CN101456882B - Acylated ferrocene solid phase synthesis method - Google Patents
Acylated ferrocene solid phase synthesis method Download PDFInfo
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- CN101456882B CN101456882B CN2007101794906A CN200710179490A CN101456882B CN 101456882 B CN101456882 B CN 101456882B CN 2007101794906 A CN2007101794906 A CN 2007101794906A CN 200710179490 A CN200710179490 A CN 200710179490A CN 101456882 B CN101456882 B CN 101456882B
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- ferrocene
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- phosphoric acid
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 239000011973 solid acid Substances 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 2
- 238000013375 chromatographic separation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical class CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- -1 carboxylic acid halides Chemical class 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 4
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- SPKJCVZOZISLEI-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylethanone;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC(=O)C1=CC=C[CH-]1 SPKJCVZOZISLEI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 235000014666 liquid concentrate Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007867 post-reaction treatment Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a method for the synthesizing acidylated ferrocene by solid phase. The method comprises: taking solid acid generated by loading liquid phosphoric acid with the certain mass onto the surface of silicon dioxide as a catalyst, mixing the catalyst fully with ferrocene, taking anhydride as an acidylating agent, and carrying out heated reaction for between 2 and 6 hours at 40 to 80 DEG C to obtain the reactant. The mol ratio of the reaction raw materials to the catalyst is as follows: ferrocene: anhydride: phosphoric acid is equal to 1.0:1.0-5.0:0.9-4.0. The product is obtained by processing the reactant via a crystallization method or directly via column chromatographic separation. The method has easily obtained raw materials, and the stable product yield and quality. The treatment after the reaction is simple and produces no wastewater; and the reclaimed solid carrier of silicon dioxide can be used repeatedly.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of method of acylated ferrocene solid phase synthesis.
Technical background
Acylated ferrocene also has application for the intermediate (W.Tang andX.Zhang, Chem.Rev., 2003,103,3029.) of the chiral ferrocene phosphine part of even phase asymmetric hydrogenation catalyzer composition in other material field.Adopt liquid phase reaction traditionally, be Preparation of Catalyst (J.Graham with liquid protonic acid, R..V.Lindsey, G.W.Parshall, M.L.Peterson, and G.M.Whitman, J.Am.Chem.Soc., 1957,79,3416.), post-reaction treatment produces a large amount of waste water, and reaction conditions is difficult to control and causes reaction yield to be difficult for improving also unstable.The Lewis acid of employing single component is aluminum chloride (M.D.Rausch, L.E.Coleman (Jr.), J.Org.Chem., 1958,23,107.) for example; With unsettled catalyzer in air and volatile and in air unsettled reagent acyl chloride make acylating agent, the gained yield is also lower and make subsequent operations numerous and diverse, other Lewis acid is made catalyzer as utilizing boron trifluoride, is acylating agent (V.A.Darin with the acid anhydrides; A.Federman Neto; Et al, J.prakt.Chem., 1999,341 (6), 588.); Zinc Chloride Anhydrous is made catalyzer, is acylating agent (N.Tto with acid anhydrides or carboxylic acid halides; T.Umeda, Jpn.Kokai Tokkyl KotoJP231579,2004); Or utilize carboxylic acid and phosphorus trichloride original position to generate acyl chlorides catalysis substitution reaction generation acylated ferrocene (M.D.Vukicevic again; R.D.Vukieevic, Tetrahedron, 2002,58 (44), 9001.) and the lewis acid catalyst (CN1948324A) that adopts two-pack in recent years, equally also can produce the problem that operational difficulty and aftertreatment produce a large amount of waste water.Polynite carrying metal ion is made catalyzer also report (B.M.Choudary; K.S.Reddy; M.L.Kantum; K.V.Raghavan, US US6239302,2000), catalyst preparation process is loaded down with trivial details, and reaction also need be carried out under liquid phase, and the reagent that consumes in the reaction process is many, the temperature of reaction height.
Summary of the invention
The object of the present invention is to provide that a kind of raw material is easy to get, easy and simple to handle, stable yield and do not have the method for preparing acylated ferrocene of the three wastes.
Have now found that, adopt the method (abbreviation solid phase method) of acylated ferrocene solid phase synthesis of the present invention can realize above-mentioned purpose.
Technical scheme of the present invention is: at first liquid phosphoric acid is carried on and prepares solid acid catalyst on the silica supports, then with solid acid catalyst and ferrocene thorough mixing, again with acid anhydrides prepared in reaction acylated ferrocene under solid phase.
