CN102993155B - Preparation method of polysubstituted-diarylnaphthopyran photochromic compounds - Google Patents
Preparation method of polysubstituted-diarylnaphthopyran photochromic compounds Download PDFInfo
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- CN102993155B CN102993155B CN201110275393.3A CN201110275393A CN102993155B CN 102993155 B CN102993155 B CN 102993155B CN 201110275393 A CN201110275393 A CN 201110275393A CN 102993155 B CN102993155 B CN 102993155B
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Abstract
The invention relates to organic photochromic materials, particularly a preparation method of polysubstituted-diarylnaphthopyran photochromic compounds, which comprises the following steps: 1. synthesis of naphthopyranyl-2-one; and 2. synthesis of polysubstituted-diarylnaphthopyrane photochromic compounds. The structural general formula of the prepared polysubstituted-diarylnaphthopyrane photochromic compounds is disclosed in the specification. In the method, high boiling solvents THF (tetrahydrofuran) and toluene are used in the reaction process and heating is performed under reflux in a dark place, so the completion of the final cyclization dehydration reaction is ensured, and the yield is enhanced to 40-60%.
Description
Technical field
Technical scheme of the present invention relates to organic photochromic material, specifically the preparation method of polysubstituted-diaryl naphthopyran class photochromic compound.
Background technology
Polysubstituted-diaryl naphthopyran class photochromic compound have solid-state and liquid state all can discoloration, variable color and colour killing speed slow, bright in luster, mostly be beautiful redness and the high feature of productive rate, be widely used in optical storage material, the light regulation and control of biomolecule activity, photochromic computer, allochroic clothes and the high-technology field such as ornaments and light-sensitive sunglasses.
SCI (2000; 21 (5) .717-720) and CN1634916 in disclose 2; 2-diaryl naphthopyran compounds and preparation method thereof; Tetrahedron (2006; 62; 4900-4906) describe again such photochromic compound nanoassemble character and photochromic properties; but it is not high to adopt above preparation method to synthesize the productive rate of such photochromic compound; be generally the productive rate of 10% ~ 30%, the demand of above-mentioned new technical field fast development can not be met.
Prior art polysubstituted-preparation method of diaryl naphthopyran class photochromic compound adopts in reaction process is low boiling point solvent ether, although ether has been the best solvent of grignard reaction, can ensure that synthesis grignard reagent has higher productive rate, but when utilizing grignard reagent to carry out next step pass ring dehydration reaction, temperature can not be high, and too high grignard reagent easily forms linked reaction.But for pass this step of ring dehydration reaction, again must under relatively hot conditions, what close that ring dehydration reaction just carries out is more complete.Exactly because the boiling point of ether is low, low the making of temperature finally closes ring dehydration reaction not exclusively, and cause productive rate to reduce, general productive rate is 10 ~ 30%.
The present invention is polysubstituted-and the preparation method of diaryl naphthopyran class photochromic compound is for the shortcoming of prior art, have employed and change high boiling solvent twice in reaction process, namely first in the ring dehydration reaction of pass, use high boiling THF for solvent, pass ring dehydration reaction is made to be able to carry out substantially completely, then using high boiling toluene instead is solvent, lucifuge reflux simultaneously, ensures that not completing pass ring dehydration reaction intermediate all can complete pass ring dehydration reaction.Pass through theoretical research and repeatedly practise and also shown that pass this step of ring dehydration reaction must first select THF to be solvent, and can not first select toluene to be solvent.This is because first select toluene to be that solvent will be favourable to linked reaction, most of grignard reagent has carried out linked reaction, causes the productive rate of product very low, even can not obtain product.And first select THF to be solvent, after pass ring dehydration reaction completes substantially, to be solvent extract the product be obtained by reacting and the intermediate product that not yet completes pass ring dehydration reaction to replacing toluene again, the high boiling point of recycling toluene, lucifuge reflux, ensure that not completing the intermediate product closing ring dehydration reaction all can complete pass ring dehydration reaction, thus improve its productive rate further.Lucifuge then avoids the carrying out that ring dehydration reaction is closed in the photochemical reaction impact occurred under light illumination.
The present invention is polysubstituted-and the outstanding marked improvement of the preparation method of diaryl naphthopyran class photochromic compound is: have employed and change high boiling solvent twice in reaction process, productive rate is made to bring up to 40 ~ 60%, far above the productive rate of 10 ~ 30% of prior art, to meet relevant high-technology field development increasing the demand of polysubstituted-diaryl naphthopyran class photochromic compound further.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method providing polysubstituted-diaryl naphthopyran class photochromic compound, adopt the method changing high boiling solvent THF and toluene in reaction process for twice, lucifuge reflux, ensure completing of last pass ring dehydration reaction, make productive rate bring up to 40 ~ 60%.
