CN109721593A - The preparation method for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace - Google Patents
The preparation method for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace Download PDFInfo
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Abstract
The preparation method for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics of the invention replace, is related to organic photochromic material, step is: the first step, the synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-；Second step, 1,2- dimethyl -5-R1The synthesis of -3- bromo indole；Third step, the synthesis for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace.The absorbing wavelength red shift of obtained photochromic compound reaches 50~100nm, is the bistable state of heat irreversible, can be applied in terms of optical information storage, anti-counterfeit recognition, hidden material and camouflage material.
Description
Technical field
Technical solution of the present invention is related to organic photochromic material, the hexafluoro ring penta that specifically two heteroaromatics replace
The preparation method of alkenes photochromic compound.
Background technique
Find that diaryl ethylene photochromic compound endurance is good through years of researches such as Japanese professors Irie,
Speed of photoresponse is fast, has the characteristics that heat irreversible, is considered most possibly being developed into the optical information storage material of a new generation
Material, while it is also possible to be applied to the high-technology fields such as the regulation of biomolecule activity light, photoswitch, optical computer.Irie
Professor and other researchers once delivered more survey articles and research paper, such as Chem.Rev.2000, and 100,1685-1716, always
The some synthetic methods and performance introduction of this kind of compound are tied.But it not yet finds about with the such of the infrared optical property of absorption
The report of compound and its synthetic method.Material is stored in optical information with the such photochromic material for absorbing infrared optical property
It can be applied in terms of material, antiforge material, hidden camouflage material and camouflage material, it is therefore necessary to which research and development absorb
The diaryl ethylene photochromic compound of infrared optical property.
Summary of the invention
The technical problems to be solved by the present invention are: providing the hexafluoro cycolpenfene photochrmism chemical combination that two heteroaromatics replace
The preparation method of object, this method introduce special functional group, and synthesized compound absorbing wavelength red shift reaches 50~100nm,
It is the bistable state of heat irreversible, can be answered in terms of optical information storage, anti-counterfeit recognition, hidden material and camouflage material
With.
The present invention solves technical solution used by the technical problem: the hexafluoro cyclopentene class that two heteroaromatics replace is photic
The preparation method of electrochromic compound, steps are as follows:
The first step, the synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
(1) synthesis of the bromo- 2 thiophene carboxaldehyde of 5- methyl -4-
In 1000mL there-necked flask, 0.4mmol 5- methyl -2 thiophene carboxaldehyde is dissolved in 400mL glacial acetic acid, at room temperature
Under stirring, the 200mL glacial acetic acid solution of the bromine containing 0.5mmol is slowly added dropwise, was added dropwise with 9 hours, it is anti-to continue stirring at room temperature
It answers 16 hours, thus obtained reaction solution is poured into 3L saturated sodium carbonate solution, three times with ether extraction, combined ether layer
It is washed with water three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, precipitation obtains the bromo- 2- thiophene of brown solid 5- methyl -4-
Pheno formaldehyde, yield 80%；
(2) synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
Take the first step 1. bromo- 2 thiophene carboxaldehyde of 0.05mmol 5- methyl -4- obtained, 47mL triethyl orthoformate,
100mg p-methyl benzenesulfonic acid is added in 500mL round-bottomed flask, and 150mL dehydrated alcohol is then added, and is stirred 15 hours at room temperature,
It is detected with TLC to raw material point and is disappeared, is extracted with ethyl acetate three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, is taken off
It is molten, obtain the bromo- 2 thiophene carboxaldehyde diethyl acetal of product 5- methyl -4-, yield 79%；
Second step, 1,2- dimethyl -5-R1The synthesis of -3- bromo indole
(1) 2- methyl -5-R1The synthesis of -3- bromo indole
In above formula, R1=H or OCH3,
Under nitrogen protection, by 4mmol 2- methyl -5-R1Indoles, 5mL CH2Cl2, 100mg silica gel be added to 50mL burning
In bottle, it is added with stirring 4mmol NBS, is stirred 30 minutes at room temperature, 30mL water is added in end of reaction, uses CH2Cl2Extraction 3 times,
Precipitation obtains product 2- methyl -5-R1- 3- bromo indole；
(2) 1,2- dimethyl -5-R1The synthesis of -3- bromo indole
In above formula, R1=H or OCH3,
Under nitrogen protection, 3.5mmol 2- methyl -5-R1-3- bromo indole made from second step (1) is dissolved in 10mL
THF is stirred 10 minutes, and 5mmol NaH is added, and is stirred 30 minutes at room temperature, and 5mmol CH is added3It is small to stir 15 at room temperature by I
When, 20mL water is added in end of reaction, is extracted 3 times with ether, and then dry with anhydrous magnesium sulfate, precipitation obtains product 1,2- diformazan
Base -5-R1- 3- bromo indole；
Third step, the synthesis for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace
I.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro
The synthesis of cyclopentene photochromic compound
R in above formula1=H or OCH3,
Under nitrogen protection, by 3.5mmol 1 made from second step (2), 2- dimethyl -5-R1- 3- bromo indole is added
In 50mL flask, 20mL THF is added, under stirring, so that reaction system is cooled to -78 DEG C with liquid nitrogen, the positive fourth of 3.5mmol is added
Base lithium is kept for -78 DEG C, adds 3.5mmol octafluoro cyclopentene, is maintained -78 DEG C to react 4 hours, is warmed to room temperature, TLC detect to
Reaction raw material point disappears substantially, and 20mL water is added, uses CH2Cl2Extraction 3 times, precipitation is separated with silica gel column chromatography, obtains intermediate product
(1- (1,2- dimethyl -5-R1-3- indyl) seven fluorine cyclopentene).
