CN109053671A - A kind of photochromic compound and preparation method thereof - Google Patents
A kind of photochromic compound and preparation method thereof Download PDFInfo
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- CN109053671A CN109053671A CN201810883304.5A CN201810883304A CN109053671A CN 109053671 A CN109053671 A CN 109053671A CN 201810883304 A CN201810883304 A CN 201810883304A CN 109053671 A CN109053671 A CN 109053671A
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Abstract
The invention discloses a kind of photochromic compounds, which is characterized in that the basic structure indicated with structure formula (I), wherein R1For substituted or unsubstituted C1-C6 alkyl；R2For substituted or unsubstituted C1-C6 alkyl.The invention discloses a kind of preparation methods of photochromic compound.Photochromic compound in the present invention can become red from colourless under ultraviolet light irradiation, and after ultraviolet heading line off, and can become colorless from red, photochromism is obvious.The main transformer color tone that the different structure of such compound is shown all is red, discoloration is all in pale red within the scope of dark red, and after circulation is faded in 10000 discolorations, its discoloration does not significantly decrease, simultaneously, it is tested by high temperature, which can be resistant to 350 DEG C of high temperature, can be used as the application of photochromic material.
Description
Technical field
The invention belongs to chemosynthesis technical field, it is related to a kind of photochromic compound and preparation method thereof.
Background technique
It is photochromic to refer to that certain compounds molecular structure under the light action of certain wavelength and intensity become
Change, so as to cause its corresponding change of absorption peak, that is, color to light, and this change is generally reversible.Photochromic material
Material is classified as follows:
1, inorganic photochromic material: the photochromic effect of typical inorganic system is anti-along with reversible oxidationreduction
It answers, there is good invertibity and fatigue performance；The disadvantage is that photochromic efficiency is lower, adhesive force is weak, dispersion is uneven, band
There is background color and opaque.Inorganic photochromic compound mainly has transition metal oxide, metal halide and rare earth compounding
Three categories.
2, organic photochromic material: organic photochromic material is many kinds of, and reaction mechanism is also not quite similar, reaction
Mode specifically includes that valence link isomery, cis-trans isomerism, key fracture, polymerization, oxidationreduction, pericyclic reaction etc..With azo
For closing object, cis-trans isomerization reaction of the photochromic effect based on azo group-N=N- in molecule, usual azo-compound
Cis-trans isomer has different absorption peaks, though the general difference of the two is little, molar extinction coefficient often differs greatly, in addition,
There are also apparent light polarization effect, i.e. photochromic effect are related with the polarization state of light for azo-compound.The photochromic material of biology
The ligh-induced effect of material such as bacteria rhodopsin also belongs to this kind of reaction mechanisms.
Photochromic compound is added in transparent resin, photochromic material is made, can be used for resin eyeglass, it is domestic
Start to apply in terms of external light-sensitive sunglasses.Photochromism is obtained as a result, obviously and can guarantee main transformer color tone range
Photochromic compound, be an important topic of this field.
Summary of the invention
Present invention design has synthesized a kind of novel photochromic compound, and structural formula is shown in formula I:
Such compound can become red from colourless under ultraviolet light irradiation, and after ultraviolet heading line off, and can become from red
To be colourless, photochromism is obvious, and has lasting discoloration fade properties；The master that such compound different structure is shown
Discoloration tone be all it is red, discoloration is all in pale red within the scope of dark red.
The invention adopts the following technical scheme:
A kind of photochromic compound, which is characterized in that the basic structure indicated with following structural formula (I):
Wherein, R1For substituted or unsubstituted C1-C6 alkyl；R2For substituted or unsubstituted C1-C6 alkyl.
A kind of preparation method of photochromic compound, which comprises the steps of:
(1) compound HF-1 cyclization occurs in acid condition obtains HF-2, and reaction equation is as follows:
(2) HF-2 and 1- (4- methoxyphenyl) -2- propine -1- alcohol generate HF-3 under acid catalysis, and reaction equation is such as
Under:
(3) HF-3 is reacted with alkyl Grignard reagent or alkyl lithium reagents generates HF-4, and reaction equation is as follows:
(4) HF-4, which reacts under acid anhydrides and boron trifluoride ether solution effect with alcohol, generates photochromic compound I, reaction
Formula is as follows:
Preferably, acid used in step (1) is in acetic acid, trifluoroacetic acid, methanesulfonic acid, phosphoric acid, sulfuric acid or polyphosphoric acids
One kind；The reaction dissolvent used is toluene, dimethylbenzene or not solubilizer.
