CN103450284B - One prepares 3-methyl isophthalic acid, the method for 3-diferrocenyl propylene-1-ketone - Google Patents
One prepares 3-methyl isophthalic acid, the method for 3-diferrocenyl propylene-1-ketone Download PDFInfo
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- CN103450284B CN103450284B CN201310337655.3A CN201310337655A CN103450284B CN 103450284 B CN103450284 B CN 103450284B CN 201310337655 A CN201310337655 A CN 201310337655A CN 103450284 B CN103450284 B CN 103450284B
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- CN
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- Prior art keywords
- ketone
- diferrocenyl
- propylene
- isophthalic acid
- methyl isophthalic
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 13
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 title claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 12
- CBJYXYXOISWSDQ-UHFFFAOYSA-M cyclopenta-1,3-diene;1-cyclopenta-2,4-dien-1-ylideneethanolate;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC([O-])=C1C=CC=C1 CBJYXYXOISWSDQ-UHFFFAOYSA-M 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract 2
- -1 methyl 1,3 diferrocenyl propylene Chemical group 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000767 anti-ulcer Effects 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000812 cholinergic antagonist Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002048 spasmolytic effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides one and prepare 3 methyl 1; the method of 3 diferrocenyl propylene 1 ketone; according to A:B:C=2:(1.5～3.5): the ratio of (0～3.5), in reaction vessel, add A mmol ferrocenyl methyl ketone, B mmol alkali and C mmol K2CO3, grind 10～30min, then stand, obtain mixture；Adding water again in mixture makes it be uniformly dispersed, and then sucking filtration by Cake Wash, is dried, obtains 3 methyl 1,3 diferrocenyl propylene 1 ketone.The present invention uses polishing to prepare target product, with ferrocenyl methyl ketone as raw material, with K2CO3And alkali is catalyst or independent with alkali as catalyst, reaction is without solvent, easy and simple to handle, reacts easily controllable, and the response time is short, and equipment requirements is low, and post processing is simple, and productivity is high.
Description
Technical field
The invention belongs to the field of chemical synthesis, prepare 3-methyl isophthalic acid, 3-diferrocenyl propylene particularly to one
The method of-1-ketone.
Background technology
From nineteen fifty-one after Kealy and Pauson is found that ferrocene, this metallo-organic compound is just only with it
Special structure and character attract attention.Owing to it has armaticity, thermodynamic stability, photochemical
Learn stability, electrophilicity, hypotoxicity and redox reversible, and be applied to various aspects, such as:
Asymmetry catalysis, electrochemical sensor, optics, liquid crystal material etc..Meanwhile, ferrocene can be through thin
After birth, directly acts on desmoenzyme, DNA or RNA etc., therefore at biology and medicine also
It is widely used equally, such as: antitumor, antiulcer, spasmolytic, antiinflammatory, sterilization etc..Therefore, right
The research of ferrocene compounds is the most meaningful.
Didier Villemin etc. at Journal of Organometallic Chemistry, 1994, pp.27～31
In the Dry synthesis under microwave irradiation:synthesis of ferrocenylenones of table, report
Road 3-methyl isophthalic acid, the synthetic method of 3-diferrocenyl propylene-1-ketone.It is by ferrocenyl methyl ketone, toluenediamine
And potassium hydroxide is heated to reflux 4h, sucking filtration, column chromatography for separation goes out product, and productivity is 52%.The method is anti-
Between Ying Shi long, operate relative complex, post processing bothers, and productivity is the highest.
Summary of the invention
It is an object of the invention to provide a kind of easy and simple to handle, the response time is short, post processing is simple and productivity is high
Preparation 3-methyl isophthalic acid, the method for 3-diferrocenyl propylene-1-ketone.
To achieve these goals, technical scheme comprises the following steps:
The first step, according to A:B:C=2:(1.5～3.5): the ratio of (0～3.5), in reaction vessel, add A mmol
Ferrocenyl methyl ketone, B mmol alkali and C mmol K2CO3, grind 10～30min, then stand, obtain mixed
Compound；
Second step, adds water in mixture and makes it be uniformly dispersed, and then sucking filtration by Cake Wash, is dried,
Obtain 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-ketone.
