CN113135883A - chrysene [1,2, f ] pyran photochromic compound and preparation method and application thereof - Google Patents

chrysene [1,2, f ] pyran photochromic compound and preparation method and application thereof Download PDF

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CN113135883A
CN113135883A CN202110429135.XA CN202110429135A CN113135883A CN 113135883 A CN113135883 A CN 113135883A CN 202110429135 A CN202110429135 A CN 202110429135A CN 113135883 A CN113135883 A CN 113135883A
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pyran
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刘宗
许铮
严泰山
席志强
张丽鑫
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Tianjin Uvos Technology Co ltd
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Abstract

The invention discloses a
Figure DSA0000240083760000011
And [1,2, f ]]Pyran photochromic compounds, and preparation methods and applications thereof. In particular to a compound with a structure shown as a formula I
Figure DSA0000240083760000012
And [1,2, f ]]Pyran compounds in which R1，R2Each independently selected from CH3O，CH3CH2O，CH3CH2CH2O，CH3，CH3CH2，CH3CH2CH2，(CH3)2N，(CH3CH2)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperidinyl, morpholinyl. The compounds can pass through 6-
Figure DSA0000240083760000014
Phenol and alkynol compounds. The
Figure DSA0000240083760000013
And [1,2, f ]]The pyran photochromic compound can be applied to the fields of photochromic glasses, intelligent windows, photochromic clothes and the like, and has the advantages of quick photoresponse, fast fading, excellent fatigue resistance and the like.

