CN102924358A - N-methyl-indole-3-styrene compound synthesis method - Google Patents
N-methyl-indole-3-styrene compound synthesis method Download PDFInfo
- Publication number
- CN102924358A CN102924358A CN2012102140055A CN201210214005A CN102924358A CN 102924358 A CN102924358 A CN 102924358A CN 2012102140055 A CN2012102140055 A CN 2012102140055A CN 201210214005 A CN201210214005 A CN 201210214005A CN 102924358 A CN102924358 A CN 102924358A
- Authority
- CN
- China
- Prior art keywords
- methyl
- indoles
- reaction
- indole
- styrene compound
- 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.)
- Pending
Links
Images
Landscapes
- Indole Compounds (AREA)
Abstract
The present invention discloses an N-methyl-indole-3-styrene compound synthesis method. According to the synthesis method, a reaction starts from indole-3-carboxaldehyde substituting, indole-3-carboxaldehyde reacts with a methylating reagent in a polar solvent under an alkaline condition, such that nitrogen and hydrogen on the indole ring are substituted by methyl; and then the obtained compound and substituted diethyl benzylphosphonate are subjected to a Wittig-Homer reaction in an aprotic solvent under a strong base effect to introduce styryl. Compared with the method in the prior art, the method of the present invention has the following advantages that: after the substituted indole-3-methanol compound is obtained, a one-step method is adopted to synthesize the target product so as to simplify reaction steps and improve the whole yield; and the easily available raw materials are adopted so as to reduce cost.
Description
Technical field
The invention belongs to technical field of chemistry, relate to the synthetic method of a kind of N-methyl-indoles-3-styrene compound.
Background technology
Two aromatic groups link to each other by the π key and obtain a conjugated system, form intramolecular stream of electrons, and such as N-methyl-indoles-3-vinylbenzene, its structure is seen shown in the right figure.This compounds can show excellent photovoltaic effect; can be applied to all respects such as sensitization equipment, white dyes, laserable material, optical data storage, photo-conductor; also can be used as research and wish that Huang is mould, the model of carotenoid isoline type compound, the research photobiology is very helpful.When making up the conjugated system that links to each other with the π key, mainly contain following several method at home and abroad:
(1) " chemical reagent "; 2006; 28 (6): the 373-374 report; the people such as Ge Yuhua, Jin Qingxian adopts Wittig method synthesizing styrene based compound; both refluxed in chloroform by Benzyl Chloride and triphenylphosphine and made the Benzyl Chloride triphenylphosphine, then obtained trans-5-methyloxy-3-styrenylindole with the reaction of 5-methoxyindole-3-carboxaldehyde.Synthetic route as shown in Figure 1.
Wittig reaction is a relatively method of structure π key commonly used, but this reaction is relatively more responsive to airborne oxygen and used alkali.The product stereoselectivity that reaction generates is not high yet, and is to have phosphorous by product to be difficult to remove at separating-purifying.
(2) " Organic Letters ", 2005,7 (10): 1414-1418 report, take various replacements Gramine as raw material, react in acetonitrile solvent and tributylphosphine with substituted benzaldehyde and to obtain the conjugated system that links to each other by the π key.Synthetic route as shown in Figure 2.
This is the novel method of the synthesizing styrene base indoles found of the Nabi Magomedov professor of Rochester University, and he obtains 15 various substituted phenylethylene base indoles altogether by this method.
(3) " Journal of Physical Organic Chemistry ", 2006,19:43-52 report take indole-3-formaldehyde as raw material, is introduced styryl with the substituted phenylacetic acid reaction under the katalysis of hexahydropyridine.Synthetic route as shown in Figure 3.
The bibliographical information of setting up two keys with this route is fewer, and major cause is that productive rate is very low, generally below 10%.
Summary of the invention
In order to overcome the defective that exists in the prior art, the invention provides the synthetic method that a kind of synthetic yield is high, synthesize simple, as to be fit to suitability for industrialized production N-methyl-indoles-3-styrene compound.Take indole-3-formaldehyde as raw material, on the indole ring nitrogen-atoms with after the methyl protection, adopt the synthetic a series of N-methyl-indoles of Wittig-Honor method-3-vinylbenzene.
Its technical scheme is as follows:
The synthetic method of a kind of N-methyl-indoles-3-styrene compound, from substituted indole-3-formaldehyde, under polar solvent and the alkaline condition with methylating reagent reaction after, the nitrogen hydrogen of its indole ring is replaced by methyl, and then under the effect of aprotic solvent and highly basic, introduce styryl with the substituted-phenyl diethyl phosphonate by the Wittig-Horner reaction, generate N-methyl-indoles-3-styrene compound
Synthetic route as shown in Figure 4.