Specific embodiments of the present invention is as follows:
Being carried on the solid acid that generates on the surface of silicon-dioxide with the liquid phosphoric acid of certain mass was catalyzer, behind substrate ferrocene thorough mixing, is acylating agent with the acid anhydrides, obtained reactant at 40-80 ℃ of following reacting by heating 2-6 hour.The feed ratio of each reaction raw materials and catalyzer is counted with mole, ferrocene: acid anhydrides: phosphoric acid equals 1.0: 1.0-5.0: 0.9-4.0.After reaction finished, solid reactant was with sherwood oil heating leaching, and the gained leaching liquid concentrates and cooling, obtains crystalline acylated ferrocene product; Or the ethyl acetate room temperature is leached, the gained leaching liquid concentrates, and obtains crystalline acylated ferrocene product; Or solid reactant is that the direct column chromatography separation of elutriant obtains the purpose product with the petrol ether/ethyl acetate mixed solution.
Below further preferred control condition and working method can improve the catalytic efficiency of solid acid among the present invention and more help the carrying out of solid state reaction.As the specific surface area of the silicon-dioxide of carrier at 200-500m
2Be advisable in/g the scope; The loading of phosphoric acid is that the 10-40% of solid acid catalyst weight is advisable, and down makes the solid acid that is generated be fluidized state in dry two hours in 100 ℃, makes its thorough mixing and reaches more than 150 orders by abrasive catalyst and reaction substrate ferrocene.Stir on the mixture that will spray as the acid anhydrides of acylating agent down behind solid acid and the reaction raw materials ferrocene thorough mixing (nozzle diameter of spray acid anhydrides is advisable with the 0.1-0.5 millimeter), secluding air heated above-mentioned reaction mixture 2-6 hour (can to adopt water-bath or oil bath) afterwards in 40-80 ℃ of scope.When feeding quantity is big, adopts stirring more to help successful reaction and carry out.The comparatively preferred feed ratio of each reaction raw materials and catalyzer is counted with mole: ferrocene: acid anhydrides: phosphoric acid equals 1.0: 1.5-4.0: 1.0-2.5.Suitable acylating agent is selected from C
1-C
8Aliphatic anhydride.Adopting thin-layer chromatography or liquid chromatography tracking monitor not to have the raw material ferrocene is reaction end.After reaction finished, reactant was cooled to room temperature, and with the sherwood oil that the sherwood oil heating is leached, about 2/3 volume is removed in air distillation, cooling concentration liquid obtains the crystallization of acylated ferrocene product; Perhaps use ethyl acetate drip washing reaction product, the combined ethyl acetate leacheate also is concentrated into the sherwood oil crystallization of dried back; Perhaps will react the back solid product and be elutriant, adopt silica gel column chromatography directly to separate, concentrated elution fraction and obtain crystalline acylated ferrocene product with petrol ether/ethyl acetate mixed solution (volume ratio is 4/1).
The method of acylated ferrocene solid phase synthesis of the present invention has the following advantages: thereby 1. owing to utilize solid carrier silicon-dioxide to make the phosphoric acid uniform distribution avoid the local overrich of acid in reaction system, take place thereby suppress its side reaction of decomposing ferrocene, the effect of acid catalysis ferrocene acidylate is strengthened; The surface of silicon-dioxide also provides ferrocene and the place that anhydrides reagent well contacts simultaneously, and reaction is carried out smoothly.2. can suppress usually the generation of 1,1 '-two acylated ferrocene by product that brings by Louis acid catalysis.3. raw material is easy to get, and post-reaction treatment is easy and simple to handle, does not produce waste water.The solid carrier silicon-dioxide of Hui Shouing can reuse, the yield and the steady quality of purpose product.
Embodiment
The following stated is implemented to describe the present invention in detail, and in these examples of implementation, unless Special Statement is arranged, the nozzle diameter of spray usefulness is 0.1 millimeter, and used silicon-dioxide specific surface area is 300m
2/ g (100-140 order), phosphorus acid content 85%, ferrocene content 98%, the sherwood oil boiling range is 30-60 ℃.
