 2～3 times), the add-on of alkali is 2～8 times (wt) (preferred 3～5 times) of diamido diethyl acyl chlorides, and metal ion is a transition metal ion.
The said amino acid of step 1 of the present invention is glycine, 2-methyl aminoacetic acid or 2,2-dimethylamino acetate;
The used diacid chloride of step 1 of the present invention is selected from oxalyl chloride, malonyl chloride, 2-methyl malonyl chloride, 2,2-dimethyl propylene diacid chloride a kind of;
The used solvent of step 1 of the present invention is acetone, tetrahydrofuran (THF), benzene or toluene compound, is preferably acetone;
The said reaction alkali of step 1 of the present invention is sodium hydroxide, potassium hydroxide mineral alkali, or a kind of in the diethylamine, triethylamine, sodium-acetate organic bases.
The said range of reaction temperature of step 1 of the present invention is preferably-10 ℃～10 ℃.
The said chlorination reagent of step 2 of the present invention also has phosphorus trichloride, phosphorus pentachloride or sulfur oxychloride except that preferred two (trichloromethyl) carbonic ether.
The said diamines of step 3 of the present invention is quadrol, O-Phenylene Diamine and derivative thereof, 1,8-naphthylene diamine and derivative thereof;
The said solvent of step 3 of the present invention is acetone, tetrahydrofuran (THF), trichloromethane or tetracol phenixin;
The said transition metal ion of step 3 of the present invention, chosen from Fe ion, chromium ion, cupric ion, cobalt ion, mn ion, zine ion or nickel ion.Be preferably iron ion, cupric ion, cobalt ion and mn ion.
Compare with existing patented technology, the present invention is a template with the metal ion under the condition that organic solvent, alkali and nitrogen etc. exist, and diamido diacid chloride, diamines and metal ion single step reaction obtain tetra-substituted amino macrocyclic ligand metal title complex.Its chlorination reagent adopts two (trichloromethyl) carbonic ether, has reduced the pollution to environment, has improved reaction efficiency; The two-step reaction that generates E, F product is merged into a step, need not carry out in very rare solution, the solvent usage quantity significantly reduces, and can use common organic bases, and reaction yield reaches 75.8%.Present method technology is simple, and selectivity and yield are higher, realizes industrialization easily.
Embodiment
Embodiment 1:
In the there-necked flask of 125ml, add 40ml acetone solvent, 6ml oxalyl chloride and 12ml triethylamine, pass to nitrogen protection.In two hours, add 10g glycine raw material in batches, cool off with ice bath.Behind the reaction 4h, filter, obtain solid.This solid is put into frozen water, stir for some time, filter, filter cake is dissolved in the sodium hydroxide solution, removes insolubles, separates out product behind the adding hydrochloric acid, use the 3*100ml distilled water wash at last, obtain 10.9g oxamido-oxalic acid intermediate product I, yield 80.2%;
Then, adding 10g oxamido-oxalic acid intermediate product I in the there-necked flask of 125ml is raw material and 35g two (trichloromethyl) carbonic ether, and heating is stirred, and refluxes 3 hours.After reaction finished, cooling added 50ml toluene, distilled in rotatory evaporator, and with the washing of 3*20ml trichloromethane, oven dry obtains 10.8g oxamido-diethyl acyl chlorides intermediate product II again, and yield is 91.5%;
Then, adding 2.5g oxamido-diethyl acyl chlorides intermediate product II in the there-necked flask of 250ml is raw material, 2g iron trichloride and 7.5ml acetone solvent, passes to nitrogen protection, and cools off with ice bath.1.8gl, 8-naphthylene diamine, 7ml acetone and 10ml triethylamine are put into constant pressure funnel, are added drop-wise in the reaction flask in one hour, and dropping was reacted 6 hours after finishing.After reaction finishes, filter, use the 3*20ml washing with alcohol, handle with aqueous sodium hydroxide solution, obtain the result product III of 3.3g tetra-substituted amino macrocyclic part Fe title complex, yield is 75.8%.