The present invention solves this technical problem adopted technical scheme: the preparation method of polysubstituted-diaryl naphthopyran class photochromic compound, and its step is as follows:
The first step, the synthesis of aphthopyrans-2-ketone
In 100ml there-necked flask, add 0.1mol2-hydroxyl-1-naphthaldehyde, 0.2mol anhydrous acetic acid acid anhydride, 0.2mol anhydrous sodium acetate, be warming up to 160 DEG C, reflux 6 hours, TLC tracking monitor, after question response object point disappears, stop heating, after cooling, adding mass percent concentration is in the aqueous sodium carbonate of 10% and unreacted diacetyl oxide, regulate pH to 6.8 ~ 7.2, add chloroform, dissolve the solid generated, separatory, with anhydrous magnesium sulfate drying, filter, boil off chloroform, add sherwood oil, generation is precipitated, filter, solid drying, m.p.115 DEG C ~ 116 DEG C of products therefrom aphthopyrans-2-ketone, productive rate is 88%,
Second step, polysubstituted-diaryl naphthopyran photochromic compound synthesis
In the structural formula of above-claimed cpd:
When
time,
Have: R
1=H and R
2=4-SCH
3, R
1=H and R
2=4-OCH
3, R
1=2-OCH
3and R
2=4-OCH
3, R
1=2-OCH
3and R
2=4-CH
3, R
1=2-OCH
3and R
2=4-Cl, R
1=2-CH
3and R
2=4-F, R
1=2-OC
6h
13-n and R
2=4-OC
6h
13-n or R
1=2-OC
8h
17-n and R
2=4-OC
8h
17-n;
When
Have: R
1=R
2=H,
1. under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the R shown in the above-mentioned reaction equation of 0.05 ~ 0.07mol
1(R
2)-M aryl replaces the 30ml anhydrous ether solution of bromide, just do not have magnesium chips, and added a microgram iodine, under stirring, warm reaction flask, to initiation reaction, then drips the R shown in remaining above-mentioned reaction equation
1(R
2)-M aryl replaces the 30ml anhydrous ether solution of bromide, dropwise, reflux 0.5 ~ 1 hour, obtain R
1(R
2)-M-MgBr, 2. the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan is then dripped, dropwise, continue backflow 4 ~ 8 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, 3. toluene extraction is for several times added, until it is colourless for extracting the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4to filter after dry, then lucifuge backflow 2 ~ 5 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained above-mentioned polysubstituted-diaryl replaces photochromic compound of naphtho-pyrans product.
Above-mentioned polysubstituted-preparation method of diaryl naphthopyran class photochromic compound in, used amount of substance expand by equal proportion or reduce do not affect final obtained polysubstituted-diaryl naphthopyran photochromic compound product.
Above-mentioned polysubstituted-preparation method of diaryl naphthopyran class photochromic compound in, the Chinese of described THF is tetrahydrofuran (THF).
Above-mentioned polysubstituted-preparation method of diaryl naphthopyran class photochromic compound in, used raw material reaction thing and solvent are all by commercially available.
Above-mentioned polysubstituted-preparation method of diaryl naphthopyran class photochromic compound in, the apparatus adopted and operating procedure are all known by those skilled in the art.
The invention has the beneficial effects as follows:
The present invention is polysubstituted-and the outstanding substantive distinguishing features of the preparation method of diaryl naphthopyran class photochromic compound is:
Embodiment
Embodiment 1
Preparation 2,2-bis-(4-methylthio group phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
In 100ml there-necked flask, add 0.1mol2-hydroxyl-1-naphthaldehyde, 0.2mol anhydrous acetic acid acid anhydride, 0.2mol anhydrous sodium acetate, be warming up to 160 DEG C, reflux 6 hours, TLC tracking monitor, after question response object point disappears, stop heating, after cooling, adding mass percent concentration is in the aqueous sodium carbonate of 10% and unreacted diacetyl oxide, regulate pH to 7, add chloroform, dissolve the solid generated, separatory, with anhydrous magnesium sulfate drying, filter, boil off chloroform, add sherwood oil, produce precipitation, filter, solid drying, m.p.115 ~ 116 DEG C of products therefrom aphthopyrans-2-ketone, productive rate is 88%.
Second step, the synthesis of 2,2-bis-(4-methylthio group phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution to methylthio group bromobenzene shown in the above-mentioned reaction equation of 0.05mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution to methylthio group bromobenzene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 0.5 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 4 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 2 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(4-methylthio group phenyl) photochromic compound of naphtho-pyrans product, productive rate is 56%.