Preferably, the reaction temperature of step (1) is 30~130 DEG C.
Preferably, acid used in step (2) is acetic acid, in trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, phosphoric acid, sulfuric acid
One kind；The reaction dissolvent used is benzene,toluene,xylene, in methylene chloride, chloroform, tetrahydrofuran, methyltetrahydrofuran
It is a kind of.
Preferably, the reaction temperature of step (2) is 10~100 DEG C.
Preferably, alkyl grignard reagent described in step (3) is alkylmagnesium chloride or alkyl bromination magnesium；Alkyl lithium reagents
For lithium alkylide；Solvent used in reaction is one of ether, tetrahydrofuran or methyltetrahydrofuran.
Preferably, the alkylated reaction temperature of step (3) is -50~20 DEG C.
Preferably, acid anhydrides described in step (4) is acetic anhydride, trifluoroacetic anhydride；The alcohol is C1-C6 alkylol；
Reaction dissolvent is one of ether, acetonitrile, toluene, dimethylbenzene, tetrahydrofuran or methyltetrahydrofuran.
Preferably, the alkylated reaction temperature of step (4) is -10~50 DEG C.
It is of the invention preferred the preparation method comprises the following steps:
(1) compound HF-1 cyclization occurs in acid condition obtains intermediate 5- hydroxyl -7H- benzo [c] fluorenes -7- ketone
(HF-2), acid used in reaction is acetic acid, trifluoroacetic acid, methanesulfonic acid, phosphoric acid, sulfuric acid or polyphosphoric acids；The molal quantity of acid
It is 6-18 times of compound HF-1；Reaction temperature is 30-130 DEG C, and the reaction time is 1-8 hours；The solvent is toluene, two
Toluene or not solubilizer.
(2) HF-2 and 1- (4- methoxyphenyl) -2- propine -1- alcohol generate photochromic chemical combination under to acid catalysis
Object HF-3；Wherein, relative to the HF-2 of 1mol, the amount of 1- (4- methoxyphenyl) -2- propine -1- alcohol is 1.0-1.4mol, is made
Acid is acetic acid, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, phosphoric acid or sulfuric acid；Relative to the HF-2 of 1mol, sour amount is
0.1-0.3mol；Reaction temperature is 10-100 DEG C, and the reaction time is 2-16 hours；Reaction dissolvent is benzene,toluene,xylene, two
One of chloromethanes, chloroform, tetrahydrofuran, methyltetrahydrofuran.
(3) compound HF-3 reacts to obtain compound HF-4 with alkyl grignard reagent, used in alkyl grignard reagent
For alkylmagnesium chloride or alkyl bromination magnesium, alkyl lithium reagents are lithium alkylide, and molal quantity used is 1-5 times of HF-3, alkylation
Reaction temperature is -50~20 DEG C；Reaction time is 1-8 hours；Solvent used in reaction is ether, tetrahydrofuran or methyl four
Hydrogen furans.
(4) compound HF-4, which reacts under acid anhydrides and boron trifluoride ether solution effect with alcohol, generates photochromic compound
I, acid anhydrides used are acetic anhydride, trifluoroacetic anhydride, and molal quantity used is 1-3 times of HF-4, and the alcohol used is C1-C6 alkyl
Alcohol；Such as methanol, ethyl alcohol, isobutanol, molal quantity used are 1-2 times of HF-4；Reaction temperature is -10~50 DEG C；When reaction
Between be 1-8 hours；Solvent used in reaction is ether, acetonitrile, toluene, dimethylbenzene, tetrahydrofuran or methyltetrahydrofuran etc..
A kind of photochromic compound of the present invention can be used as the application of photochromic material.
A kind of photochromic compound of the present invention can be applied to resin eyeglass.The resins such as the styrene by compound of formula I
Monomer is made into clear solution, in addition appropriate V65, is poured, is heating and curing, is allowed to become colourless transparent resin eyeglass.