Under nitrogen protection, by the bromo- 2 thiophene carboxaldehyde diethyl acetal of 2.2mmol 5- methyl -4- made from the first step (2)
It is dissolved in 40mL THF, is added in the flask for filling 2.3mmol n-BuLi, reacts 30 minutes under the conditions of stirring and -78 DEG C
Afterwards, 2.4mmol intermediate product obtained above (1- (1,2- dimethyl -5-R is added1- 3- indyl) seven fluorine cyclopentene)
20mL THF solution, being kept for -78 DEG C, the reaction was continued 2 hours, is warmed to room temperature, then react 15 hours, end of reaction, and saturation is added
NH4Cl solution, then be extracted with ethyl acetate, then dry with anhydrous magnesium sulfate, precipitation is separated with silica gel column chromatography, obtains product
1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro cyclopentene is photic
Electrochromic compound, i.e., the F-1 in above-mentioned reaction equation；
II.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro ring penta
The synthesis of alkene photochromic compound
R in above formula1=H or OCH3,
In 250mL there-necked flask, 2.2mmol F-1 is dissolved in 100mL CH2Cl2, it is added with stirring 5 drop percent concentrations
It for 10% dilute HCl and 40mg p-methyl benzenesulfonic acid, is heated to reflux, is detected with TLC, disappear substantially to raw material point, stop reaction, it is cold
But, it is washed three times with saturation NaCl solution, separates organic phase, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From obtaining product 1- (1,2- dimethyl -5-R1-3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro cyclopentene
Photochromic compound, i.e., the F-2 in above-mentioned reaction equation；
III.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene
The synthesis of photochromic compound
R in above formula1=H or OCH3,
In 250mL there-necked flask, 2.0mmol F-2 is dissolved in 100mL THF, adds 2.1mmol azanol, is kept for 25 DEG C
Stirring 4 hours, is detected with TLC, is disappeared substantially to raw material point, stops reaction, and precipitation is extracted with ethyl acetate, with saturation NaCl
Solution washs three times, separates organic phase, then dry with anhydrous magnesium sulfate, and precipitation is separated with silica gel column chromatography, obtains product 1-
(1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- cyano -3- thienyl) photochromic chemical combination of hexafluoro cyclopentene
Object, i.e., the F-3 in above-mentioned reaction equation.
IV.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thiophene
Base) hexafluoro cyclopentene photochromic compound synthesis
R in above formula1=H or OCH3,
In 100mL there-necked flask, 2.0mmol F-2 is dissolved in 50mL THF, 4~5 drop pyridines and 2.1mmol the third two is added
Nitrile is kept for 25 DEG C stir 15 hours, is detected with TLC, disappeared substantially to raw material point, stops reaction, and precipitation is extracted with ethyl acetate
It takes, is washed three times with saturation NaCl solution, separate organic phase, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From obtaining product 1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thiophene
Base) hexafluoro cyclopentene photochromic compound, i.e., the F-4 in above-mentioned reaction equation.
The preparation method for the hexafluoro cycolpenfene photochrmism compounds that above-mentioned two heteroaromatic replaces, raw material used and molten
By commercially available, related operation is known to those skilled in the art for agent.
