CN103030652A - Benzopyran derivative, its preparation method and application - Google Patents
Benzopyran derivative, its preparation method and application Download PDFInfo
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Abstract
The invention provides a benzopyran derivative and a preparation method of the benzopyran derivative. Under sunlight or ultraviolet irradiation, the benzopyran derivative provided in the invention can change from colorless to yellow or orange red, thus being a compound with excellent photochromic performance. Also, relative to naphthopyran derivatives, the benzopyran derivative involved in the invention has a simple synthesis method and low-cost raw materials, thus being suitable for large-scale industrial production. The invention also provides application of the benzopyran derivative.
Description
Technical field
The present invention relates to a kind of photochromic material, relate in particular to a kind of 1-benzopyran derivatives (or 2,1,3-diazosulfide) derivative and preparation method thereof and application thereof.
Background technology
Organic photochromic material is a kind of optical information storage and optical recording material with potential application foreground, has caused in recent years people's very big interest.
Pyran compounds is owing to having preferably optical Response, faster fading rate and good light stability, and the combination of liquid crystal liquid crystal property and photochromic characteristic in molecular system, also can produce some unique optical properties, therefore become the photochromic material that a class has very high use value, and caused the concern of researchers, such as the disclosed naphtho-pyrans compounds of patent CN101215282A.
Chinese patent CN101346663A discloses a kind of 2H-naphtho-[1,2-b] pyrylium compound, Chinese patent CN1634916A further discloses a kind of 2,2-diaryl-2H-naphtho-pyrans compounds, wherein, 2, the two phenyl of 2--2H-naphtho-[1,2-b] pyrans (2,2-bisphenyl-2H-naphtho[1,2-b] pyran) and the two phenyl of 2,2--3H-naphtho-[2,1-b] pyrans (2,2-bisphenyl-3H-naphtho[2,1-b] pyran) derivative (hereinafter referred " phenylbenzene aphthopyrans derivative ", its precursor structure is respectively shown in structural formula A and B) is the compound that a class has good photochromic properties, also is the present more aphthopyrans derivative of research.
Such as people such as Hu Weilin, Xie Minggui in phenylbenzene aphthopyrans derivative (Sichuan University's journal, 2007,39 (1): 108～112) of preparing under the consisting of phase-transferring agent existence condition on No. 9 position carbon atoms with long flexible chain; The people such as Campredon 4 ' and 4 " compounds (J.Photochem.Photobiol.A., 2003:159:7～16) of halogen atom gained are introduced in the position; Favaro etc. 4 ' and 4 " methoxyl group is introduced in the position, introduces methyl gained compounds (J.Photochem.Photobiol.A., 2008,196:190～196) at 5,6 simultaneously; Favaro etc. introduce dimethylaminos or Pyrrolidine base at 9, simultaneously 4 ', 4 " position introducing methoxyl group, dimethylamino or piperidyl, and introduced methylol gained compound (ChemPhysChem., 2008,9:768～775) at 5; Samat etc. are connected bimolecular naphthopyran compounds or a part naphthopyran compounds by two key bridgings Yu the Luo oxazine, consisted of two chromic systems (Tetrahedron, 2001,57:7349～7359).
In recent years, modification to such photochromic compound not only is confined to introduce different substituting groups at the aphthopyrans parent molecule, but different aromatic nucleus or other structural unit are incorporated on the naphthalene nucleus by the mode that covalent linkage shares, reach the purpose of improving its performance, as color or the quickening of regulating the open loop body be colour solid fade rates etc., thereby be applied to better the commercial fields such as light-sensitive sunglasses.Such as Oliveira etc. carbazole unit has been incorporated on the naphthalene nucleus, because steric effect in the open loop body molecule after the illumination, constructed the stable naphthopyran compounds (J.Photochem.Photobio.A:Chem., 2008,198:242～249) that significantly improves of a series of colour generation body heats; Favaro group and Coelho group successively just are incorporated into fluorenes and Fluorenone unit on the naphthalene nucleus in a different manner, studied its impact (Photochem.Photobiol.Sci. on character such as product photochemistry and thermostabilitys in great detail, 2002,1:803～808; J.Photochem.Photobio.A:Chem., 2005,172:300～307); Then introduced the indenes ring among the patent CN101341141A.