R represents fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl or ester group in the formula; R ' expression fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl or ester group.
Described substituted-phenyl diethyl phosphonate be reactant be again solvent.
Described polar solvent is: methylene dichloride, trichloromethane, acetone, tetrahydrofuran (THF), second cyanogen or DMF.
Described methylating reagent is: methylcarbonate, methyl-sulfate or sodium iodide.
Described alkaline condition refers under the condition of sodium hydroxide, potassium hydroxide, salt of wormwood or sodium carbonates' presence.
Described aprotic solvent is for comprising tetrahydrofuran (THF), DMSO or DMF.
Described highly basic is potassium amide, sodium amide, sodium hydride, potassium tert.-butoxide, potassium ethylate and sodium ethylate by alkaline power successively.
Alkalescence is stronger, and the stereoselectivity of reaction is better.
Further preferred, described highly basic is potassium amide.
Beneficial effect of the present invention: the synthetic method of N-methyl-indoles of the present invention-3-styrene compound, with respect to prior art, owing to adopted so new synthetic route, that is: from substituted indole-3-formaldehyde, under polar solvent and the alkaline condition with methylating reagent reaction after, the nitrogen hydrogen of its indole ring is replaced by methyl, obtain corresponding N-methyl-indole-3-formaldehyde.And then under the effect of aprotic solvent and highly basic, introduce styryl with the substituted-phenyl diethyl phosphonate by the Wittig-Horner reaction, make N-methyl-indoles-3-styrene compound.The present invention overcomes above-mentioned the deficiencies in the prior art, and a kind of N-of preparation methyl-indoles-3-styrene compound novel method is provided.The most outstanding advantage of the present invention is to have adopted the Wittig-Honor reaction, and the Wittig-Honor reaction is the improvement of Wittig reaction, and it is found at first in 1958 by people such as Honor, is one of main method of synthesizing at present in alkene.There is following advantage it and classical Wittig reacting phase ratio: stronger than phosphorus ylide nucleophilicity, thereby easier and aldehyde ketone reaction; Because what reaction generated is that Hypophosporous Acid, 50, phosphoric acid and phosphoric acid derivatives are water-soluble, so easy and principal product separation of olefins; Phosphorus ylide needs more expensive phosphorus to prepare, and phosphonic acids vinegar then easily conveniently makes through the Michaelis-Arbuzov reaction from more cheap phosphonous acid vinegar; Phosphono reagent is generally insensitive to alkali, with in the air steam reaction is also slow, thereby experimental implementation is more convenient; Topmost advantage is that the stereoselectivity of this reaction is very strong, and product mainly is trans.Secondly, the present invention is synthetic simple, and feed stock conversion is high, not high to equipment requirements yet, and each step aftertreatment is all very simple, only needs to add after reaction finishes a certain amount of water, can separate out product from reaction system, productive rate can reach more than 90%, more than the purity to 98%.
Description of drawings
Fig. 1 is the synthetic route chart in first reference document of background technology part of the present invention;
Fig. 2 is the synthetic route chart in second reference document of background technology part of the present invention;
Fig. 3 is the synthetic route chart in the 3rd reference document of background technology part of the present invention;
Fig. 4 is the synthetic route chart of N-methyl-indoles of the present invention-3-styrene compound;
Fig. 5 is first reaction formula in the embodiment of the invention 1;
Fig. 6 is second reaction formula in the embodiment of the invention 1;
Fig. 7 is first reaction formula in the embodiment of the invention 2;
Fig. 8 is second reaction formula in the embodiment of the invention 2;
Fig. 9 is first reaction formula in the embodiment of the invention 3;
Figure 10 is second reaction formula in the embodiment of the invention 3.
Embodiment
Below in conjunction with specific embodiment method of the present invention is described in more detail.
The object of the invention realizes, mainly designed a kind of new synthetic route, namely from substituted indole-3-formaldehyde, under polar solvent and the alkaline condition with methylating reagent reaction after, the nitrogen hydrogen of its indole ring is replaced by methyl, and then under the effect of aprotic solvent and highly basic, introduce styryl with the substituted-phenyl diethyl phosphonate by the Wittig-Horner reaction.
Synthetic route of the present invention is as shown in Figure 4:
R represents the arbitrarily group such as fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl and ester group in the formula.R ' also represents the arbitrarily group such as fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl and ester group.