The beneficial effects of the present invention are:
Compared with prior art, the preparation side for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics of the invention replace
The substantive distinguishing features outstanding of method are that the method for the present invention is used connects aldehyde radical, cyano or dicyanoethenyl suction in heteroaromatic
The hexafluoro cycolpenfene photochrmism compounds absorbing wavelength red shift that two heteroaromatics that obtain synthesized by electric function group replace is
50~100nm, the hexafluoro cyclopentene class that two heteroaromatics than not being connected with these functional groups, or with electron functional group replace
Compound absorbing wavelength red shift wants much farther away.Such as (1, the 2- dimethyl -5- methoxyl group -3- Yin of the 1- as made from following embodiments 8
Diindyl base) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thienyl) photochromic chemical combination of hexafluoro cyclopentene is molten in toluene
Absorbing wavelength is λ max=755nm in liquid, and without electron withdrawing group in corresponding heteroaromatic, or the class with electron donating group
Like the compound of structure, absorbing wavelength is generally λ max=590~600nm in toluene solution.
Compared with prior art, the preparation side for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics of the invention replace
The marked improvement of method is that the hexafluoro cyclopentene light-induced variable of aldehyde radical, cyano or dicyanoethenyl is had in synthesized heteroaromatic
Color compound is in light yellow or khaki in open loop body state, after ultraviolet light, can be changed to green or glaucous closed loop
Body, then with Infrared irradiation, become light yellow or khaki open loop body again again quickly, be the bistable state of heat irreversible, for this purpose, with
Two heteroaromatics made from the method for the present invention replace hexafluoro cycolpenfene photochrmism compounds can be used for optical storage material,
Antiforge material, hidden camouflage material and camouflage material high-technology field.
Specific embodiment
Embodiment 1
1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro cyclopentene
The preparation of photochromic compound
The first step, the synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
(1) synthesis of the bromo- 2 thiophene carboxaldehyde of 5- methyl -4-
In 1000mL there-necked flask, 0.4mmol 5- methyl -2 thiophene carboxaldehyde is dissolved in 400mL glacial acetic acid, at room temperature
Under stirring, the 200mL glacial acetic acid solution of the bromine containing 0.5mmol is slowly added dropwise, was added dropwise with 9 hours, it is anti-to continue stirring at room temperature
It answers 16 hours, thus obtained reaction solution is poured into 3L saturated sodium carbonate solution, three times with ether extraction, combined ether layer
It is washed with water three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, precipitation obtains the bromo- 2- thiophene of brown solid 5- methyl -4-
Pheno formaldehyde, yield 80%；
(2) synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
Take the first step 1. bromo- 2 thiophene carboxaldehyde of 0.05mmol 5- methyl -4- obtained, 47mL triethyl orthoformate,
100mg p-methyl benzenesulfonic acid is added in 500mL round-bottomed flask, and 150mL dehydrated alcohol is then added, and is stirred 15 hours at room temperature,
It is detected with TLC to raw material point and is disappeared, is extracted with ethyl acetate three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, is taken off
It is molten, obtain the bromo- 2 thiophene carboxaldehyde diethyl acetal of product 5- methyl -4-, yield 79%；
Second step, the synthesis of 1,2- dimethyl -3- bromo indole
(1) synthesis of 2- dimethyl -3- bromo indole
Under nitrogen protection, by 4mmol 2 methyl indole, 5mL CH2Cl2, 100mg silica gel is added in 50mL flask, stirs
Lower addition 4mmol NBS is mixed, is stirred at room temperature 30 minutes, 30mL water is added in end of reaction, uses CH2Cl2Extraction 3 times, precipitation must produce
Object 2- dimethyl -3- bromo indole, yield 95%.
The synthesis of (2) 1,2- dimethyl -3- bromo indole
Under nitrogen protection, 3.5mmol 2- methyl -3- bromo indole is dissolved in 10mL THF, stirred 10 minutes, is added
5mmol NaH is stirred at room temperature 30 minutes, and 5mmol CH is added3I is stirred at room temperature 15 hours, end of reaction, and 20mL water is added, and uses
Ether extracts 3 times, then dry with anhydrous magnesium sulfate, and precipitation obtains product 1,2- dimethyl -3- bromo indole, yield 97%.