Because existing phenylbenzene aphthopyrans derivative is difficult to the mass-producing preparation, therefore developing the novel phenylbenzene aphthopyrans derivative that is easy to the mass-producing preparation just becomes the technical issues that need to address of the present invention.
Summary of the invention
The invention provides a kind of 1-benzopyran derivatives and (or be called 2; 1; the 3-diazosulfide derivative); has good photochromic properties; this compound can be prepared by amino benzenes compounds simultaneously; raw materials cost is cheap, and synthetic method is simple, has solved the difficult problem that phenylbenzene aphthopyrans derivative is difficult to the mass-producing preparation.
First purpose of the present invention provides a kind of 1-benzopyran derivatives, and described aphthopyrans derivative has the molecular structure shown in structural formula (I), wherein: R
1Can be H, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain in the alkylamino radical of 1～12 carbon any one; R
2Can be H also, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain in the alkylamino radical of 1～12 carbon any one.
Wherein, in the above-mentioned 1-benzopyran derivatives molecular structure of the present invention, R
1And R
2Be preferably respectively alkoxyl group; And more preferably contain the alkoxyl group of 1～6 carbon atom, more have and elect the alkoxyl group that contains 1～3 carbon atom as.Such as: first sulfydryl, second sulfydryl, the third sulfydryl, isopropyl sulfydryl, uncle's fourth sulfydryl, positive fourth sulfydryl, penta sulfydryl, the ninth of the ten Heavenly Stems sulfydryl, dodecane sulfydryl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, tert.-butoxy, n-butoxy, pentyloxy, the ninth of the ten Heavenly Stems oxygen base, dodecyloxy, methylamino, ethylamino-, Propylamino, isopropylamine base, TERTIARY BUTYL AMINE base, n-butylamine-based, amylamine base, nonyl amine base, dodecane amido etc.
The present invention has the 1-benzopyran derivatives of molecular structure shown in the structural formula (I), can be by 5-halo-2,1, and the 3-diazosulfide is raw material, by the condensation reaction of Williamson ether, generates 5-alkoxyl group-2,1, the 3-diazosulfide; Then make alkoxyl group generate hydroxyl by the ether-splitting solution, obtain 5-hydroxyl-2,1, the 3-diazosulfide; The Claisen rearrangement reaction occurs with the propargyl alcohol derivative with molecular structure shown in the structural formula (II) and prepares in last 5-hydroxyl-2,1,3-diazosulfide.Described 5-halo-2,1,3-diazosulfide can be 5-chloros-2,1,3-diazosulfide or 5-bromo-2,1,3-diazosulfide.
The method of the described 1-benzopyran derivatives of the another kind of preparation of the present invention, step comprises:
Step 1 take o-Nitraniline as raw material, is carried out halo in phenyl ring nitro contraposition position, obtains 4-halo-2-N-methyl-p-nitroaniline;
Step 2 generates amino with nitroreduction, obtains 4-halo-O-Phenylene Diamine;
Step 3 adds trialkylamine and halogenation sulfoxide and carries out 5-halo-2,1 shown in the generation of diazosulfide annulation, 3-diazosulfide;
Step 4 by the condensation reaction of Williamson ether, replaces halogen atom with alkoxyl group, generates 5-alkoxyl group-2,1, the 3-diazosulfide; Then make alkoxyl group form hydroxyl by the reaction of ether-splitting solution, generate 5-hydroxyl-2,1, the 3-diazosulfide;
Step 5,5-hydroxyl-2,1, the reaction of propiolic alcohol compound shown in 3-diazosulfide and the structural formula (II) is by 1-benzopyran derivatives shown in the Claisen rearrangement reaction generating structure formula (I).
Wherein:
In the step 1, the used halogenating agent of halo can be NIS (N-N-iodosuccinimide), NBS (N-bromo-succinimide), NCS (N-chlorosuccinimide); Reaction conditions is preferably: with acetic acid as reaction solvent, with o-Nitraniline and NBS back flow reaction.
In the step 2, it is reduced iron powder and the sour system that forms that nitroreduction is generated the amino used original reagent of going back, and reaction conditions is preferably: react under slight boiling condition or the reflux conditions; Perhaps going back original reagent is SnCl
2With the system that acid forms, reaction conditions is preferably: react under the reflux conditions.Described acid can be hydrochloric acid, alkene sulfuric acid, rare nitric acid, Hydrogen bromide.