Embodiment 1
Take by weighing phosphatase 11 .9 gram, silicon-dioxide 4.0 grams respectively and silicon-dioxide is transferred in the beaker.Stir silicon-dioxide, simultaneously phosphoric acid sprayed to silicon-dioxide, till whole phosphoric acid add.Continue to stir after 10 minutes, this mixture is moved under the infrared lamp, controlled temperature stirred once mixture every l0 minute about 100 ℃, stop after about l hour mixture is fluidized.This mixture is transferred in the mortar, and adding 1.9 gram ferrocene fully are ground to mixture and can pass through 200 mesh sieves.Mixture after transfer is ground stirs 4.9 milliliters of propionic anhydrides of spray down to the single port flask of l00 milliliter.After propionic anhydride all adds, flask was transferred in 60 ℃ the water-bath secluding air heating 4 hours.Reaction finishes to remove water-bath, and reaction mixture is cooled to room temperature naturally.Divide heating leaching resultant three times with 180 milliliters sherwood oils, merge leaching liquid, air distillation steams about 130 milliliters of liquid, and concentrated solution was placed 24 hours in refrigerator after naturally cooling to room temperature in the matrass, and filtering for crystallizing gets propionyl ferrocene product 2.1 grams.
Nuclear magnetic data is as follows:
1HNMR (300MHz, CDCl
3): δ (ppm): 1.20 (3H), 2.74 (2H), 4.18 (5H), 4.49 (2H), 4.79 (2H).
Embodiment 2
The feeding quantity of solid acid catalyst preparation, various materials, reaction conditions and operation are with example 1.After reaction finished, reaction mixture was cooled to room temperature naturally.With this mixture is sample, on application of sample to the 150 gram silicagel column, is elutriant with petrol ether/ethyl acetate mixed solution (volume ratio is 4/1), and separated product gets 160 milliliters of elutriants that contain product.Concentrating under reduced pressure gets propionyl ferrocene 2.2 grams.
Embodiment 3
The solid acid catalyst preparation is with example 1.It is transferred in the mortar, and adding 2.0 gram ferrocene fully are ground to mixture and can pass through 200 mesh sieves.In the single port flask of the mixture to 100 after shift grinding milliliter, stir 3.7 milliliters of propionic anhydrides of spray down.After propionic anhydride all adds, flask was transferred in 60 ℃ the water-bath secluding air heating 4 hours.After reaction finished, reactant was cooled to room temperature naturally.With this mixture is sample, on application of sample to the 150 gram silicagel column, is elutriant with petrol ether/ethyl acetate mixed solution (volume ratio is 4/1), and separated product gets product propionyl ferrocene 1.8 grams.
Embodiment 4
Take by weighing phosphatase 24 .7 gram, silica 1 0.0 gram respectively, the operation of preparation solid acid catalyst is with example 1.This mixture is transferred in the mortar, adds 7.4 gram ferrocene, fully be ground to mixture and can pass through 200 mesh sieves.In the single port flask of the mixture to 100 after shift grinding milliliter, stir spray 16.0 ml acetic anhydride down.After diacetyl oxide all adds, flask is transferred in 60 ℃ the water-bath secluding air heating reaction in 4 hours and finishes.Remove water-bath, reaction mixture is cooled to room temperature naturally.With ethyl acetate (5 * 100 milliliters) leaching gained solid, check no ferrocene.The concentrating under reduced pressure lixivium is to doing, and is residue obtained with the sherwood oil recrystallization, gets the red needle crystal of 8.1 grams, is verified as acetylferrocene through nuclear-magnetism.
Nuclear magnetic data is as follows:
1HNMR (300MHz, CDCl
3): δ (ppm): 2.40 (3H), 4.21 (5H), 4.51 (2H), 4.78 (2H).
Embodiment 5
Take by weighing phosphatase 11 8.8 grams, silicon-dioxide 40.0 grams respectively, the operation of preparation solid acid catalyst is with example 1.This mixture is transferred in the mortar, and adding 19.7 gram ferrocene fully are ground to mixture and can pass through 200 mesh sieves.In the single port flask of the mixture to 250 after shift grinding milliliter, stir 49 milliliters of propionic anhydrides of spray down.After propionic anhydride all adds, flask is transferred in 60 ℃ the water-bath secluding air heating reaction in 5 hours and finishes.Remove water-bath, reaction mixture is cooled to room temperature naturally.With ethyl acetate (5 * 100 milliliters) leaching gained solid, merge lixivium and be evaporated to dried, the sherwood oil recrystallization, solid 21.3 grams, TLC is verified as the propionyl ferrocene.
Embodiment 6
Take by weighing phosphatase 11 .8 gram, silicon-dioxide 5.0 grams respectively, the operation of preparation solid acid catalyst is with example 1.This mixture is transferred in the mortar, adds 1.9 gram ferrocene, fully be ground to mixture and can pass through 200 mesh sieves.In the single port flask of the mixture to 50 after shift grinding milliliter, stir spray 4.1 ml acetic anhydride down.After diacetyl oxide all adds, flask is transferred in 60 ℃ the water-bath secluding air heating reaction in 6 hours and finishes.Remove water-bath, reaction mixture is cooled to room temperature naturally.With ethyl acetate (3 * 50 milliliters) leaching gained solid, merge lixivium and be evaporated to dried, the sherwood oil recrystallization, solid 1.8 grams, TLC is verified as acetylferrocene.