In the present invention, in Formulas I, R1For substituted or unsubstituted C1-C6 alkyl；It can be methyl, ethyl, isopropyl, fourth
Base etc.；R2For substituted or unsubstituted C1-C6 alkyl；It can be methyl, ethyl, isopropyl, butyl etc..Except implementation of the invention
Exception, Formulas I include but is not limited to such as flowering structure:
Beneficial effects of the present invention: the present invention designs to have obtained a kind of photochromic compound, under ultraviolet light irradiation, energy
Become red from colourless, and after ultraviolet heading line off, and can become colorless from red, photochromism is obvious.Such compound
The main transformer color tone that shows of different structure be all it is red, discoloration is all in pale red within the scope of dark red.And pass through 10000
Secondary discoloration is faded after circulation, and discoloration does not significantly decrease.Meanwhile being tested by high temperature, which can be resistance to
By 350 DEG C of high temperature.
Detailed description of the invention
The nuclear magnetic spectrogram of Fig. 1 HF-2.
The nuclear magnetic spectrogram of Fig. 2 HF-3.
Photochromic compound 3- phenyl -3- (4- methoxyphenyl) -13- methyl-1 3- methoxy prepared by Fig. 3 embodiment 1
The nuclear magnetic spectrogram of base -3,13- dihydrobenzo [h] indenes [2,1-f] pyrans.
Specific embodiment
The present invention will be further described in detail below with reference to specific embodiments.
In following embodiments, for nuclear magnetic resonance by Bruker AMX-400 type nmr determination, TMS is internal standard, chemistry
Displacement unit is ppm；Efficient liquid phase (HPLC) is detected by Agilent 1100；TLC silica gel plate GF254 is Haiyang Chemical Plant, Qingdao
Production, is developed the color using ultraviolet lamp；If unspecified operating method in embodiment, reduced pressure refers to will be prepared with Rotary Evaporators
Solvent in compound solution steams；Dry refer to is dried with anhydrous sodium sulfate or magnesium sulfate, and vacuum drying, which refers to, uses vacuum oven
Middle vacuum drying prepare compound.
English abbreviation involved in text: MeOH is methanol；TLC is tlc analysis；DCM is methylene chloride.
Embodiment 1:
Photochromic compound 3- phenyl -3- (4- methoxyphenyl) -13- methyl-1 3- methoxyl group -3,13- dihydrobenzo
The preparation of [h] indenes [2,1-f] pyrans:
(1) preparation of HF-2
In 10L three-necked flask, compound HF-1 (300g, 1.14mo1), dimethylbenzene (3000mL) and 800g methylsulphur is added
Acid is heated to 120 DEG C, reacts 4h, reaction solution is poured into 500mL water, filters, filter residue 100mL water washing, air dry oven
It is dry, obtain field gray solid 260g, yield 92.6%.
ESI-MS:[M+H]+=247.2
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3)δ7.99–7.92(m,1H),7.79(s,1H),7.63(dd,J
=11.2,4.5Hz, 1H), 7.55-7.43 (m, 1H), 7.36-7.27 (m, 1H), 3.65 (s, 1H), 2.54 (s, 1H)
(2) preparation of HF-3
HF-2 (246.2g, 1.0mo1), 1- (4- methoxyphenyl) -2- propine -1- alcohol are sequentially added into reaction flask
(333g, 1.4mo1), toluene 2.5L, methanesulfonic acid 30g；Reaction temperature is 90-100 DEG C, is stirred 8-10 hours, reaction was completed, has
Solvent is evaporated off in decompression (T < 40 DEG C) after machine layer is dry, is dried in vacuo to obtain aubergine solid 405g, yield about 87.1%；
ESI-MS:[M+H]+=467.5
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3) δ 8.46-8.28 (m, 1H), 7.91 (d, J=10.0Hz,
1H), 7.85 (d, J=7.6Hz, 1H), 7.63-7.48 (m, 2H), 7.48-7.40 (m, 1H), 7.36 (t, J=7.4Hz, 1H),
7.32-7.25 (m, 1H), 7.20 (t, J=7.4Hz, 1H), 6.91-6.76 (m, 1H), 6.35 (d, J=10.0Hz, 1H), 3.78
(s,1H).
(3) preparation of HF-4
HF-3 (400g, 0.856mo1) is put into there-necked flask, 5L tetrahydrofuran is added, cooling system is to -30 DEG C；Dropwise
About 500mL lithium methide is added, keeping system temperature is -25 DEG C hereinafter, the reaction time is 4 hours；Fully reacting is slowly added dropwise full
With ammonium chloride solution 2000ml quenching reaction；Liquid separation takes organic layer, and anhydrous sodium sulfate is dry, is spin-dried for, obtains black solid；Very
Empty dry HF-4.It direct plunges into and reacts in next step.