In the step 3, described trialkylamine can be Trimethylamine, triethylamine, and described halogenation sulfoxide can be sulfur oxychloride, thionyl bromide; Reaction conditions is preferably: methylene dichloride is solvent, triethylamine, thionyl chloride and 4-bromine O-Phenylene Diamine back flow reaction.
And above-mentioned Williamson ether condensation catalyst is preferably anhydrous cupric sulfate, and reaction conditions is preferably: take methyl alcohol as solvent, and 5-bromo-2,1,3-diazosulfide and sodium methylate back flow reaction.Above-mentioned ether-splitting solution catalysts is preferably anhydrous AlCl
3, or strong acid (Zeisel ether-splitting solution), reaction conditions is preferably: take toluene as solvent, reflux; Described strong acid example hydrochloric acid, Hydrogen bromide, dilute sulphuric acid, rare nitric acid etc.
5-hydroxyl-2,1, the reaction of propiolic alcohol compound shown in 3-diazosulfide and the structural formula (II), catalyzer can be acidic alumina, reaction conditions is preferably: toluene is solvent refluxing; Perhaps catalyzer can be tosic acid or tosilate also, and such as paratoluenesulfonic acid sodium salt, reaction conditions is preferably, and acetonitrile is solvent, refluxes.
In the above-mentioned propiolic alcohol derivant structure formula (II): R
1And R
2Be respectively H, contain 1～12 carbon alkyl, contain the alkoxyl group of 1～12 carbon or contain the alkylamino radical of 1～12 carbon.
The present invention also provides a kind of application of 1-benzopyran derivatives in photochromic material with molecular structure shown in the structural formula (I).
1-benzopyran derivatives of the present invention, with 2,1,3-benzothiazole group is introduced in the photochromic benzopyran compounds, obtain a kind of compound with good photochromic properties, under sunlight or UV-irradiation, can from the colourless yellow or orange red that becomes, in many fields such as light-sensitive sunglasses, molecular switch, optical information storage, molecular wire, supramolecular chemistry, textile materials, building and ornament materials, printing ink printing and dyeing, anti-counterfeit recognition technology, all have considerable application prospect.
Described 1-benzopyran derivatives is preferably and is applied in the optical fiber resin material, and described optical fiber resin component comprises body material and has the 1-benzopyran derivatives of the molecular structure shown in the structural formula (I).Described body material can be for macromolecule resin or is also contained processing of high molecular material typical additives or auxiliary agent.
With respect to the aphthopyrans derivative, the synthetic method of 1-benzopyran derivatives of the present invention is simple, and step is less, and raw materials cost is cheap, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is 1-benzopyran derivatives synthetic route chart of the present invention; Wherein, R
1Can be H, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain in the alkylamino radical of 1～12 carbon any one; R
2Can be H also, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain in the alkylamino radical of 1～12 carbon any one; R is alkyl; X is halogen atom.
Fig. 2 is the 1-benzopyran derivatives absorption spectrum change curve (solvent: toluene of the embodiment of the invention 1 preparation; Detectable level: 5.0 * 10
-5Mol/L);
Fig. 3 is 1-benzopyran derivatives chromoplastid extinction curve (solvent: toluene under illumination of the embodiment of the invention 1 preparation; Detectable level: 5.0 * 10
-5Mol/L).
Embodiment
The invention provides a kind of 1-benzopyran derivatives, have the molecular structure shown in the structural formula (I).
The present invention also provides a kind of method of synthetic described 1-benzopyran derivatives, with reference to Fig. 1, take o-Nitraniline as starting raw material, reset through halo, nitroreduction, diazosulfide Cheng Huan, the condensation of Williamson ether, ether-splitting solution and Claisen successively and obtain target compound.
Below by specific embodiment 1-benzopyran derivatives of the present invention and synthetic method thereof are described in detail and describe, so that better understand the present invention, but following embodiment does not limit the scope of the invention.