Embodiment 2:
According to the identical synthesis step of embodiment 1, in the there-necked flask of 125ml, add 40ml acetone, 7ml malonyl chloride and 12ml triethylamine, logical nitrogen protection.In two hours, add the 10g glycine in batches, obtain the amino oxalic acid intermediate product of 11.9g malonyl-I, yield 82.1%;
Add amino oxalic acid of 10g malonyl-and 33g two (trichloromethyl) carbonic ether in the there-necked flask of 125ml, oven dry obtains the amino diethyl acyl chlorides of 10.6g malonyl-intermediate product II, and yield is 90.6%;
Add the amino diethyl acyl chlorides of 2.5g malonyl-, 1.7g cupric chloride and 7.5ml acetone in the there-necked flask of 250ml, logical nitrogen protection is cooled off with ice bath.1.1g O-Phenylene Diamine, 7ml acetone and 10ml triethylamine are put into constant pressure funnel, finally obtain the result product III of 2.9g tetra-substituted amino macrocyclic part Cu title complex, yield is 78.4%.
Embodiment 3～7:
According to each identical synthesis step of embodiment 1, wherein raw material, reaction mass and auxiliary material, reaction conditions such as tabular:
| Embodiment | 3 | 4 | 5 | 6 | 7 | |
| 1: 1 part of raw material (wt) weight part | Glycine | The 2-methyl aminoacetic acid | 2,2-dimethylamino acetate | 2-methyl-2-aminobutyric acid | 2-ethyl-2-aminobutyric acid | |
| Reaction mass is an amount of | Oxalyl chloride | Malonyl chloride | 2,2-dimethyl propylene diacid chloride | 2,2-diethyl malonyl chloride | 2,2-difluoro malonyl chloride | |
| The solvent adding amount weight part | Acetone 1 | Tetrahydrofuran (THF) 3 | Benzene 5 | Toluene 7 | Acetone 9 | |
| Alkali add-on weight part | Diethylamine 1 | Triethylamine 1.5 | Sodium-acetate 2 | Sodium hydroxide 3 | Potassium hydroxide 4 | |
| Temperature of reaction ℃ | -20 | -10 | 10 | 20 | 40 | |
| Reaction times hour | 4 | 5 | 6 | 7 | 8 | |
| Step 1 intermediate product I | The oxamido-oxalic acid | Malonyl-amino-two (2-methyl) acetate | [2 ', 2 '-dimethyl propylene diamido]-two (2, the 2-dimethyl) acetate | [2 ', 2 '-diethyl malonyl-amino]-two (2-methyl-2-ethyl) acetate | [2 ', 2 '-difluoro malonyl-amino]-two (2, the 2-diethyl) acetate | |
| 2: 1 part of raw material (wt) weight part | The oxamido-oxalic acid | Malonyl-amino-two (2-methyl) acetate | [2 ', 2 '-dimethyl propylene diamido]-two (2, the 2-dimethyl) acetate | [2 ', 2 ' diethyl malonyl-amino]-two (2-methyl-2-ethyl) acetate | [2 ', 2 '-difluoro malonyl-amino]-two (2, the 2-diethyl) acetate | |
| Chlorination reagent | Two (trichloromethyl) carbonic ether | Two (trichloromethyl) carbonic ether | Two (trichloromethyl) carbonic ether | Two (trichloromethyl) carbonic ether | Two (trichloromethyl) carbonic ether | |
| Two (trichloromethyl) carbonic ether weight part | 1 | 2 | 3 | 4 | 5 | |
| Temperature of reaction ℃ | 40～80℃ | 40℃～80℃ | 40℃～80℃ | 40℃～80℃ | 40℃～80℃ | |
| Reaction times hour | 2 | 3 | 3 | 4 | 2 | |
| Step 2 intermediate product II | Diamido diethyl acyl chlorides | Malonyl-amino-two (2-methyl) Acetyl Chloride 98Min. | [2 ', 2 '-dimethyl propylene diamido]-two (2, the 2-dimethyl) Acetyl Chloride 98Min. | [2 ', 2 '-diethyl malonyl-amino]-two (2-methyl-2-ethyl) Acetyl Chloride 98Min. | [2 ', 2 '-difluoro malonyl-amino]-two (2, the 2-diethyl) Acetyl Chloride 98Min. | |
| 3: 1 part of raw material (wt) weight | Diamido diethyl acyl chlorides | Malonyl-amino-two (2-methyl) Acetyl Chloride 98Min. | [2 ', 2 '-dimethyl propylene diamido]-two (2, the 2-dimethyl) Acetyl Chloride 98Min. | [2 ', 2 '-diethyl malonyl-amino]-two (2-methyl-2-ethyl) Acetyl Chloride 98Min. | [2 ', 2 '-difluoro malonyl-amino]-two (2, the 2-diethyl) Acetyl Chloride 98Min. |
| Reaction mass is an amount of | 1, the 8-naphthylene diamine | O-Phenylene Diamine | Quadrol | 1, the 8-naphthylene diamine | O-Phenylene Diamine |
| The organic solvent weight part | Acetone 2 | Tetrahydrofuran (THF) 3 | Trichloromethane 4 | Tetracol phenixin 5 | Acetone 8 |
| Alkali | 2 | 3 | 4 | 5 | 8 |
| Shielding gas | Nitrogen | Nitrogen | Nitrogen | Nitrogen | Nitrogen |
| Transition metal ion | Iron ion | Cupric ion | Cobalt ion | Mn ion | Zine ion |
| Result product III | The tetra-substituted amino macrocyclic iron complex | The tetra-substituted amino macrocyclic copper complex | The tetra-substituted amino macrocyclic cobalt complex | The tetra-substituted amino macrocyclic manganese complex | The tetra-substituted amino macrocyclic Zn complex |
Embodiment shown in the table is an experiment part.In the present invention program's scope, good efficiency of pcr product and effect are arranged all in the preferable range particularly.