(4) 3- phenyl -3- (4- methoxyphenyl) -13- methyl-1 3- methoxyl group -3,13- dihydrobenzo [h] indenes [2,1-
F] pyrans preparation
Dried HF-4 is added in acetonitrile 4L, is stirred, ice bath is < 5 DEG C cooling, add trifluoroacetic anhydride (400g), Gu
Body all dissolves, and reacts at room temperature 2h, is cooled to 15~30 DEG C, and methanol 50g is added and boron trifluoride ether 200g solution, room temperature are anti-
3h is answered, end of reaction is added dropwise saturated sodium bicarbonate and is quenched, and ethyl acetate (8L) liquid separation is added, and organic layer anhydrous sodium sulfate is dry,
It is spin-dried for, obtains crude product, crude product chromatographs (petroleum ether: ethyl acetate=15:1 is eluted) through column and obtains off-white color product I: 285g, yield:
67.1%.
ESI-MS:[M+H]+=497.5
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3) δ 8.53 (t, J=10.4Hz, 1H), 8.47 (d, J=
8.4Hz, 1H), 8.08 (d, J=7.7Hz, 1H), 7.65-7.47 (m, 6H), 7.46-7.24 (m, 7H), 6.92-6.77 (m,
2H), 6.26 (t, J=9.6Hz, 1H), 3.75 (dd, J=11.0,6.4Hz, 3H), 3.24 (dd, J=11.2,6.4Hz, 3H),
1.84–1.73(m,3H).
Embodiment 2:
The photochromic test of photochromic compound
The styrene resin alicyclic monomer of photochromic compound prepared by embodiment 1 is made into clear solution, in addition appropriate
V65 is poured, is heating and curing, and is allowed to become colourless transparent resin eyeglass, later, using solution after ultraviolet light about 2s by
Red is crossfaded into, and the intensity of absorption peak is also enhancing as the irradiation time increases, the liquid color depth after discoloration is gradually
It deepens.After ultraviolet heading line off, the color of solution rapidly takes off to colourless, time about 90s again.This illustrates photochromicization
It closes object and photochromic reactions has occurred under the action of uv light, reaction equation is as follows:
After circulation is faded in 10000 discolorations, discoloration does not significantly decrease.
Embodiment 3:
High temperature resistant test
Photochromic compound solid prepared by 10g embodiment 1 is placed in crucible, then crucible is transferred to Muffle furnace
In, 350 DEG C are warming up to, and keep the temperature 1 hour at such a temperature.Solid is taken out, 30mg is taken to be dissolved in 100mL styrene resin alicyclic monomer
It is made into clear solution, in addition appropriate V65, is poured, is heating and curing, is allowed to become colourless transparent resin eyeglass, later, use is ultraviolet
Light irradiation, resin lens redden deepen rapidly, then solution is transferred under visible light conditions, and about 90s or so is taken off substantially to colourless.
The compound can be resistant to 350 DEG C of high temperature as a result,.
Embodiment 4:
Photochromic compound 3- phenyl -3- (4- methoxyphenyl) -13- ethyl -13- ethyoxyl -3,13- dihydrobenzo
The preparation of [h] indenes [2,1-f] pyrans:
(1) preparation of HF-2
In 10L three-necked flask, compound HF-1 (300g, 1.14mo1), toluene (3000mL) and 6.84mol vinegar is added
Acid is heated to 30 DEG C, reacts 8h, reaction solution is poured into 500mL water, filters, filter residue 100mL water washing, air dry oven
It is dry, obtain field gray solid 242.6g, yield 86.4%.
ESI-MS:[M+H]+=247.2
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3)δ7.99–7.92(m,1H),7.79(s,1H),7.63(dd,J
=11.2,4.5Hz, 1H), 7.55-7.43 (m, 1H), 7.36-7.27 (m, 1H), 3.65 (s, 1H), 2.54 (s, 1H)
(2) preparation of HF-3
HF-2 (246.2g, 1.0mo1), 1- (4- methoxyphenyl) -2- propine -1- alcohol are sequentially added into reaction flask
(333g, 1.4mo1), benzene 2.5L, p-methyl benzenesulfonic acid 0.1mol；Reaction temperature is 100 DEG C, is stirred 2 hours, reaction was completed, organic
Solvent is evaporated off in decompression (T < 40 DEG C) after layer is dry, is dried in vacuo to obtain aubergine solid 372.9g, yield about 80.2%；
ESI-MS:[M+H]+=467.5
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3) δ 8.46-8.28 (m, 1H), 7.91 (d, J=10.0Hz,
1H), 7.85 (d, J=7.6Hz, 1H), 7.63-7.48 (m, 2H), 7.48-7.40 (m, 1H), 7.36 (t, J=7.4Hz, 1H),
7.32-7.25 (m, 1H), 7.20 (t, J=7.4Hz, 1H), 6.91-6.76 (m, 1H), 6.35 (d, J=10.0Hz, 1H), 3.78
(s,1H).