Embodiment 1
Step 1, synthetic 4-bromo-2-N-methyl-p-nitroaniline
As reaction solvent, add the 0.15mol o-Nitraniline with 120g acetic acid, reflux adds 0.15mol or more NBS several times, continues to reflux.Reaction after finishing is poured into water reaction system, filters, and collects solid, and second alcohol and water recrystallization obtains 4-bromo-2-N-methyl-p-nitroaniline, productive rate 86.8%.Reaction formula is as follows:
Step 2, synthetic 4-bromo-O-Phenylene Diamine
Under the oxygen free condition, 150ml ethanol is solvent, adds 4-bromo-2-N-methyl-p-nitroaniline 10g, with SnCl
2/ HCl system is reductive agent, reacts under the reflux conditions, obtains 4-bromine O-Phenylene Diamine, productive rate 59.2%.Reaction formula is as follows:
Step 3,5-bromo-2,1,3-diazosulfide synthetic
Triethylamine 10g, 4-bromine O-Phenylene Diamine 5g are dissolved in the 150ml dichloromethane solvent, drip thionyl chloride 6.5g.Reflux after reaction finishes, is filtered; Collect filtrate, washing is take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 50: 1) is as eluent carries out column chromatography for separation, obtains 5-bromo-2,1,3-diazosulfide, productive rate 68%.Reaction formula is as follows:
Step 4, preparation 5-hydroxyl-2,1,3-diazosulfide
Under the anhydrous and oxygen-free environment, 200ml methyl alcohol is solvent, and the 3g anhydrous cupric sulfate is catalyzer, 0.15mol sodium methylate and 1.5mmol 5-bromo-2,1,3-diazosulfide back flow reaction.Reaction is filtered after finishing, and filtrate is poured into water, and hydrochloric acid is adjusted to neutrality, dichloromethane extraction is take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 5: 1) is as eluent carries out column chromatography for separation, obtains 5-methoxyl group-2,1,3-diazosulfide.Reaction formula is as follows:
1H-NMR(400Hz，CDCl
3，ppm)：δ7.83(d，J＝9.5Hz，1H，phenyl-H)；7.29(dd，J
1＝2.4Hz，J
2＝9.5Hz，1H，phenyl-H)；7.20(s，1H，phenyl-H)；3.93(s，3H，-OCH
3)
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
7H
6N
2OS)，167.0279，found：167.0272
Can find out by nucleus magnetic resonance and mass spectroscopy structure, obtain 5-methoxyl group-2,1,3-diazosulfide, productive rate 20%.
Toluene is solvent, Hydrogen bromide, 5-methoxyl group-2,1, and 3-diazosulfide back flow reaction after reaction finishes, is filtered, and the washing filter cake obtains 5-hydroxyl-2,1, the 3-diazosulfide.Reaction formula is as follows:
1H-NMR(400Hz，DMSO-d
6，ppm)：δ10.6(s，1H，-OH)；7.97(d，J＝9.4Hz，1H，phenyl-H)；7.40(dd，J
1＝9.4Hz，J
2＝2.4Hz，1H，phenyl-H)；7.21(s，1H，phenyl-H)
Magnetic resonance detection result shows, obtains 5-hydroxyl-2,1,3-diazosulfide, productive rate 65.7%.
Step 5, Claisen resets preparation purpose product
5-hydroxyl-2,1, propargyl alcohol derivative 3mmol shown in 3-diazosulfide 2mmol, the structural formula (II-1), tosic acid 5.8g, acetonitrile 100ml, under the anhydrous and oxygen-free condition, the lucifuge back flow reaction.After reaction finishes, filter, collect filtrate, take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 1: 1) is as eluent carries out column chromatography for separation, obtains 1-benzopyran derivatives shown in the structural formula (I-1), reaction formula is as follows:
1H-NMR(400MHz，CDCl
3，ppm)：δ7.75(d，J＝9.4Hz，1H，＝CH)；7.45(d，J＝7.5Hz，2H，phenyl-H)；7.38-7.28(m，7H，phenyl-H)；6.86(d，2H，J＝8.8Hz，phenyl-H)；6.19(d，J＝9.9Hz，1H，＝CH)；3.78(s，3H，-OCH
3)
13C-NMR(100MHz，CDCl
3，ppm)：δ159.20，152.92，152.42，151.45，144.54，136.33，128.56，128.22，127.74，127.48，126.84，123.83，121.05，118.76，113.55，110.03，83.86，55.27
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
22H
16N
2O
2S)，373.1011；found：373.1015
By nucleus magnetic resonance and simple the analysis, obtained the purpose product, productive rate 45%.