Among the present invention:
Substituted indole-3-formaldehyde refers to contain various substituting groups at 4,5,6 and 7 of indole ring, comprising fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl and ester group etc.
Polar solvent plays the dissolving raw material, is conducive to strengthen the reaction contact surface, and reaction is carried out in homogeneous phase, reduces the reaction required time.It can be the polar solvent such as but not limited to methylene dichloride, trichloromethane, acetone, tetrahydrofuran (THF), acetonitrile, DMF etc. of commonly using.Test preferably DMF, its solvability to substituted indole-3-formaldehyde is better, and what more be conducive to react is thorough.
Alkaline condition during methylation reaction refers to the alkali of laboratory normal operation, such as sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash etc., but be not limited only to that these are several.
Methylating reagent refers at the reagent that can introduce at the nitrogen-atoms of indoles a methyl.The main purpose of introducing methyl is because the nitrogen hydrogen on the indole ring is more active, under the strong alkali environment of next step Wittig-Honor reaction, nitrogen hydrogen is replaced by the electrophilic reagent in the reaction system easily and introduces impurity, and this also is often to mention but open question in the top bibliographical information.Methylating reagent used in the present invention is methylcarbonate, methyl-sulfate and sodium iodide.Test preferably methylcarbonate, it is much smaller than other two kinds of toxicity, and low price.
Phosphorus ylide reagent in the Wittig-Honor reaction is relatively more responsive to protic solvents such as water, and solvent need to dewater in advance when therefore reacting, and generally will use aprotic polar solvent.They are difficult for providing proton, but specific inductivity and molecular polarity are all very large, the negative charge end of molecule is exposed to the outside mostly, the positive charge end wraps in inside, to negative charge solvation seldom, therefore reaction is very favorable to aprotic polar solvent to Wittig-Honor, and is suitable for the reaction system of highly basic.These solvents can be commonly use such as but not limited to tetrahydrofuran (THF), DMSO, DMF etc.
The highly basic of using in the Wittig-Honor reaction is potassium amide, sodium amide, sodium hydride, potassium tert.-butoxide, potassium ethylate and sodium ethylate by alkaline power successively.It is generally acknowledged that used alkalescence is stronger, the stereoselectivity of reaction is better.The used alkali of the present invention is 60% sodium hydride, and its alkalescence is relatively strong, but inflammable and explosive dangerous less when using.
The substituted-phenyl diethyl phosphonate refers to that ortho position, a position and the contraposition on phenyl ring contains various substituting groups, comprising fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl and ester group etc.
In addition:
On the amount of using solvent and reagent, during the first step methylation reaction, the add-on of polar solvent satisfies gets final product its dissolving, and for example 1g substituted indole-3-formaldehyde is dissolved in 10mL to the 40mL polar solvent.The consumption of alkali is roughly at 1.1 to 2 equivalents, and little excessive getting final product is too much unnecessary.Other methylating reagent, such as methylcarbonate, methyl-sulfate or sodium iodide, consumption keeps identical with alkali, and namely 1.1 to 2 equivalents are too much unnecessary.During second step Wittig-Honor reaction, the consumption of aprotic polar solvent is also to be advisable in right amount, and for example 1gN-methyl substituted indole-3-formaldehyde needs among the 10mL to 40mL, and is too much unnecessary, but solvent must dewater before using.The consumption of highly basic and substituted-phenyl diethyl phosphonate all is 1.1 to 2 equivalents, and is too much unnecessary.
In temperature of reaction with on the reaction times, during the first step methylation reaction, the control temperature generally about the reflux temperature of solvent for use, if use methylene dichloride, then at 30 to 40 ℃, is used acetone, then at 45 to 57 ℃, uses DMF, then at 120 to 145 ℃.Alkalescence is stronger according to also difference is very large with the difference of alkali reaction times in addition, and the time is shorter, if use potassium hydroxide, then at 1 to 2 hour, uses salt of wormwood, then at 8 to 12 hours.Can pass through thin-layer chromatography (TLC) and detect, judge whether reaction finishes fully.During second step Wittig-Honor reaction, temperature of reaction is generally in room temperature or lower temperature, because at high temperature can generate the by product of cis for thermodynamic control, however when low temperature be kinetic control take trans product as main, be advisable so will be controlled at 0 to 25 ℃.Reaction times changes along with the difference of reaction conditions, generally at 1 to 8 hour.Can pass through thin-layer chromatography (TLC) and detect, judge whether reaction finishes fully.