Third step, 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro
The synthesis of cyclopentene photochromic compound
Under nitrogen protection, by 3.5mmol 1 made from second step (2), 50mL flask is added in 2- dimethyl -3- bromo indole
In, 20mL THF is added, under stirring, so that reaction system is cooled to -78 DEG C with liquid nitrogen, 3.5mmol n-BuLi is added, protect
- 78 DEG C are held, 3.5mmol octafluoro cyclopentene is added, maintains -78 DEG C to react 4 hours, is warmed to room temperature, TLC is detected to reaction raw materials
Point is basic to disappear, and 20mL water is added, uses CH2Cl2Extraction 3 times, precipitation is separated with silica gel column chromatography, obtains intermediate product (1- (1,2-
Dimethyl -3- indyl) seven fluorine cyclopentene)；Under nitrogen protection, 2.2mmol5- methyl -4- made from the first step (2) is bromo-
2 thiophene carboxaldehyde diethyl acetal is dissolved in 40mL THF, is added under the conditions of stirring and -78 DEG C and fills 2.3mmol n-BuLi
In flask, after reaction 30 minutes, 2.4mmol intermediate product obtained above (1- (1,2- dimethyl -3- indyl) seven fluorine are added
Cyclopentene) 20mL THF solution, keep -78 DEG C the reaction was continued 2 hours, be warmed to room temperature, then react 15 hours, end of reaction,
Saturation NH is added4Cl solution, then be extracted with ethyl acetate, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From obtaining product 1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro
Cyclopentene photochromic compound, i.e., the F-1a in above-mentioned reaction equation, yield 78%.
59~62 DEG C of .1HNMR (400MHz, DMSO) δ: 7.40-7.38 (d, J=8.8Hz, 1H) of MP, 7.10 (s, 1H),
6.81-6.77 (d, J=8.5Hz, 1H), 6.68 (s, 1H), 5.69 (s, 1H), 3.64 (s, 3H), 3.51-3.42 (m, 4H),
2.00 (s, 3H), 1.13-1.10 (t, J=7.0Hz, 6H), HRMS (ESI) m/z:[M+H]+472.1009. λ max=612nm
(toluene).
Embodiment 2
1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro cyclopentene light-induced variable
The preparation of color compound
The first step, with embodiment 1；
Second step, with embodiment 1；
Third step, 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro cyclopentene
The synthesis of photochromic compound
In 250mL there-necked flask, F-1a made from 2.2mmol embodiment 1 is dissolved in 100mLCH2Cl2, it is added with stirring 5
Dilute HCl and 40mg p-methyl benzenesulfonic acid that percent concentration is 10% is dripped, is heated to reflux, is detected with TLC, disappeared substantially to raw material point
It loses, stops reaction, it is cooling, it is washed three times with saturation NaCl solution, separates organic phase, then dry with anhydrous magnesium sulfate, precipitation,
It is separated with silica gel column chromatography, obtains product 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) six
Fluorine cyclopentene photochromic compound, i.e., the F-2a in above-mentioned reaction equation, yield 75%.
162~163 DEG C of .1HNMR (400MHz, CDCl3) δ: 9.84 (s, 1H) of MP, 7.82 (s, 1H), 7.55-7.53 (d,
J=8.0Hz, 1H), 7.29-7.28 (d, J=8.1Hz, 1H), 7.24-7.22 (d, J=8.3Hz, 1H), 7.16-7.12 (t, J
=7.5Hz, 6H), 3.64 (s, 3H), 2.00 (s, 3H), 1.87 (s, 3H) .HRMS (ESI) m/z:[M+H]+444.0851. λ max
=653nm (toluene).
Embodiment 3
1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene is photochromic
The preparation of compound
The first step, with embodiment 1；
Second step, with embodiment 1；
Third step, 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene light
Cause the synthesis of electrochromic compound
In 250mL there-necked flask, F-2a made from 2.0mmol embodiment 2 is dissolved in 100mL THF, adds 2.1mmol
Azanol is kept for 25 DEG C stir 4 hours, is detected with TLC, disappeared substantially to raw material point, stops reaction, and precipitation is extracted with ethyl acetate
It takes, is washed three times with saturation NaCl solution, separate organic phase, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From it is photochromic to obtain product 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene
Compound, i.e., the F-3a in above-mentioned reaction equation, yield 76%.