The alkali added in the described first step is NaOH or KOH.
Grinding in the described first step is carried out in mortar.
Time of repose in the described first step is 1～2h.
The described first step is carried out in anhydrous conditions.
The described first step is at room temperature carried out.
Described second step adds in mixture X mL water, X=(25～40) A.
By Cake Wash to pH=6～7 in described second step.
Described second step washes filter cake with water.
Being dried in described second step is dried for room temperature.
Compared with prior art, the method have the advantages that
The invention provides a kind of 3-methyl isophthalic acid, the preparation method of 3-diferrocenyl propylene-1-ketone, the method with
Ferrocenyl methyl ketone is raw material, K2CO3And alkali is catalyst or independent with alkali as catalyst, by grinding
Prepare 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-ketone.The present invention is easy and simple to handle, without molten in course of reaction
Agent, and react easily controllable, the response time is shorter, only 10-30min, and equipment requirements is low, locates afterwards
Reason is simple, only need to carry out common sucking filtration, washing, and productivity is more than 85%, has higher productivity,
Therefore the present invention is a kind of the simplest, economic preparation 3-methyl isophthalic acid, the side of 3-diferrocenyl propylene-1-ketone
Method.
Detailed description of the invention
The present invention is with K2CO3And KOH or NaOH is base catalysis, grinds under room temperature and prepare 3-methyl isophthalic acid, 3-
Diferrocenyl propylene-1-ketone, its reaction equation as the formula (1):
Below in conjunction with the present invention preferably specific embodiment, the present invention is described in further detail.
Embodiment 1
The first step, adds 2mmol ferrocenyl methyl ketone, 1.5mmol NaOH and 3.5mmol in mortar
K2CO3, grind 10min, then stand 2h, obtain mixture；
Second step, adds 50mL water in mixture and makes it be uniformly dispersed, and filter cake is washed by then sucking filtration
Drying to its pH=7, room temperature, the dark red powder obtained is 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-
Ketone, productivity is 85%；M.p is 120～121 DEG C.
IR (KBr) (cm-1): 3091,1109,1006,819 (C-H of ferrocene ring)；1637(C=O);
1586(C=C)。
Embodiment 2
The first step, adds 2mmol ferrocenyl methyl ketone, 2mmol KOH and 2.5mmol in mortar
K2CO3, grind 15min, then stand 1.5h, obtain mixture；
Second step, adds 65mL water in mixture and makes it be uniformly dispersed, and filter cake is washed by then sucking filtration
Drying to its pH=6, room temperature, the dark red powder obtained is 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-
Ketone, productivity is 89%；M.p is 120～121 DEG C.
Embodiment 3
The first step, adds 2mmol ferrocenyl methyl ketone and 3.5mmol NaOH in mortar, grinds 20
Min, then stands 2h, obtains mixture；
Second step, adds 60mL water in mixture and makes it be uniformly dispersed, and filter cake is washed by then sucking filtration
Drying to its pH=7, room temperature, the dark red powder obtained is 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-
Ketone, productivity is 92%；M.p is 120～121 DEG C.
Embodiment 4
The first step, adds 2mmol ferrocenyl methyl ketone, 1.5mmol KOH and 3mmol in mortar
K2CO3, grind 25min, then stand 1h, obtain mixture；
Second step, adds 75mL water in mixture and makes it be uniformly dispersed, and filter cake is washed by then sucking filtration
Drying to its pH=7, room temperature, the dark red powder obtained is 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-
Ketone, productivity is 90%；M.p is 120～121 DEG C.
Embodiment 5
The first step, adds 2mmol ferrocenyl methyl ketone, 2.5mmol NaOH and 1.5mmol in mortar
K2CO3, grind 30min, then stand 1.5h, obtain mixture；
Second step, adds 80mL water in mixture and makes it be uniformly dispersed, and filter cake is washed by then sucking filtration
Dry to its pH=6.5, room temperature, obtain dark red powder and be 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-
Ketone, productivity is 89%；M.p is 120～121 DEG C.