Below in conjunction with three specific embodiments; essence of the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the total technical scheme of the present invention is limited; some are In the view of the technician; the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment 1
Synthesizing of N-skatole-3-formaldehyde.
In the 100mL three-necked bottle, add 1.45g indole-3-formaldehyde (10mmol), 1.35g methylcarbonate (15mmol), 2.07g salt of wormwood (15mmol) and 20mLDMF, then be warming up to 130 ℃ of reactions 9 hours, thin-layer chromatography (TLC) detection reaction terminal point.
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filter, and washing, oven dry obtains white solid N-skatole-3-formaldehyde 1.5g, productive rate 94%, HPLC 〉=98%, 67 ℃～69 ℃ of fusing points, IR (KBr, cm
-1) 3130,2830,1650,1540,1480,1410,1390,1340,1200,1130,1080,800,750.
1H-NMR(300MHz，DMSO)δ3.80(s，3H)，7.27-7.37(m，2H)，7.61-7.77(m，2H)，8.34(s，1H)，9.97(s，1H)。
Reaction formula as shown in Figure 5.
Synthesizing of trans-the N-methyl-3-styryl indoles.
Under the nitrogen protection, in the 100mL three-necked bottle, add the DMF that 2.74g phenyl-phosphonic acid diethyl ester (12mmol) and 30mL remove water treatment, be cooled to 0 ℃ after, add 0.48g sodium hydride (12mmol, 60%) in batches, return back to room temperature reaction half hour.And then cool off 0 ℃, at room temperature reacted thin-layer chromatography (TLC) detection reaction terminal point 2 hours behind adding 1.59gN-methyl-indole-3-formaldehyde (10mmol).
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filters, the washing, the oven dry obtain white solid trans-N-methyl-3-styryl indoles 2.15g,, productive rate 92.3%, HPLC 〉=98%, 92 ℃～94 ℃ of fusing points, IR (KBr, cm-1) 3450,3100,2940,1640,1540,1480,1440,1380,1340,1080,960,740,700.1H-NMR(300MHz，DMSO)δ3.80(s，3H)，7.05-7.26(m，4H)，7.32-7.49(m，4H)，7.57-7.63(m，3H)，8.02(d，1H，J＝9.9Hz)。
Reaction formula as shown in Figure 6.
Embodiment 2
Synthesizing of N-methyl-6-chloro-indole-3-formaldehyde.
In the 100mL three-necked bottle, add 1.79g6-chloro-indole-3-formaldehyde (10mmol), 1.56g methyl iodide (11mmol), 0.44g sodium hydroxide (11mmol) and 25mL acetone, then be warming up to 55 ℃ of reactions 3 hours, thin-layer chromatography (TLC) detection reaction terminal point.
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filters, washing, oven dry obtains yellow solid N-methyl-6-chloro-indole-3-formaldehyde 1.81g, productive rate 93.8%, HPLC 〉=98%, 150 ℃～151 ℃ of fusing points, IR (KBr, cm-1) 3100,2810,1660,1540,1480,1460,1400,1370,1070,850,840,740.1H-NMR(300MHz，DMSO)δ3.88(s，3H)，7.28(dd，1H，J1＝8.4Hz，J2＝2.1Hz)，7.74(d，1H，J＝2.1Hz)，8.07(d，1H，J＝8.4Hz)，8.31(s，1H)，9.88(s，1H)。
Reaction formula as shown in Figure 7.
Synthesizing of trans-the N-methyl-6-chloro-3-styryl indoles.
Under the nitrogen protection, in the 100mL three-necked bottle, add the THF that 4.56g phenyl-phosphonic acid diethyl ester (20mmol) and 40mL remove water treatment, be cooled to 0 ℃ after, add 1.36g sodium ethylate (20mmol) in batches, return back to room temperature reaction half hour.And then cool off 0 ℃, at room temperature reacted thin-layer chromatography (TLC) detection reaction terminal point 8 hours behind adding 1.94g N-methyl-6-chloro-indole-3-formaldehyde (10mmol).
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filters washing, the oven dry obtain yellow solid trans-N-methyl-6-chloro-3-styryl indoles 2.49g,, productive rate 93.2%, HPLC 〉=98%, 92 ℃～94 ℃ of fusing points, IR (KBr, cm-1) 3450,3150,2940,1630,1530,1470,1400,1380,1330,1070,960,840,800,700.1H-NMR(300MHz，DMSO)δ3.79(s，3H)，7.04-7.21(m，3H)，7.32-7.41(m，3H)，7.56-7.62(m，3H)，7.66(s，1H)，8.03(d，1H，J＝9.0Hz)。
Reaction formula as shown in Figure 8.