214~216 DEG C of .1HNMR (400MHz, CDCl3) δ: 7.70 (s, 1H) of MP, 7.45 (d, J=8.3Hz, 1H),
7.35-7.31 (m, 4H), 7.25-7.09 (m, 2H), 3.70 (s, 3H), 2.10 (s, 3H), 1.90 (s, 3H) .HRMS (ESI) m/
Z:[M+H]+440.0775. λ max=628nm (toluene).
Embodiment 4
1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thienyl) hexafluoro
The preparation of cyclopentene photochromic compound
The first step, with embodiment 1；
Second step, with embodiment 1；
Third step 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thiophene
Base) hexafluoro cyclopentene photochromic compound synthesis
In 100mL there-necked flask, F-2a made from 2.0mmol embodiment 3 is dissolved in 50mL THF, be added 4 drop pyridines and
2.1mmol malononitrile is kept for 25 DEG C stir 15 hours, is detected with TLC, disappeared substantially to raw material point, stops reaction, and precipitation is used
Ethyl acetate extraction is washed three times with saturation NaCl solution, separates organic phase, and then dry with anhydrous magnesium sulfate, precipitation uses silicon
Plastic column chromatography separation, obtains product 1- (1,2- dimethyl -3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3-
Thienyl) hexafluoro cyclopentene photochromic compound, i.e., the F-4a in above-mentioned reaction equation, yield 85%.
194~195 DEG C of .1HNMR (400MHz, CDCl3) δ: 7.80 (s, 1H) of MP, 7.76 (s, 1H), 7.52-7.49 (d,
J=7.9Hz, 1H), 7.35-7.33 (d, J=8.1Hz, 1H), 7.28-7.26 (d, J=8.1Hz, 1H), 7.19-7.15 (t, J
=7.4Hz, 3H), 3.69 (s, 3H), 2.06 (s, 3H), 1.97 (s, 3H) .HRMS (ESI) m/z:[M+H]+492.0964. λ max
=748nm (toluene).
Embodiment 5
1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) six
The preparation of fluorine cyclopentene photochromic compound
The first step, the synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
With embodiment 1.
Second step, the synthesis of 1,2- dimethyl -5- methoxyl group -3- bromo indole
(1) synthesis of 2- methyl -5- methoxyl group -3- bromo indole
Under nitrogen protection, by 4mmol 2- methyl -5- methoxy-Indole, 5mL CH2Cl2It is added to 100mg silica gel
In 50mL flask, it is added with stirring 4mmol NBS, is stirred 30 minutes at room temperature, 30mL water is added in end of reaction, uses CH2Cl2Extraction
It takes 3 times, precipitation, obtains product 2- methyl -5- methoxyl group -3- bromo indole, yield 93%.
The synthesis of (2) 1,2- dimethyl -5- methoxyl group -3- bromo indole
Under nitrogen protection, 3.5mmol 2- methyl -5- methoxyl group -3- bromo indole made from second step (1) is dissolved in
10mL THF is stirred 10 minutes, and 5mmol NaH is added, and is stirred 30 minutes at room temperature, and 5mmol CH is added3I is stirred at room temperature
15 hours, 20mL water was added in end of reaction, was extracted 3 times with ether, and then dry with anhydrous magnesium sulfate, precipitation obtains product 1,2-
Dimethyl -5- methoxyl group -3- bromo indole, yield 91%.
Third step, 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thiophene
Pheno base) hexafluoro cyclopentene photochromic compound synthesis
Under nitrogen protection, by 3.5mmol 1 made from second step (2), 2- dimethyl -5- methoxyl group -3- bromo indole adds
Enter in 50mL flask, add 20mL THF, under stirring, so that reaction system is cooled to -78 DEG C with liquid nitrogen, 3.5mmol is being added just
Butyl lithium is kept for -78 DEG C, adds 3.5mmol octafluoro cyclopentene, is maintained -78 DEG C to react 4 hours, is warmed to room temperature, TLC detection
It disappears substantially to reaction raw material point, 20mL water is added, uses CH2Cl2Extraction 3 times, precipitation is separated with silica gel column chromatography, obtains intermediate production
Object (1- (1,2- dimethyl -5- methoxyl group -3- indyl) seven fluorine cyclopentene)；Under nitrogen protection, the first step (2) is obtained
The bromo- 2 thiophene carboxaldehyde diethyl acetal of 2.2mmol 5- methyl -4- is dissolved in 40mL THF, is added under the conditions of stirring and -78 DEG C
In the flask for filling 2.3mmol n-BuLi, reaction 30 minutes after, be added 2.4mmol intermediate product obtained above (1- (1,
2- dimethyl -5- methoxyl group -3- indyl) seven fluorine cyclopentene) 20mL THF solution, keep -78 DEG C the reaction was continued 2 hours,
It is warmed to room temperature, then reacts 15 hours, end of reaction, saturation NH is added4Cl solution, then be extracted with ethyl acetate, then with anhydrous
Magnesium sulfate is dry, and precipitation is separated with silica gel column chromatography, obtains product 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2-
Methyl -5- diethoxymethyl -3- thienyl) hexafluoro cyclopentene photochromic compound, i.e., the F-1b in above-mentioned reaction equation produces
Rate is 83%.