(3) preparation of HF-4
HF-3 (400g, 0.856mo1) is put into there-necked flask, 5L ether is added, cooling system is to -30 DEG C；It is added dropwise
About 500mL ethyl-lithium, keeping system temperature is -35 DEG C, and the reaction time is 1 hour；Saturated ammonium chloride is slowly added dropwise in fully reacting
Solution 2000ml quenching reaction；Liquid separation takes organic layer, and anhydrous sodium sulfate is dry, is spin-dried for, obtains black solid；It is dried in vacuo
HF-4.It direct plunges into and reacts in next step.
(4) 3- phenyl -3- (4- methoxyphenyl) -13- ethyl -13- ethyoxyl -3,13- dihydrobenzo [h] indenes [2,1-
F] pyrans preparation
Dried HF-4 is added in ether 4L, is stirred, ice bath is < 5 DEG C cooling, add acetic anhydride (0.856mol), Gu
Body all dissolves, and reacts at room temperature 2h, is cooled to 15~30 DEG C, and ethyl alcohol 50g is added and boron trifluoride ether 200g solution, room temperature are anti-
3h is answered, end of reaction is added dropwise saturated sodium bicarbonate and is quenched, and ethyl acetate (8L) liquid separation is added, and organic layer anhydrous sodium sulfate is dry,
It is spin-dried for, obtains crude product, crude product chromatographs (petroleum ether: ethyl acetate=15:1 is eluted) through column and obtains off-white color product I: 214.9g, receives
Rate: 50.6%.
ESI-MS:[M+H]+=525.7
Embodiment 5:
Photochromic compound 3- phenyl -3- (4- methoxyphenyl) -13- butyl -13- isobutoxy -3,13- dihydrobenzene
And the preparation of [h] indenes [2,1-f] pyrans:
(1) preparation of HF-2
In 10L three-necked flask, compound HF-1 (300g, 1.14mo1), dimethylbenzene (3000mL) and 20.52mol is added
Trifluoroacetic acid is heated to 130 DEG C, reacts 1h, reaction solution is poured into 500mL water, filters, filter residue 100mL water washing, air blast
Drying box is dry, obtains field gray solid 254.7g, yield 90.7%.
ESI-MS:[M+H]+=247.2
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3)δ7.99–7.92(m,1H),7.79(s,1H),7.63(dd,J
=11.2,4.5Hz, 1H), 7.55-7.43 (m, 1H), 7.36-7.27 (m, 1H), 3.65 (s, 1H), 2.54 (s, 1H)
(2) preparation of HF-3
HF-2 (246.2g, 1.0mo1), 1- (4- methoxyphenyl) -2- propine -1- alcohol are sequentially added into reaction flask
(333g, 1.4mo1), methylene chloride 2.5L, phosphoric acid 0.3mol；Reaction temperature is 10 DEG C, is stirred 16 hours, reaction was completed, organic
Solvent is evaporated off in decompression (T < 40 DEG C) after layer is dry, is dried in vacuo to obtain aubergine solid 357.1g, yield about 76.8%；
ESI-MS:[M+H]+=467.5
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3) δ 8.46-8.28 (m, 1H), 7.91 (d, J=10.0Hz,
1H), 7.85 (d, J=7.6Hz, 1H), 7.63-7.48 (m, 2H), 7.48-7.40 (m, 1H), 7.36 (t, J=7.4Hz, 1H),
7.32-7.25 (m, 1H), 7.20 (t, J=7.4Hz, 1H), 6.91-6.76 (m, 1H), 6.35 (d, J=10.0Hz, 1H), 3.78
(s,1H).