Embodiment 7
Take by weighing phosphoric acid 23.0 grams, silicon-dioxide 50.0 grams respectively, the operation of preparation solid acid catalyst is with example 1.This mixture is transferred in the mortar, adds 28.0 gram ferrocene, fully be ground to mixture and can pass through 200 mesh sieves.In the single port flask of the mixture to 250 after shift grinding milliliter, stir 65.4 milliliters of propionic anhydrides of spray down.After propionic anhydride all adds, flask is transferred in 60 ℃ the water-bath secluding air heating reaction in 6 hours and finishes.Remove water-bath, reaction mixture is cooled to room temperature naturally.With ethyl acetate (5 * 100 milliliters) leaching gained solid, merge lixivium and be evaporated to dried, the sherwood oil recrystallization, solid 29.5 grams, TLC is verified as the propionyl ferrocene.
Claims (7)
1. the method for an acylated ferrocene solid phase synthesis, comprise: being carried on the solid acid that generates on the surface of silicon-dioxide with liquid phosphoric acid is catalyzer, after catalyzer and ferrocene ground and mixed, be acylating agent with the acid anhydrides, obtained product at 40-80 ℃ of following reacting by heating 2-6 hour; The feed ratio of each reaction raw materials and catalyzer is counted with mole, ferrocene: acid anhydrides: phosphoric acid equals 1.0: 1.0-5.0: 0.9-4.0.
2. it is characterized in that in accordance with the method for claim 1: the specific surface area that is used as the silicon-dioxide of carrier is 200-500m
2/ g, the loading of phosphoric acid are the 10-40% of solid acid catalyst weight.
3. according to claim 1 or 2 described methods, it is characterized in that: the feed ratio of each reaction raw materials and catalyzer is counted with mole, ferrocene: acid anhydrides: phosphoric acid equals 1.0: 1.5-4.0: 1.0-2.5.
4. it is characterized in that in accordance with the method for claim 1: abrasive catalyst and ferrocene make its thorough mixing and reach more than 150 orders.
5. it is characterized in that in accordance with the method for claim 1: described acylating agent is selected from C
1-C
8Aliphatic anhydride.
6. it is characterized in that in accordance with the method for claim 1: adopt crystallization process to handle product and obtain acylated ferrocene.
7. it is characterized in that in accordance with the method for claim 1: product is directly carried out column chromatography separate the acquisition acylated ferrocene.
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| CN107011390B (en) * | 2014-09-30 | 2019-10-18 | 浙江工业大学 | A kind of synthetic method being alkylated ferrocene derivatives |
| CN107488200A (en) * | 2016-06-13 | 2017-12-19 | 苏州天允金属材料有限公司 | A kind of synthetic method of ferrocenyl methyl ketone |
| CN110479377B (en) * | 2019-08-06 | 2021-11-16 | 南方医科大学 | Catalyst for reaction of 4-iodonitrobenzene and phenylacetylene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6239302B1 (en) * | 2000-04-07 | 2001-05-29 | Council Of Scientific & Industrial Research | Process for the preparation of acylferrocenes |
| CN1775788A (en) * | 2005-12-06 | 2006-05-24 | 三峡大学 | Method for synthesizing acyl ferrocene |
| CN1948324A (en) * | 2005-10-11 | 2007-04-18 | 上海化学试剂研究所 | Preparation method of acetyl cyclopentadienyl iron |
| CN101037452A (en) * | 2007-03-27 | 2007-09-19 | 武汉大学 | Method for preparing acyl Ferrocene |
-
2007
- 2007-12-14 CN CN2007101794906A patent/CN101456882B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6239302B1 (en) * | 2000-04-07 | 2001-05-29 | Council Of Scientific & Industrial Research | Process for the preparation of acylferrocenes |
| CN1948324A (en) * | 2005-10-11 | 2007-04-18 | 上海化学试剂研究所 | Preparation method of acetyl cyclopentadienyl iron |
| CN1775788A (en) * | 2005-12-06 | 2006-05-24 | 三峡大学 | Method for synthesizing acyl ferrocene |
| CN101037452A (en) * | 2007-03-27 | 2007-09-19 | 武汉大学 | Method for preparing acyl Ferrocene |
Non-Patent Citations (1)
| Title |
|---|
| 卓馨.乙酰二茂铁的合成与性质测定.《宿州学院学报》.2006,第21卷(第6期),97-99，120. * |
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