56~57 DEG C of .1HNMR (400MHz, DMSO) δ: 7.42-7.39 (d, J=8.9Hz, 1H) of MP, 7.12 (s, 1H),
6.83-6.79 (d, J=8.8Hz, 1H), 6.71 (s, 1H), 5.70 (s, 1H), 3.69 (s, 3H), 3.66 (s, 3H), 3.56-
3.45 (m, 4H), 2.08 (s, 3H), 1.15-1.11 (t, J=7.0Hz, 6H), HRMS (ESI) m/z:[M+H]+502.1279. λ
Max=602nm (toluene).
Embodiment 6
1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro ring penta
The preparation of alkene photochromic compound
The first step, with embodiment 5；
Second step, with embodiment 5；
Third step, 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl)
The synthesis of hexafluoro cyclopentene photochromic compound
In 250mL there-necked flask, F-1b made from 2.2mmol embodiment 5 is dissolved in 100mLCH2Cl2, it is added with stirring 5
Dilute HCl and 40mg p-methyl benzenesulfonic acid that percent concentration is 10% is dripped, is heated to reflux, is detected with TLC, disappeared substantially to raw material point
It loses, stops reaction, it is cooling, it is washed three times with saturation NaCl solution, separates organic phase, then dry with anhydrous magnesium sulfate, precipitation,
It is separated with silica gel column chromatography, obtains product 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- formoxyl -3-
Thienyl) hexafluoro cyclopentene photochromic compound, i.e., the F-2b in above-mentioned reaction equation, yield 83%.
158~159 DEG C of .1HNMR (400MHz, CDCl3) δ: 9.77 (s, 1H) of MP, 7.76 (s, 1H), 7.10-7.08 (d,
J=8.9Hz, 1H), 6.89 (s, 1H), 6.82-6.79 (d, J=9.8Hz, 1H), 3.73 (s, 3H), 3.54 (s, 3H), 1.91
(s, 3H), 1.80 (s, 3H) .HRMS (ESI) m/z:[M+H]+474.0957. λ max=702nm (toluene).
Embodiment 7
1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene
The preparation of photochromic compound
The first step, with embodiment 5；
Second step, with embodiment 5；
Third step, 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) six
The synthesis of fluorine cyclopentene photochromic compound
In 250mL there-necked flask, F-2b made from 2.0mmol embodiment 6 is dissolved in 100mL THF, adds 2.1mmol
Azanol is kept for 25 DEG C stir 4 hours, is detected with TLC, disappeared substantially to raw material point, stops reaction, and precipitation is extracted with ethyl acetate
It takes, is washed three times with saturation NaCl solution, separate organic phase, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From obtaining product 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro ring penta
F-3b in alkene photochromic compound, that is, above-mentioned reaction equation, yield 85%.
150~151 DEG C of .1HNMR (400MHz, CDCl3) δ: 7.68 (s, 1H) of MP, 7.18-7.16 (d, J=8.7Hz,
1H), 6.89 (s, 1H), 6.87-6.86 (d, J=8.9Hz, 1H), 3.79 (s, 3H), 3.62 (s, 3H), 1.99 (s, 3H), 1.86
(s, 3H) .HRMS (ESI) m/z:[M+H]+471.0966. λ max=672nm (toluene).