Claims (9)
1. the synthetic method of a tetra-substituted amino macrocyclic ligand metal title complex is characterized in that it may further comprise the steps:
1), the diamido diacid is synthetic
Under the condition that organic solvent, alkali and nitrogen exist, obtain the diamido diacid by amino acid and diacid chloride reaction, wherein the add-on of solvent is raw material amino acid/11～10 times weight, the add-on of alkali is amino acid whose 1～4 times an of raw material, temperature of reaction is at-20 ℃～40 ℃, reacted 4～8 hours, and came the purified reaction mixture by washing, alkali cleaning, pickling then;
2), the diamido diacid chloride is synthetic
By the diamido diacid that obtains is raw material, obtain the diamido diacid chloride with the chlorination reagent reaction, the consumption of chlorination reagent is 1～5 times of weight of raw material diamido diacid, temperature of reaction is between 40 ℃～80 ℃, reaction times is 2～4 hours, with the method for underpressure distillation, purification diamido diacid chloride from reaction mixture; Wherein chlorination reagent is two (trichloromethyl) carbonic ether, phosphorus trichloride, phosphorus pentachloride or sulfur oxychloride;
3), tetra-substituted amino macrocyclic ligand metal title complex is synthetic
Diamido diacid chloride with acquisition is a raw material, under the condition that organic solvent, alkali and nitrogen exist, obtain tetra-substituted amino macrocyclic ligand metal title complex with diamines, metal ion single step reaction, the add-on of organic solvent is 2～8 times of weight of diamido diacid chloride, the add-on of alkali is 2～8 times of diamido diacid chloride, and metal ion is a transition metal ion.
2. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said amino acid of step 1) is glycine, 2-methyl aminoacetic acid or 2,2-dimethylamino acetate.
3. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the used diacid chloride of step 1) is selected from oxalyl chloride, malonyl chloride, 2-methyl malonyl chloride, 2,2-dimethyl propylene diacid chloride a kind of.
4. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the used solvent of step 1) is acetone, tetrahydrofuran (THF), benzene.
5. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said reaction alkali of step 1) is sodium hydroxide, potassium hydroxide mineral alkali, or a kind of in the diethylamine, triethylamine, sodium-acetate organic bases.
6. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said range of reaction temperature of step 1) is-10 ℃～10 ℃.
7. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said diamines of step 3) is quadrol, O-Phenylene Diamine, 1, the 8-naphthylene diamine.
8. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said solvent of step 3) is acetone, tetrahydrofuran (THF), trichloromethane or tetracol phenixin.