(3) preparation of HF-4
HF-3 (400g, 0.856mo1) is put into there-necked flask, 5L methyltetrahydrofuran is added, cooling system is to -30 DEG C；
About 500mL butylmagnesium chloride is added dropwise, keeping system temperature is 20 DEG C, and the reaction time is 8 hours；Fully reacting is slowly dripped
Add saturated ammonium chloride solution 2000ml quenching reaction；Liquid separation takes organic layer, and anhydrous sodium sulfate is dry, is spin-dried for, and it is solid to obtain black
Body；It is dried in vacuo to obtain HF-4.It direct plunges into and reacts in next step.
(4) 3- phenyl -3- (4- methoxyphenyl) -13- butyl -13- isobutoxy -3,13- dihydrobenzo [h] indenes [2,
1-f] pyrans preparation
Dried HF-4 is added in toluene 4L, is stirred, ice bath is < 5 DEG C cooling, adds trifluoroacetic anhydride
(2.568mol), solid all dissolve, and react at room temperature 2h, are cooled to -10 DEG C, and isobutanol 0.856mol and boron trifluoride second is added
Ether 200g solution reacts at room temperature 1h, and end of reaction is added dropwise saturated sodium bicarbonate and is quenched, and ethyl acetate (8L) liquid separation is added, organic
Layer anhydrous sodium sulfate is dry, is spin-dried for, and obtains crude product, and crude product through column chromatographs (petroleum ether: ethyl acetate=15:1 is eluted), and to obtain class white
Color product I: 248g, yield: 58.4%.
ESI-MS:[M+H]+=581.8
Embodiment 6:
Photochromic compound 3- phenyl -3- (4- methoxyphenyl) -13- (1- chloro-2-methyl propoxyl group) -13- (3- ring
Amyl butyl) -3,13- dihydrobenzo [h] indenes [2,1-f] pyrans preparation:
(1) preparation of HF-2
In 10L three-necked flask, compound HF-1 (300g, 1.14mo1) and 11.4mol phosphoric acid is added, is heated to 90 DEG C,
5h is reacted, reaction solution is poured into 500mL water, is filtered, filter residue 100mL water washing, air dry oven is dry, and it is solid to obtain field gray
Body 233.6g, yield 83.2%.
ESI-MS:[M+H]+=247.2
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3)δ7.99–7.92(m,1H),7.79(s,1H),7.63(dd,J
=11.2,4.5Hz, 1H), 7.55-7.43 (m, 1H), 7.36-7.27 (m, 1H), 3.65 (s, 1H), 2.54 (s, 1H)
(2) preparation of HF-3
HF-2 (246.2g, 1.0mo1), 1- (4- methoxyphenyl) -2- propine -1- alcohol are sequentially added into reaction flask
(333g, 1.4mo1), methyltetrahydrofuran 2.5L, trifluoroacetic acid 0.2mol；Reaction temperature is 70 DEG C, is stirred 2 hours, is terminated anti-
It answers, solvent is evaporated off in decompression (T < 40 DEG C) after organic layer is dry, is dried in vacuo to obtain aubergine solid 371.5g, yield about 79.9%；
ESI-MS:[M+H]+=467.5
Nuclear magnetic resonance data:1H NMR(400MHz,CDCl3) δ 8.46-8.28 (m, 1H), 7.91 (d, J=10.0Hz,
1H), 7.85 (d, J=7.6Hz, 1H), 7.63-7.48 (m, 2H), 7.48-7.40 (m, 1H), 7.36 (t, J=7.4Hz, 1H),
7.32-7.25 (m, 1H), 7.20 (t, J=7.4Hz, 1H), 6.91-6.76 (m, 1H), 6.35 (d, J=10.0Hz, 1H), 3.78
(s,1H).
(3) preparation of HF-4
HF-3 (400g, 0.856mo1) is put into there-necked flask, 5L tetrahydrofuran is added, cooling system is to -30 DEG C；Dropwise
About 500mL3- cyclopentylbutyl magnesium bromide is added, keeping system temperature is -50 DEG C, and the reaction time is 6 hours；Fully reacting, slowly
It is slow that saturated ammonium chloride solution 2000ml quenching reaction is added dropwise；Liquid separation takes organic layer, and anhydrous sodium sulfate is dry, is spin-dried for, obtains black
Solid；It is dried in vacuo to obtain HF-4.It direct plunges into and reacts in next step.