Embodiment 8
1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thiophene
Pheno base) the photochromic chemical combination of hexafluoro cyclopentene preparation
The first step, with embodiment 5；
Second step, with embodiment 5；
Third step, 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- (2,2- dicyanoethylenes
Base) -3- thienyl) the photochromic chemical combination of hexafluoro cyclopentene synthesis
In 100mL there-necked flask, F-2b made from 2.0mmol embodiment 6 is dissolved in 50mL THF, be added 5 drop pyridines and
2.1mmol malononitrile is kept for 25 DEG C stir 15 hours, is detected with TLC, disappeared substantially to raw material point, stops reaction, and precipitation is used
Ethyl acetate extraction is washed three times with saturation NaCl solution, separates organic phase, and then dry with anhydrous magnesium sulfate, precipitation uses silicon
Plastic column chromatography separation, obtains product 1- (1,2- dimethyl -5- methoxyl group -3- indyl) -2- (2- methyl -5- (2,2- dicyano second
Alkenyl) -3- thienyl) the photochromic chemical combination of hexafluoro cyclopentene, i.e., the F-4b in above-mentioned reaction equation, yield 76%.
189~192 DEG C of .1HNMR (400MHz, CDCl3) δ: 7.73 (s, 1H) of MP, 7.56 (s, 1H), 7.42-7.40 (d,
J=7.5Hz, 1H), 7.31-7.29 (d, J=7.9Hz, 1H), 7.26-7.23 (d, J=7.5Hz, 1H), 7.15-7.12 (t, J
=7.1Hz, 3H), 3.71 (s, 3H), 3.65 (s, 3H), 2.01 (s, 3H), 1.95 (s, 3H) .HRMS (ESI) m/z:[M+H]+
522.1234. λ max=755nm (toluene).
In above-mentioned all embodiments, by commercially available, related operation is this technology for raw material used and solvent
Known to the those of ordinary skill in field.
Claims (1)
1. the preparation method for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace, it is characterised in that steps are as follows:
The first step, the synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
(1) synthesis of the bromo- 2 thiophene carboxaldehyde of 5- methyl -4-
In 1000mL there-necked flask, 0.4mmol 5- methyl -2 thiophene carboxaldehyde is dissolved in 400mL glacial acetic acid, is stirred at room temperature
Under, the 200mL glacial acetic acid solution of the bromine containing 0.5mmol is slowly added dropwise, was added dropwise with 9 hours, continues to be stirred to react 16 at room temperature
Hour, thus obtained reaction solution is poured into 3L saturated sodium carbonate solution, three times with ether extraction, combined ether layer water
It washes three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, precipitation obtains the bromo- 2- thiophene first of brown solid 5- methyl -4-
Aldehyde, yield 80%；
(2) synthesis of the bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-
Take the first step 1. bromo- 2 thiophene carboxaldehyde of 0.05mmol 5- methyl -4- obtained, 47mL triethyl orthoformate, 100mg pairs
Toluenesulfonic acid is added in 500mL round-bottomed flask, and 150mL dehydrated alcohol is then added, and is stirred 15 hours, is examined at room temperature with TLC
It surveys to raw material point and disappears, be extracted with ethyl acetate three times, it is then dry with anhydrous magnesium sulfate, desiccant is filtered off, precipitation obtains product
The bromo- 2 thiophene carboxaldehyde diethyl acetal of 5- methyl -4-, yield 79%；
Second step, the synthesis of 1,2- dimethyl -5-R1-3- bromo indole
(1) 2- methyl -5-R1The synthesis of -3- bromo indole
In above formula, R1=H or OCH3,
Under nitrogen protection, by 4mmol 2- methyl -5-R1Indoles, 5mL CH2Cl2, 100mg silica gel is added in 50mL flask,
It is added with stirring 4mmol NBS, is stirred 30 minutes at room temperature, 30mL water is added in end of reaction, uses CH2Cl2Extraction 3 times, precipitation,
Obtain product 2- methyl -5-R1- 3- bromo indole；
(2) 1,2- dimethyl -5-R1The synthesis of -3- bromo indole
In above formula, R1=H or OCH3,
Under nitrogen protection, by 3.5mmol 2- methyl -5-R made from second step (1)1- 3- bromo indole is dissolved in 10mL THF, stirs
It mixes 10 minutes, 5mmol NaH is added, stir 30 minutes at room temperature, 5mmol CH is added3I is stirred 15 hours at room temperature, reaction
It finishes, 20mL water is added, extracted 3 times with ether, then dry with anhydrous magnesium sulfate, precipitation obtains product 1,2- dimethyl -5-
R1- 3- bromo indole；
Third step, the synthesis for the hexafluoro cycolpenfene photochrmism compounds that two heteroaromatics replace
I.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro ring penta
The synthesis of alkene photochromic compound
R in above formula1=H or OCH3,
Under nitrogen protection, by 3.5mmol 1 made from second step (2), 2- dimethyl -5-R150mL flask is added in -3- bromo indole
In, 20mL THF is added, under stirring, so that reaction system is cooled to -78 DEG C with liquid nitrogen, 3.5mmol n-BuLi is added, protect
- 78 DEG C are held, 3.5mmol octafluoro cyclopentene is added, maintains -78 DEG C to react 4 hours, is warmed to room temperature, TLC is detected to reaction raw materials
Point is basic to disappear, and 20mL water is added, uses CH2Cl2Extraction 3 times, precipitation is separated with silica gel column chromatography, obtains intermediate product (1- (1,2-
Dimethyl -5-R1-3- indyl) seven fluorine cyclopentene).