Embodiment 2
With reference to embodiment 1, the present embodiment synthesis step is as follows:
Step 1, synthetic 4-chloro-2-nitroaniline
As reaction solvent, add the 0.15mol o-Nitraniline with 120g acetic acid, reflux adds 0.15mol or more NCS several times, continues to reflux.Reaction after finishing is poured into water reaction system, filters, and collects solid, and recrystallization obtains the 4-chloro-2-nitroaniline.
Step 2, synthetic 4-chloro-O-Phenylene Diamine
Under the oxygen free condition, 150ml ethanol is solvent, and take reduced iron powder/HCl system as reductive agent, back flow reaction obtains 4-chlorine O-Phenylene Diamine.
Step 3,5-chloro-2,1,3-diazosulfide synthetic
Triethylamine, 4-chlorine O-Phenylene Diamine are dissolved in the 150ml dichloromethane solvent, drip thionyl chloride.Reflux after reaction finishes, is filtered; Collect filtrate, washing is take silica-gel plate as stationary phase, sherwood oil/methylene dichloride is as eluent carries out column chromatography for separation, obtains 5-chloro-2,1, the 3-diazosulfide.
Step 4, preparation 5-hydroxyl-2,1,3-diazosulfide
Under the anhydrous and oxygen-free environment, 200ml methyl alcohol is solvent, and anhydrous cupric sulfate is catalyzer, 0.15mol sodium methylate and 1.5mmol 5-chloro-2,1,3-diazosulfide back flow reaction.Filter after reaction finishes, filtrate is poured into water, and hydrochloric acid is adjusted to neutrality, and dichloromethane extraction is take silica-gel plate as stationary phase, sherwood oil/methylene dichloride is as eluent carries out column chromatography for separation, obtains 5-methoxyl group-2,1, the 3-diazosulfide.
1H-NMR(400Hz，CDCl
3，ppm)：δ7.83(d，J＝9.5Hz，1H，phenyl-H)；7.29(dd，J
1＝2.4Hz，J
2＝9.5Hz，1H，phenyl-H)；7.20(s，1H，phenyl-H)；3.93(s，3H，-OCH
3)
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
7H
6N
2OS)，167.0279，found：167.0272
Can find out by nucleus magnetic resonance and mass spectroscopy, obtain 5-methoxyl group-2,1, the 3-diazosulfide.
Toluene is solvent, Aluminum chloride anhydrous, 5-methoxyl group-2,1, and 3-diazosulfide back flow reaction after reaction finishes, is filtered, and the washing filter cake obtains 5-hydroxyl-2,1, the 3-diazosulfide.
1H-NMR(400Hz，DMSO-d
6，ppm)：δ10.6(s，1H，-OH)；7.97(d，J＝9.4Hz，1H，phenyl-H)；7.40(dd，J
1＝9.4Hz，J
2＝2.4Hz，1H，phenyl-H)；7.21(s，1H，phenyl-H)
Magnetic resonance detection result shows, obtains 5-hydroxyl-2,1, the 3-diazosulfide.
Step 5, Claisen resets preparation purpose product
5-hydroxyl-2,1, propargyl alcohol derivative 3mmol shown in 3-diazosulfide 2mmol, the structural formula (II-2), tosic acid 6g, acetonitrile 100ml, under the anhydrous and oxygen-free condition, the lucifuge back flow reaction.After reaction finishes, filter, collect filtrate, take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 2: 1) is as eluent carries out column chromatography for separation, obtains 1-benzopyran derivatives shown in the structural formula (I-2), reaction formula is as follows:
1H-NMR(400MHz，CDCl
3，ppm)：δ7.75(d，J＝9.4Hz，1H，＝CH)；7.46(d，J＝7.2Hz，4H，phenyl-H)；7.34(t；J＝8.4Hz，6H，phenyl-H)；7.29(d，7H，J＝7.0Hz，2H，phenyl-H)；6.23(d，2H，J＝9.8Hz，1H，＝CH)
13C-NMR(100MHz，CDCl
3，ppm)：δ152.91，152.39，151.47，144.27，128.26，127.88，127.35，127.01，125.99，123.79，121.11，118.95，110.08，84.01
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
21H
14N
2OS)，343.0905；found：343.0901
By nucleus magnetic resonance and simple the analysis, obtained the purpose product, productive rate 41%.