Embodiment 2
Preparation 2,2-bis-(4-p-methoxy-phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(4-p-methoxy-phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution to methoxybromobenzene shown in the above-mentioned reaction equation of 0.06mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution to methoxybromobenzene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 0.7 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 4.5 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 3 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(4-p-methoxy-phenyl) photochromic compound of naphtho-pyrans product, productive rate is 60%.
Embodiment 3
Preparation 2,2-bis-(2,4-p-methoxy-phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2,4-p-methoxy-phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add 2 shown in the above-mentioned reaction equation of 0.055mol, the 30ml anhydrous ether solution of 4-dimethoxy bromobenzene, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then 2 shown in remaining above-mentioned reaction equation are dripped, the 30ml anhydrous ether solution of 4-dimethoxy bromobenzene, dropwise, reflux 1 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 6 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 4 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2,4-p-methoxy-phenyl) photochromic compound of naphtho-pyrans product, productive rate is 42%.
Embodiment 4
Preparation 2,2-bis-(2-methoxyl group-4-aminomethyl phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2-methoxyl group-4-aminomethyl phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution of the 2-methoxyl group-4-methyl bromobenzene shown in the above-mentioned reaction equation of 0.05mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution of the 2-methoxyl group-4-methyl bromobenzene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 1 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 7 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 4 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2-methoxyl group-4-aminomethyl phenyl) photochromic compound of naphtho-pyrans product, productive rate is 43%.
Embodiment 5
Preparation 2,2-bis-(2-methoxyl group-4-chloro-phenyl-) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2-methoxyl group-4-chloro-phenyl-) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution of the 2-methoxyl group-4-chloro-bromobenzene shown in the above-mentioned reaction equation of 0.06mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution of the 2-methoxyl group-4-chloro-bromobenzene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 0.8 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 5 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 4 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2-methoxyl group-4-chloro-phenyl-) photochromic compound of naphtho-pyrans product, productive rate is 53%.
Embodiment 6
Preparation 2,2-bis-(2-methyl-4-fluorophenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2-methyl-4-fluorophenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution of the 2-methyl-4-bromofluorobenzene shown in the above-mentioned reaction equation of 0.05mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution of the 2-methyl-4-bromofluorobenzene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 1 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 5 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 4 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2-methyl-4-fluorophenyl) photochromic compound of naphtho-pyrans product, productive rate is 55%.
Embodiment 7
Preparation 2,2-bis-(2,4-bis-normal hexane oxygen base phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2,4-bis-normal hexane oxygen base phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add 2 shown in the above-mentioned reaction equation of 0.05mol, the 30ml anhydrous ether solution of 4-bis-normal hexane methoxyl bromobenzene, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then 2 shown in remaining above-mentioned reaction equation are dripped, the 30ml anhydrous ether solution of 4-bis-normal hexane methoxyl bromobenzene, dropwise, reflux 1 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 8 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 5 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2,4-bis-normal hexane oxygen base phenyl) photochromic compound of naphtho-pyrans product, productive rate is 48%.
Embodiment 8
Preparation 2,2-bis-(2,4-bis-octane oxygen base phenyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2,4-bis-octane oxygen base phenyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add 2 shown in the above-mentioned reaction equation of 0.05mol, the 30ml anhydrous ether solution of 4-bis-octane methoxyl bromobenzene, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then 2 shown in remaining above-mentioned reaction equation are dripped, the 30ml anhydrous ether solution of 4-bis-octane methoxyl bromobenzene, dropwise, reflux 1 hour, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 7 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 5 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2,4-bis-octane oxygen base phenyl) photochromic compound of naphtho-pyrans product, productive rate is 53%.
Embodiment 9
Preparation 2,2-bis-(2-thienyl) aphthopyrans
The first step, the synthesis of aphthopyrans-2-ketone
With embodiment 1;
Second step, the synthesis of 2,2-bis-(2-thienyl) aphthopyrans
Under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the 30ml anhydrous ether solution of the 2-bromothiophene shown in the above-mentioned reaction equation of 0.07mol, just do not have magnesium chips, add a microgram iodine, under stirring, warm reaction flask is to initiation reaction, then the 30ml anhydrous ether solution of the 2-bromothiophene shown in remaining above-mentioned reaction equation is dripped, dropwise, reflux 40 minutes, right Hou drips the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan, dropwise, continue backflow 5 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, to in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, add toluene extraction for several times, until it is substantially colourless to extract the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4filter after dry, then lucifuge refluxes 4 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained 2,2-bis-(2-thienyl) photochromic compound of naphtho-pyrans product, productive rate is 59%.