Under nitrogen protection, the bromo- 2 thiophene carboxaldehyde diethyl acetal of 2.2mmol 5- methyl -4- made from the first step (2) is dissolved in
40mL THF is added in the flask for filling 2.3mmol n-BuLi under the conditions of stirring and -78 DEG C, after reaction 30 minutes, is added
Enter 2.4mmol intermediate product obtained above (1- (1,2- dimethyl -5-R1- 3- indyl) seven fluorine cyclopentene) 20mL THF
Solution, being kept for -78 DEG C, the reaction was continued 2 hours, is warmed to room temperature, then react 15 hours, end of reaction, and saturation NH is added4Cl solution,
It is extracted with ethyl acetate again, then dry with anhydrous magnesium sulfate, precipitation is separated with silica gel column chromatography, obtains product 1- (1,2- diformazan
Base -5-R1- 3- indyl) -2- (2- methyl -5- diethoxymethyl -3- thienyl) hexafluoro cyclopentene photochromic compound,
F-1 in i.e. above-mentioned reaction equation；
II.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro cyclopentene is photic
The synthesis of electrochromic compound
R in above formula1=H or OCH3,
In 250mL there-necked flask, 2.2mmol F-1 is dissolved in 100mL CH2Cl2, being added with stirring 5 drop percent concentrations is
10% dilute HCl and 40mg p-methyl benzenesulfonic acid, is heated to reflux, is detected with TLC, disappears substantially to raw material point, stops reaction, cold
But, it is washed three times with saturation NaCl solution, separates organic phase, then dry with anhydrous magnesium sulfate, precipitation, with silica gel column chromatography point
From obtaining product 1- (1,2- dimethyl -5-R1-3- indyl) -2- (2- methyl -5- formoxyl -3- thienyl) hexafluoro cyclopentene
Photochromic compound, i.e., the F-2 in above-mentioned reaction equation；
III.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene is photic
The synthesis of electrochromic compound
R in above formula1=H or OCH3,
In 250mL there-necked flask, 2.0mmol F-2 is dissolved in 100mL THF, adds 2.1mmol azanol, keeps 25 DEG C of stirrings
It 4 hours, is detected with TLC, is disappeared substantially to raw material point, stop reaction, precipitation is extracted with ethyl acetate, with saturation NaCl solution
Washing three times, separates organic phase, then dry with anhydrous magnesium sulfate, and precipitation is separated with silica gel column chromatography, obtains product 1- (1,2-
Dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- cyano -3- thienyl) hexafluoro cyclopentene photochromic compound, i.e., on
State the F-3 in reaction equation.
IV.1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thienyl) six
The synthesis of fluorine cyclopentene photochromic compound
R in above formula1=H or OCH3,
In 100mL there-necked flask, 2.0mmol F-2 is dissolved in 50mL THF, 4~5 drop pyridines and 2.1mmol malononitrile is added,
It is kept for 25 DEG C stir 15 hours, is detected with TLC, disappeared substantially to raw material point, stop reaction, precipitation is extracted with ethyl acetate, and uses
It is saturated NaCl solution washing three times, separates organic phase, then dry with anhydrous magnesium sulfate, precipitation is separated with silica gel column chromatography, obtained
Product 1- (1,2- dimethyl -5-R1- 3- indyl) -2- (2- methyl -5- (2,2- dicyanoethenyl) -3- thienyl) hexafluoro
Cyclopentene photochromic compound, i.e., the F-4 in above-mentioned reaction equation.
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| CN113620940B (en) * | 2021-08-18 | 2023-12-15 | 北京化工大学 | Preparation of near-infrared absorption amphiphilic diaryl alkene photochromic molecules and application of amphiphilic diaryl alkene photochromic molecules in reversible photothermal and photoacoustic applications |
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