9. the synthetic method of tetra-substituted amino macrocyclic ligand metal title complex according to claim 1 is characterized in that the said transition metal ion of step 3) is iron ion, chromium ion, cupric ion, cobalt ion, mn ion, zine ion or nickel ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100507204A CN100393734C (en) | 2006-05-10 | 2006-05-10 | Process for synthesizing tetra-substituted amino macrocyclic metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100507204A CN100393734C (en) | 2006-05-10 | 2006-05-10 | Process for synthesizing tetra-substituted amino macrocyclic metal complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844128A CN1844128A (en) | 2006-10-11 |
| CN100393734C true CN100393734C (en) | 2008-06-11 |
Family
ID=37063099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100507204A Expired - Fee Related CN100393734C (en) | 2006-05-10 | 2006-05-10 | Process for synthesizing tetra-substituted amino macrocyclic metal complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100393734C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103174010A (en) * | 2011-11-24 | 2013-06-26 | 东华大学 | Application of macrocyclic polyamine bridged metal complex to low-temperature scouring and bleaching auxiliary for textiles |
| CN106083843B (en) * | 2016-05-10 | 2019-02-19 | 北京服装学院 | Macrocyclic amide metal complex and its preparation method and application |
| CN106082419B (en) * | 2016-05-10 | 2019-05-31 | 北京服装学院 | Method and application of the degradation of macrocyclic amide metal complex containing organic pollutant wastewater |
| CN106902633B (en) * | 2017-03-13 | 2020-06-16 | 华北电力大学（保定） | Bionic enzyme absorbent for removing element mercury in flue gas and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230980A (en) * | 1996-07-22 | 1999-10-06 | 卡内基梅隆大学 | Metal ligand containing bleaching compositions |
| US6051704A (en) * | 1996-07-22 | 2000-04-18 | Carnegie Mellon University | Synthesis of macrocyclic tetraamido-N ligands |
-
2006
- 2006-05-10 CN CNB2006100507204A patent/CN100393734C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230980A (en) * | 1996-07-22 | 1999-10-06 | 卡内基梅隆大学 | Metal ligand containing bleaching compositions |
| US6051704A (en) * | 1996-07-22 | 2000-04-18 | Carnegie Mellon University | Synthesis of macrocyclic tetraamido-N ligands |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1844128A (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100393734C (en) | Process for synthesizing tetra-substituted amino macrocyclic metal complex | |
| CN101045733B (en) | Preparation method of cefotiam chloride | |
| CN103333120A (en) | Mesosulfuron-methyl synthetic method | |
| CN104496917B (en) | A kind of synthetic method of Favipiravir | |
| CN109956870A (en) | A kind of Luo Shasi his synthetic method and its midbody compound | |
| CN102786516A (en) | Method for synthesizing rivaroxaban | |
| CN101589055A (en) | Process for the preparation of an (Rp)-8-substituted cAMPS | |
| CN105646368A (en) | Preparation method of 2, 4-dichloro-5-methoxy pyrimidine | |
| CN102633696A (en) | Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis | |
| CN101812032A (en) | Method for synthesizing macrocyclic tetraamido metal complex | |
| CN102952093A (en) | Method for preparing 1,2 benzo-isothiazolin-3-ketone compound | |
| CN103936759B (en) | (3aS, 6aR)-1,3-dibenzyl-tetrahydrochysene-4H-thieno-[3,4-d] imidazoles-2,4-(1H) simple and convenient process for preparing of-diketone | |
| CN101643427B (en) | Preparation method of 2,2-bis(3-amino-4-hydroxylphenyl)hexafluoropropane | |
| CN107513053A (en) | A kind of preparation method of sitafloxacin hydrate | |
| CN105418681A (en) | Preparation method of tedizolid phosphate | |
| CN103374018A (en) | Novel method for preparing ceftibuten parent nucleus 7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid diphenylmethyl ester (7-NACABH) | |
| CN101402589B (en) | Synthesis of 2-bromine-4-nitrobenzene ethane nitrile | |
| CN114213430B (en) | Preparation method of 4-aminothiophene [3,2-d ] pyrimidine-7-carboxylic acid and protein kinase inhibitor intermediate | |
| CN114805313A (en) | Method for synthesizing protease inhibitor | |
| CN108727292A (en) | A kind of preparation method of Ao Zhamode and its intermediate | |
| CN108727291A (en) | The preparation method of Ao Zhamode and its intermediate | |
| CN113372286A (en) | Method for preparing 1-phenyl-5-mercapto tetrazole by one-step method | |
| CN102560103B (en) | Method for purification production of molybdenum disulfide from molybdenum concentrate | |
| CN101774939A (en) | Trans-N-(4- hydroxyl-3-methoxybenzy)-8-methyl-5-nonenamide and preparation method thereof | |
| CN105800655A (en) | Sodium oxalate mixed seed and method for separating sodium oxalate out of sodium aluminate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080611 Termination date: 20110510 |