In above-mentioned all embodiments, used raw material reaction thing and solvent are all by commercially available.
In above-mentioned all embodiments, the apparatus adopted and operating procedure are all known by those skilled in the art.
Claims (1)
1. the preparation method of polysubstituted-diaryl naphthopyran class photochromic compound, is characterized in that step is as follows:
The first step, the synthesis of aphthopyrans-2-ketone
In 100ml there-necked flask, add 0.1mol 2-hydroxyl-1-naphthaldehyde, 0.2mol anhydrous acetic acid acid anhydride, 0.2mol anhydrous sodium acetate, be warming up to 160 DEG C, reflux 6 hours, TLC tracking monitor, after question response object point disappears, stop heating, after cooling, adding mass percent concentration is in the aqueous sodium carbonate of 10% and unreacted diacetyl oxide, regulate pH to 6.8 ~ 7.2, add chloroform, dissolve the solid generated, separatory, with anhydrous magnesium sulfate drying, filter, boil off chloroform, add sherwood oil, generation is precipitated, filter, solid drying, m.p.115 DEG C ~ 116 DEG C of products therefrom aphthopyrans-2-ketone, productive rate is 88%,
Second step, polysubstituted-diaryl naphthopyran photochromic compound synthesis
In the structural formula of above-claimed cpd:
When
time,
Have: R
1=H and R
2=4-SCH
3, R
1=H and R
2=4-OCH
3, R
1=2-OCH
3and R
2=4-OCH
3, R
1=2-OCH
3and R
2=4-CH
3, R
1=2-OCH
3and R
2=4-Cl, R
1=2-CH
3and R
2=4-F, R
1=2-OC
6h
13-n and R
2=4-OC
6h
13-n or R
1=2-OC
8h
17-n and R
2=4-OC
8h
17-n;
When
time,
Have: R
1=R
2=H,
1. under nitrogen protection, in dried 150ml there-necked flask, add 0.05mol magnesium chips, add the R shown in the above-mentioned reaction equation of 0.05 ~ 0.07mol
1(R
2)-M aryl replaces the 30ml anhydrous ether solution of bromide, just do not have magnesium chips, and added a microgram iodine, under stirring, warm reaction flask, to initiation reaction, then drips the R shown in remaining above-mentioned reaction equation
1(R
2)-M aryl replaces the 30ml anhydrous ether solution of bromide, dropwise, reflux 0.5 ~ 1 hour, obtain R
1(R
2)-M-MgBr, 2. the 0.02mol aphthopyrans-2-ketone solution obtained by the above-mentioned the first step be dissolved in 30ml anhydrous tetrahydro furan is then dripped, dropwise, continue backflow 4 ~ 8 hours, TLC monitors, after raw material point disappears, stopped reaction cools, revolve and steam removing tetrahydrofuran (THF) and ether, in residuum, add the aqueous ammonium chloride solution that mass percent concentration is 22%, until no longer produce bubble, 3. toluene extraction is for several times added, until it is colourless for extracting the toluene liquid obtained, the anhydrous MgSO of the toluene solution obtained
4to filter after dry, then lucifuge backflow 2 ~ 5 hours, revolve and steam removing toluene, with silica gel column chromatography, obtained above-mentioned polysubstituted-diaryl replaces photochromic compound of naphtho-pyrans product;
Above-mentioned polysubstituted-preparation method of diaryl naphthopyran class photochromic compound in, used amount of substance expand by equal proportion or reduce do not affect final obtained polysubstituted-diaryl naphthopyran photochromic compound product.
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| CN1687056A (en) * | 2005-04-05 | 2005-10-26 | 南开大学 | Photochromic compound of naphtho-pyrans and products |
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| JPH07252247A (en) * | 1994-01-26 | 1995-10-03 | Hodogaya Chem Co Ltd | Naphthopyran compound and photosensitive material using the same |
| GB9726361D0 (en) * | 1997-12-12 | 1998-02-11 | James Robinson Ltd | Photochromic dyes |
| JP2010180396A (en) * | 2009-01-09 | 2010-08-19 | Pilot Ink Co Ltd | Photochromic composition and photochromic laminate using the same |
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| CN1634916A (en) * | 2004-10-20 | 2005-07-06 | 南开大学 | 2,2-diaryl naphthopyran compounds and method for preparing same |
| CN1687056A (en) * | 2005-04-05 | 2005-10-26 | 南开大学 | Photochromic compound of naphtho-pyrans and products |
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| Title |
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| Nanoarchitecture self-assembly and photochromic studies of 2,2-diarylnaphthopyrans;Ting-Feng Tan等;《Tetrahedron》;20060327;第62卷;第4900页图示1，第4905页3.1, * |
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