Embodiment 3
With reference to embodiment 1, the present embodiment aphthopyrans derivative preparation method is as follows:
The 5-hydroxyl-2,1 of preparation among the embodiment 1 or 2, propargyl alcohol derivative 3mmol shown in 3-diazosulfide 2mmol, the structural formula (II-3), tosic acid 5.8g, acetonitrile 100ml, under the anhydrous and oxygen-free condition, the lucifuge back flow reaction.After reaction finishes, filter, collect filtrate, take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 10: 1) is as eluent carries out column chromatography for separation, obtains 1-benzopyran derivatives shown in the structural formula (I-3), reaction formula is as follows:
1H-NMR(400MHz，CDCl
3，ppm)：δ7.74(d，J＝9.6Hz，1H，phenyl-H)；7.36(d，J＝8.8Hz，4H，phenyl-H)；7.30(t，J＝9.2Hz，2H，phenyl-H)；6.86(d，J＝8.8Hz，4H，phenyl-H)；6.16(d，J＝10.0Hz，1H，＝CH)；3.79(s，6H，-OCH
3)
13C-NMR(100MHz，CDCl
3，ppm)：δ159.13，152.93，152.44，151.44，136.63，133.07，132.57，132.48，131.51，128.37，127.64，123.86，120.98，118.54，114.06，113.90，113.52，109.99，83.73，55.47，55.27
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
23H
18N
2O
3S)，403.1116；found：403.1117
By nucleus magnetic resonance and simple the analysis, obtained the purpose product, productive rate 36%.
Embodiment 4
5-hydroxyl-2,1, propargyl alcohol derivative 3mmol shown in 3-diazosulfide 2mmol, the structural formula (II-2), acidic alumina 10g, toluene 100ml, under the anhydrous and oxygen-free condition, the lucifuge back flow reaction.After reaction finishes, filter, collect filtrate, take silica-gel plate as stationary phase, sherwood oil/methylene dichloride (volume ratio 2: 1) is as eluent carries out column chromatography for separation, obtains 1-benzopyran derivatives shown in the structural formula (I-2), reaction formula is as follows:
1H-NMR(400MHz，CDCl
3，ppm)：δ7.75(d，J＝9.4Hz，1H，＝CH)；7.46(d，J＝7.2Hz，4H，phenyl-H)；7.34(t；J＝8.4Hz，6H，phenyl-H)；7.29(d，7H，J＝7.0Hz，2H，phenyl-H)；6.23(d，2H，J＝9.8Hz，1H，＝CH)
13C-NMR(100MHz，CDCl
3，ppm)：δ152.91，152.39，151.47，144.27，128.26，127.88，127.35，127.01，125.99，123.79，121.11，118.95，110.08，84.01
HRMS-ESI(m/z)：[M+H]
+Calcd.for(C
21H
14N
2OS)，343.0905；found：343.0901
By nucleus magnetic resonance and simple the analysis, obtained the purpose product.
The 1-benzopyran derivatives for preparing in the above embodiment of the present invention is made into 5.0 * 10
-5The toluene solution of mol/L concentration, under 25 ℃ of conditions, solar radiation, solution is by colourless brown color or the red-brown of becoming.Put back to the dark place, solution becomes again colourless again.
The 1-benzopyran derivatives of embodiment 1 preparation is made into 5.0 * 10
-5The toluene solution of mol/L concentration detects the rayed absorption spectrum and changes, and detects absorption curve behind the 365nm illumination 20s, and then illumination 20s, and accumulative total 40s detects absorption curve again, so repeats until absorbancy no longer changes, and detected result as shown in Figure 2.As can be seen from Figure 2, in UV-light and visible wavelength range, the 1-benzopyran derivatives of the present invention's preparation has higher optical density, and optical density changes very obvious.Along with the rayed time lengthening, absorbancy rises to about 0.5,3～5 minutes absorbancys by about 0.1 and reaches steady state, no longer changes, and illustrates that the 1-benzopyran derivatives of the present invention's preparation has good photochromic tint permanence.