Embodiment 3
Synthesizing of N-methyl-5-cyano group-indole-3-formaldehyde.
In the 100mL three-necked bottle, add 1.7g5-cyano group-indole-3-formaldehyde (10mmol), 1.51g methyl-sulfate (12mmol), 1.66g salt of wormwood (12mmol) and 30mL acetonitrile, then be warming up to 80 ℃ of reactions 8 hours, thin-layer chromatography (TLC) detection reaction terminal point.
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filters, washing, oven dry obtains yellow solid N-methyl-5-cyano group-indole-3-formaldehyde 1.71g, productive rate 93.0%, HPLC 〉=98%, 150 ℃～151 ℃ of fusing points, IR (KBr, cm-1) 3100,2810,1660,1540,1480,1460,1400,1370,1070,850,840,740.1H-NMR(300MHz，DMSO)δ3.88(s，3H)，7.28(dd，1H，J1＝8.4Hz，J2＝2.1Hz)，7.74(d，1H，J＝2.1Hz)，8.07(d，1H，J＝8.4Hz)，8.31(s，1H)，9.88(s，1H)。
Reaction formula as shown in Figure 9.
Trans-N-methyl-5-cyano group-3-is synthetic to bromstyrol base indoles.
Under the nitrogen protection, in the 100mL three-necked bottle, add 4.61g removes water treatment to bromophenyl diethyl phosphonate (15mmol) and 25mL DMSO; after being cooled to 0 ℃; add 0.6g sodium hydride (15mmol, 60%) in batches, return back to room temperature reaction half hour.And then cool off 0 ℃, at room temperature reacted thin-layer chromatography (TLC) detection reaction terminal point 1 hour behind adding 1.84gN-methyl-5-cyano group-indole-3-formaldehyde (10mmol).
Reaction is cooled to room temperature after finishing, and adds 60mL water, and have solid to separate out this moment, filters washing, that oven dry obtains yellow solid is trans-and N-methyl-5-cyano group-3-is to bromstyrol base indoles 3.05g,, productive rate 90.5%, HPLC 〉=98%, 92 ℃～94 ℃ of fusing points, IR (KBr, cm-1) 3450,3150,2940,1630,1530,1470,1400,1380,1330,1070,960,840,800,700.1H-NMR(300MHz，DMSO)δ3.79(s，3H)，7.04-7.21(m，3H)，7.32-7.41(m，3H)，7.56-7.62(m，3H)，7.66(s，1H)，8.03(d，1H，J＝9.0Hz)。
Reaction formula as shown in figure 10.
Claims (8)
1. the synthetic method of N-methyl-indoles-3-styrene compound, it is characterized in that, from substituted indole-3-formaldehyde, under polar solvent and the alkaline condition with methylating reagent reaction after, the nitrogen hydrogen of its indole ring is replaced by methyl, and then under the effect of aprotic solvent and highly basic, introduce styryl with the substituted-phenyl diethyl phosphonate by the Wittig-Horner reaction, generate N-methyl-indoles-3-styrene compound
Synthetic route is as follows:
R represents fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl or ester group in the formula; R ' expression fluorine, chlorine, bromine, alkyl, methoxyl group, benzyl, cyano group, nitro, ethanoyl or ester group.
2. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that, described substituted-phenyl diethyl phosphonate be reactant be again solvent.
3. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that described polar solvent is: methylene dichloride, trichloromethane, acetone, tetrahydrofuran (THF), second cyanogen or DMF.
4. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that described methylating reagent is: methylcarbonate, methyl-sulfate or sodium iodide.
5. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that described alkaline condition refers under the condition of sodium hydroxide, potassium hydroxide, salt of wormwood or sodium carbonates' presence.
6. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that described aprotic solvent is for comprising tetrahydrofuran (THF), DMSO or DMF.
7. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 1 is characterized in that described highly basic is potassium amide, sodium amide, sodium hydride, potassium tert.-butoxide, potassium ethylate and sodium ethylate by alkaline power successively.