The invention provides a kind of 3-methyl isophthalic acid, the preparation method of 3-diferrocenyl propylene-1-ketone, have employed
K2CO3With KOH, K2CO3With NaOH, KOH or NaOH as the catalyst of reaction, carry for reaction
For alkaline environment, having good catalytic effect, grinding at room temperature i.e. can get target product in anhydrous conditions,
Reaction is without solvent, easy and simple to handle, and post processing is simple and productivity is higher, is a kind of simplicity, economic 3-first
The preparation method of base-1,3-diferrocenyl propylene-1-ketone.
Claims (4)
1. prepare a 3-methyl isophthalic acid, the method for 3-diferrocenyl propylene-1-ketone, it is characterised in that include with
Lower step:
The first step, under room temperature and anhydrous condition, according to A:B:C=2:(1.5～3.5): the ratio of (0～3.5), to
Mortar adds A mmol ferrocenyl methyl ketone, B mmol alkali and C mmol K2CO3, grind 10～30min,
Then stand 1～2h, obtain mixture；Wherein alkali is NaOH or KOH；
Second step, adds X mL water in mixture and makes it be uniformly dispersed, X=(25～40) A, then sucking filtration,
By Cake Wash, it is dried, obtains 3-methyl isophthalic acid, 3-diferrocenyl propylene-1-ketone.
Preparation 3-methyl isophthalic acid the most according to claim 1, the method for 3-diferrocenyl propylene-1-ketone, its
It is characterised by: by Cake Wash to pH=6～7 in described second step.
Preparation 3-methyl isophthalic acid the most according to claim 1, the method for 3-diferrocenyl propylene-1-ketone, its
It is characterised by: described second step washes filter cake with water.
Preparation 3-methyl isophthalic acid the most according to claim 1, the method for 3-diferrocenyl propylene-1-ketone, its
It is characterised by: being dried in described second step is dried for room temperature.
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| CN201310337655.3A CN103450284B (en) | 2013-08-05 | 2013-08-05 | One prepares 3-methyl isophthalic acid, the method for 3-diferrocenyl propylene-1-ketone |
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| CN102617649A (en) * | 2012-03-13 | 2012-08-01 | 陕西科技大学 | 1-ferrocenyl-4-N-phenothiazinyl acrylketone and preparation method thereof |
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| CN102617649A (en) * | 2012-03-13 | 2012-08-01 | 陕西科技大学 | 1-ferrocenyl-4-N-phenothiazinyl acrylketone and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Dry synthesis under microwave irradiation: synthesis of ferrocenylenones;Didier Villemin等,;《Journal of Organometallic Chemistry》;19941231;第27-31页 * |
| Facile Synthesis of Ferrocenylenones in Free Solvent at Room Temperature;Shun Jun JI等,;《Chinese Chemical Letters》;20031225(第12期);第1246-1248页, 尤其是第1246页正文第2段、第1247页反应式和表1-2、参考文献11 * |
| SiCl4–ethanol as a trimerization agent for organometallics: convenient syntheses of the symmetrically substituted arenes 1,3,5-C6H3R3 where R = (C5H4)Mn(CO)3 and (C5H4)Fe(C5H5);Hari K. Gupta等,;《Can. J. Chem.》;20021130;第1546-1554页 * |
| THE SOLID STATE ALDOL CONDENSATION REACTION OF ACETYLFERROCENE AND AROMATIC ALDEHYDES;Ji Ben MENG等,;《Chinese Chemical Letters》;19931231(第06期);第475-478页 * |
| 二茂铁基查尔酮Schiff碱及其配合物的合成与抑菌性能研究;廉桂丹;《陕西科技大学硕士学位论文》;20130115;第10、13-19页 * |
| 固相缩合反应合成新型二茂铁基α,β-不饱和酮;赵文献等,;《商丘师范学院学报》;20080315(第03期);第74-76页, 尤其是第75页图1和1.3部分、第76页2.2部分 * |
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