(4) 3- phenyl -3- (4- methoxyphenyl) -13- (1- chloro-2-methyl propoxyl group) -13- (3- cyclopentylbutyl) -
The preparation of 3,13- dihydrobenzos [h] indenes [2,1-f] pyrans
Dried HF-4 is added in methyltetrahydrofuran 4L, is stirred, ice bath is < 5 DEG C cooling, adds trifluoroacetic anhydride
(400g), solid all dissolve, and react at room temperature 2h, are cooled to 50 DEG C, and 1- chloro-2-methyl propyl alcohol 1.712mol and borontrifluoride is added
Borate ether 200g solution reacts at room temperature 8h, and end of reaction is added dropwise saturated sodium bicarbonate and is quenched, ethyl acetate (8L) liquid separation is added,
Organic layer anhydrous sodium sulfate is dry, is spin-dried for, and obtains crude product, and crude product chromatographs (petroleum ether: ethyl acetate=15:1 is eluted) through column and obtains
Off-white color product I: 227.7g, yield: 53.6%.
ESI-MS:[M+H]+=684.3
Above-described embodiment is merely illustrative of the technical solution of the present invention and is not intended to limit it, all without departing from the present invention
Any modification of spirit and scope or equivalent replacement should all cover the range in technical solution of the present invention.
Claims (10)
1. a kind of photochromic compound, which is characterized in that the basic structure indicated with following structural formula (I):
Wherein, R1For substituted or unsubstituted C1-C6 alkyl；R2For substituted or unsubstituted C1-C6 alkyl.
2. a kind of preparation method of photochromic compound, which comprises the steps of:
(1) compound HF-1 cyclization occurs in acid condition obtains HF-2, and reaction equation is as follows:
(2) HF-2 and 1- (4- methoxyphenyl) -2- propine -1- alcohol generate HF-3 under acid catalysis, and reaction equation is as follows:
(3) HF-3 is reacted with alkyl Grignard reagent or alkyl lithium reagents generates HF-4, and reaction equation is as follows:
(4) HF-4, which reacts under acid anhydrides and boron trifluoride ether solution effect with alcohol, generates photochromic compound I, and reaction equation is such as
Under:
3. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that step makes in (1)
Acid is one of acetic acid, trifluoroacetic acid, methanesulfonic acid, phosphoric acid, sulfuric acid or polyphosphoric acids；The reaction dissolvent used is first
Benzene, dimethylbenzene or not solubilizer.
4. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that step (1) it is anti-
Answering temperature is 30~130 DEG C.
5. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that step makes in (2)
Acid is one of acetic acid, trifluoroacetic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, phosphoric acid, sulfuric acid；The reaction dissolvent used be benzene,
One of toluene, dimethylbenzene, methylene chloride, chloroform, tetrahydrofuran, methyltetrahydrofuran.
6. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that step (2) it is anti-
Answering temperature is 10~100 DEG C.
7. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that institute in step (3)
The alkyl grignard reagent stated is alkylmagnesium chloride or alkyl bromination magnesium；Alkyl lithium reagents are lithium alkylide；Solvent used in reaction
For one of ether, tetrahydrofuran or methyltetrahydrofuran.
8. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that the alkane of step (3)
Glycosylation reaction temperature is -50~20 DEG C.
9. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that institute in step (4)
The acid anhydrides stated is acetic anhydride, trifluoroacetic anhydride；The alcohol is C1-C6 alkylol；Reaction dissolvent is ether, acetonitrile, toluene, two
One of toluene, tetrahydrofuran or methyltetrahydrofuran.
10. a kind of preparation method of photochromic compound according to claim 2, which is characterized in that the alkane of step (4)
Glycosylation reaction temperature is -10~50 DEG C.
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| CN114031599A (en) * | 2021-09-10 | 2022-02-11 | 江苏视科新材料股份有限公司 | Preparation method of bis-benzo chromene photochromic compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004085568A2 (en) * | 2003-03-20 | 2004-10-07 | Transitions Optical, Inc. | Photochromic articles with reduced temperature dependency and methods for preparation |
| CN101454695A (en) * | 2006-05-31 | 2009-06-10 | 光学转变公司 | Photochromic materials comprising haloalkyl groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004085568A2 (en) * | 2003-03-20 | 2004-10-07 | Transitions Optical, Inc. | Photochromic articles with reduced temperature dependency and methods for preparation |
| CN101454695A (en) * | 2006-05-31 | 2009-06-10 | 光学转变公司 | Photochromic materials comprising haloalkyl groups |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031599A (en) * | 2021-09-10 | 2022-02-11 | 江苏视科新材料股份有限公司 | Preparation method of bis-benzo chromene photochromic compound |
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