8. the synthetic method of described N-methyl-indoles-3-styrene compound according to claim 7 is characterized in that described highly basic is potassium amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102140055A CN102924358A (en) | 2012-06-27 | 2012-06-27 | N-methyl-indole-3-styrene compound synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102140055A CN102924358A (en) | 2012-06-27 | 2012-06-27 | N-methyl-indole-3-styrene compound synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102924358A true CN102924358A (en) | 2013-02-13 |
Family
ID=47639320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102140055A Pending CN102924358A (en) | 2012-06-27 | 2012-06-27 | N-methyl-indole-3-styrene compound synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924358A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330333A (en) * | 1997-05-29 | 1998-12-15 | Fuji Photo Film Co Ltd | New trisubstituted ethylene compound having cycloheptanylidene structure |
| CN101544591A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | (E)-substituted styrene compound and preparation method thereof |
| CN102167679A (en) * | 2011-01-21 | 2011-08-31 | 东南大学 | Method of synthesizing styryl indole compounds |
| KR20110098673A (en) * | 2010-02-26 | 2011-09-01 | 한양대학교 산학협력단 | Synthesis method of indole derivatives using one-pot cycloisomerization |
-
2012
- 2012-06-27 CN CN2012102140055A patent/CN102924358A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330333A (en) * | 1997-05-29 | 1998-12-15 | Fuji Photo Film Co Ltd | New trisubstituted ethylene compound having cycloheptanylidene structure |
| CN101544591A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | (E)-substituted styrene compound and preparation method thereof |
| KR20110098673A (en) * | 2010-02-26 | 2011-09-01 | 한양대학교 산학협력단 | Synthesis method of indole derivatives using one-pot cycloisomerization |
| CN102167679A (en) * | 2011-01-21 | 2011-08-31 | 东南大学 | Method of synthesizing styryl indole compounds |
Non-Patent Citations (2)
| Title |
|---|
| 戴红等: "反式-6-对氟苯乙烯基吲哚的合成", 《合成化学》, vol. 14, no. 4, 31 December 2006 (2006-12-31), pages 384 - 385 * |
| 靳清贤等: "反式-5-甲氧基-3-苯乙烯基吲哚的合成", 《化学试剂》, vol. 28, no. 6, 31 December 2006 (2006-12-31), pages 373 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103772740B (en) | Phosphonium flame retardant and preparation method thereof | |
| CN103588815B (en) | A kind of preparation method of hexaphenoxy cyclotriphosphazene fire retardant | |
| CN106279104B (en) | A kind of process modification method preparing amber love song Ge Lieting | |
| CN106336435A (en) | Improved hexaphenoxycyclotriphosphazene preparation method | |
| CN103910757A (en) | Bis(4-halogenated phenyl) (3'-phosphonic phenyl)oxophosphines as well as salts and preparation methods thereof | |
| CN108997299B (en) | Efficient long-life organic room-temperature phosphorescent material and preparation method thereof | |
| CN104387367A (en) | Method for preparing disubstituted benzimidazole derivative | |
| CN102167679B (en) | Method of synthesizing styryl indole compounds | |
| CN104860910A (en) | Preparation method of 8-fluoropyran derivative | |
| CN102924358A (en) | N-methyl-indole-3-styrene compound synthesis method | |
| CN104829574A (en) | 8-bromo pyran derivative preparation method | |
| CN104844549A (en) | Preparation method of 7 - bromine pyran derivatives | |
| CN104689849A (en) | Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof | |
| CN104402880A (en) | Preparation method of imidazopyridine derivative | |
| CN105646574A (en) | Synthesizing method of 3-(alkoxy methyl phosphoryl) propionic ester, analogue and phosphinothricin | |
| CN103772433A (en) | Synthetic method of chemiluminescence reagent AMPPD for immunization analysis | |
| CN105294556A (en) | Method for preparing montelukast acid | |
| CN115260455A (en) | Low-temperature long-afterglow polymer based on biphenyl structure and preparation method thereof | |
| CN107814757A (en) | A kind of method for synthesizing polysubstituted pyrrole derivative | |
| CN108727323B (en) | Method for catalytically synthesizing trifluoromethyl substituted homoisoflavone compound by using N-heterocyclic carbene | |
| CN105017146A (en) | Synthetic method for 3,4-dihydro-7-hydroxy-2(1H)-quinolinone | |
| CN103570483A (en) | Preparation method for 3, 5-dithienylethene benzaldehyde | |
| CN103992241A (en) | Preparation method of N-substituted phenyl glycine | |
| CN105198825B (en) | A kind of preparation method of D seromycins | |
| CN102898396A (en) | Method for preparing 3-(4-fluorophenyl)-4-benzyl-2-molindone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130213 |