With reference to Fig. 3, the 1-benzopyran derivatives of embodiment 1 preparation is made into 5.0 * 10
-5The toluene solution of mol/L concentration, the 365nm ultraviolet lighting, after absorbancy reaches steady state, stop illumination, prolongation in time, the absorbancy at visible region maximum absorption place (474nm) with between prolongation reduce, drop to about 1/2 o'clock of maximum absorbance, the 546nm radiation of visible light stops to shine rear absorbancy and continues to descend, until the most initial state illustrates that the 1-benzopyran derivatives of the present invention's preparation has the good performance of fading.
Although the embodiment of the invention has only been enumerated R
1And R
2Be the situation of H or methoxyl group, still, those skilled in the art can be appreciated that according to prior art, work as R
1Or R
2During for other substituting group of mentioning in the foregoing of the present invention, described 1-benzopyran derivatives also has similar photochromic properties.
The 1-benzopyran derivatives for preparing in the above embodiment of the present invention, be prepared into the optical fiber color-changing resin with body material, can naked-eye observation in 1～15 second behind the radiation of visible light to obvious colour-change, remove illumination after, naked eyes namely can observe color fade in 1～15 second.
Above specific embodiments of the invention are described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, not breaking away from impartial conversion and the modification of doing under the spirit and scope of the present invention, all should contain within the scope of the invention.
Claims (10)
1. a 1-benzopyran derivatives is characterized in that, described 1-benzopyran derivatives has the structure shown in the structural formula (I):
Wherein:
R
1For H, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain the alkylamino radical of 1～12 carbon;
R
2For H, contain 1～12 carbon alkyl, contain 1～12 carbon alkoxyl group, contain the alkane sulfydryl of 1～12 carbon or contain the alkylamino radical of 1～12 carbon.
2. 1-benzopyran derivatives according to claim 1 is characterized in that, R
1For containing the alkoxyl group of 1～6 carbon.
3. 1-benzopyran derivatives according to claim 2, R
1For containing the alkoxyl group of 1～3 carbon.
4. 1-benzopyran derivatives according to claim 1 is characterized in that, R
2For containing the alkoxyl group of 1～6 carbon.
5. 1-benzopyran derivatives according to claim 4 is characterized in that, R
2For containing the alkoxyl group of 1～3 carbon.
6. a method for preparing the 1-benzopyran derivatives of structure shown in (I) that has structural formula is characterized in that, step comprises:
Step 1 take o-Nitraniline as raw material, is carried out halo in phenyl ring nitro contraposition position and is obtained 4-halo-2-N-methyl-p-nitroaniline;
Step 2 generates amino with nitroreduction, obtains 4-halo-O-Phenylene Diamine;
Step 3 adds trialkylamine and halogenation sulfoxide and carries out 5-halo-2,1 shown in the generation of diazosulfide annulation, 3-diazosulfide;
Step 4 by the condensation reaction of Williamson ether, replaces halogen atom with alkoxyl group, generates 5-alkoxyl group-2,1, the 3-diazosulfide; Then the ether-splitting solution makes alkoxyl group form hydroxyl, generates 5-hydroxyl-2,1, the 3-diazosulfide;
Step 5,5-hydroxyl-2,1, compound carries out 1-benzopyran derivatives shown in the Claisen rearrangement reaction generating structure formula (I) shown in 3-diazosulfide and the structural formula (III); Wherein, R
1And R
2Be respectively H, contain 1～12 carbon alkyl, contain the alkoxyl group of 1～12 carbon or contain the alkylamino radical of 1～12 carbon.
7. method according to claim 6 is characterized in that, in the step 1, the used halogenating agent of halo is N-N-iodosuccinimide, N-bromo-succinimide or N-chlorosuccinimide.
8. method according to claim 6 is characterized in that, in the step 2, it is SnCl that nitroreduction is generated amino agents useful for same
2With the system of strong acid composition or the system of reduced iron powder and strong acid composition.
9. method according to claim 6 is characterized in that, in the step 3, described trialkylamine can be Trimethylamine, triethylamine, and described halogenation sulfoxide can be sulfur oxychloride, thionyl bromide.
10. the application of 1-benzopyran derivatives as claimed in claim 1 in photochromic material, it is characterized in that, described 1-benzopyran derivatives is applied in the optical fiber resin material, and described optical fiber resin component comprises body material and has the 1-benzopyran derivatives of the molecular structure shown in the structural formula (I).
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| CN104016996A (en) * | 2014-06-04 | 2014-09-03 | 上海甘田光学材料有限公司 | Novel benzopyran photo-chromic derivative |
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