Description

chrysene [1,2, f ] pyran photochromic compound and preparation method and application thereof
The technical field is as follows:
the invention relates to the field of organic optical functional materials, in particular to a novel material
Figure BSA0000240083780000012
And [1,2, f ]]Pyran photochromic compounds, and preparation methods and applications thereof.
Background art:
the photochromic phenomenon is a phenomenon in which a structure of a compound is changed by irradiation with light having a certain intensity wavelength to form a new compound. Under the action of light or heat with another wavelength, it can be restored to its original state. The ultraviolet absorption spectra of the two isomers are obviously different and are apparent as color changes. In addition, physical parameters of the compound such as dielectric constant, refractive index, oxidation-reduction potential, fluorescence property, etc. are also changed. Currently, developed organic photochromic materials mainly include azobenzene, diarylethene, spirooxazine, naphthopyran and the like, wherein the naphthopyran photochromic materials have the advantages of easy synthesis, high chromaticity, fast color change and the like, and are widely applied to the fields of color-changing glasses, molecular switches, imaging equipment, intelligent windows and the like.
The currently reported organic photochromic materials, especially naphthopyran compounds, still face some disadvantages in use, mainly manifested by not fast fading rate and insufficient fatigue resistance to meet application requirements, especially the fading rate is always the bottleneck problem to be solved by the materials. Designing and synthesizing novel organic photochromic compounds, improving the fading rate of materials and improving the excellent fatigue resistance is a challenging problem in the field.
For this reason, the invention is easy to synthesize
Figure BSA0000240083780000013
Synthesis with aromatic ring as skeleton
Figure BSA0000240083780000014
And [1,2, f ]]Pyran compounds, which are a new class of photochromic compounds, are described in relation to naphthopyran compounds,
Figure BSA0000240083780000015
the aromatic ring has larger conjugation degree, can improve the fading rate and is also beneficial to improving the fatigue resistance.
Disclosure of Invention
An object of the present invention is to provide a compound which is quick in photoresponse, quick in discoloration and excellent in fatigue resistance
Figure BSA0000240083780000016
And [1,2, f ]]A pyran photochromic compound.
It is another object of the present invention to provide a process for preparing the above
Figure BSA0000240083780000017
And [1,2, f ]]A method of pyran photochromic compounds.
It is another object of the present invention to provide the above
Figure BSA0000240083780000018
And [1,2, f ]]Application of pyran photochromic compound is disclosed.
The technical scheme adopted by the invention for solving the technical problem is as follows:
has a structure shown in formula I:
Figure BSA0000240083780000021
wherein R is1，R2Each independently selected from CH3O，CH3CH2O，CH3CH2CH2O，CH3，CH3CH2，CH3CH2CH2，(CH3)2N，(CH3CH2)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperidinyl, morpholinyl.
Preferably, R1，R2Each independently selected from CH3O，CH3，(CH3)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperazine
A pyridyl group.
Further preferably, R1，R2Each independently selected from CH3O，CH3，H，F，Cl，Br，CF3And Ph.
More preferably, R1，R2Each independently selected from CH3O，CH3，H，F，Cl，CF3And Ph.
Most preferably, selected from the following compounds:
Figure BSA0000240083780000022
of the structure of formula I
Figure BSA0000240083780000032
And [1,2, f ]]The pyran photochromic compound can be prepared by the following method:
Figure BSA0000240083780000031
wherein the compound 1 and the compound 2 are soluble in aproticOrganic solvent reacts in the presence of acid catalyst, crude product is obtained by extraction, washing, drying and decompression concentration, the crude product is chromatographed by silica gel column to obtain compound I, R is1And R2Each independently selected from CH3O，CH3CH2O，CH3CH2CH2O，CH3，CH3CH2，CH3CH2CH2，(CH3)2N，(CH3CH2)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperidinyl, morpholinyl.
The aprotic organic solvent is selected from the group consisting of toluene, benzene, dimethyl sulfoxide, acetone, tetrahydrofuran and acetonitrile. The acid catalyst is selected from dodecylbenzene sulfonic acid, dodecylsulfuric acid and dodecylsulfonic acid.
Preferably, the molar ratio of the compound 1 to the compound 2 is 1: 1 to 1: 1.5, and more preferably 1: 1.2.
Preferably, the reaction temperature is 20-60 ℃, the reaction time is 2-5 h, more preferably 40 ℃, and the reaction time is 3 h.
Preferably, the detergent for silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 10-100: 1.
The compound shown in the formula I can be widely applied to the fields of photochromic glasses, photochromic glass, photochromic decorative articles, photochromic clothes, photochromic paint ink, anti-counterfeiting materials and the like as a photochromic material. Especially has better application prospect in the field of color-changing glasses, color-changing glass and color-changing clothes. The product can be added with photochromic material in the preparation process so as to obtain photochromic performance.
The invention has the advantages that: the invention has a structure of formula I
Figure BSA0000240083780000033
And [1,2, f ]]The pyran compound as a novel photochromic material has the characteristics of quick photoresponse color change, quick color fading, excellent fatigue resistance and the like.
Drawings
FIG. 1 is
Figure BSA0000240083780000034
And [1,2, f ]]Ultraviolet absorption spectra in the ring-off states of pyran compounds Ia, Ib, Ic, Id, Ie and If.
FIG. 2 shows UV light (365nm, 260mW)
Figure BSA0000240083780000042
And [1,2, f ]]Transient absorption spectra of pyran compounds Ia, Ib, Ic, Id, Ie and If.
FIG. 3 shows UV light (365nm, 260mW)
Figure BSA0000240083780000043
And [1,2, f ]]Pyran compounds Ia, Ib, Ic, Id, Ie and If at the wavelength of maximum absorption (. lamda.)max) Time-dependent photochromic curve of (a).
FIG. 4 is
Figure BSA0000240083780000044
And [1,2, f ]]Pyran compounds Ia, Ib, Ic, Id, Ie and If at the wavelength of maximum absorption (. lamda.)max) The fading curve of (c).
FIG. 5 is
Figure BSA0000240083780000045
And [1,2, f ]]Photochromic cycle curve of pyran compound Ie (ultraviolet light 20s, dark 20 s).
FIG. 6 is a photochromic cycling curve (UV 20s, photophobic 20s) for the naphthopyran molecule Da.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification. In the present invention, unless otherwise specified, the drugs and reagents used are commercially available or known in the art.
Example 113, 13-Diphenyl-13H-
Figure BSA0000240083780000046
And [1, 2-f ]]Preparation of pyrane (Ia)
Figure BSA0000240083780000041
Sequentially adding 6-
Figure BSA0000240083780000047
Phenol (0.31g, 1.25mmol), alkynol 2a (0.31g, 1.5mmol), was dissolved in benzene (20mL), dodecylbenzenesulfonic acid (1-2 drops) was added dropwise, stirred at 40 ℃ for 3h, monitored by TLC. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA 100: 1) to give Ia as a red solid, 179mg, 33% yield.m.p.208.8-210.4 ℃.
1H NMR(400MHz，CDCl3)δ8.56(m，1H)，8.50(m，1H)，8.39(m，2H)，7.84-7.76(m，1H)，7.67(d，J＝8.9Hz，1H)，7.64-7.51(m，6H)，7.51-7.42(m，2H)，7.39(d，J＝9.4Hz，1H)，7.21(m，4H)，7.15-7.07(m，2H)，6.09(d，J＝9.5Hz，1H).
13C NMR(101MHz，CDCl3)δ148.46，144.83，133.48，131.49，130.79，129.81，128.66，128.43，128.26，128.25，128.20，127.65，127.64，127.46，127.08，126.94，126.66，126.06，125.43，125.20，124.96，124.50，123.68，123.15，122.96，120.99，113.64，82.34.
Example 213-phenyl-13-biphenyl-13H-
Figure BSA0000240083780000052
And [1, 2-f ]]Preparation of pyran (Ib)
Figure BSA0000240083780000051
Sequentially adding 6-
Figure BSA0000240083780000053
Phenol (0.31g, 1.25mmol), alkynol 2b (0.36g, 1.25mmol), was dissolved in toluene (20mL), followed by dropwise addition of dodecylsulfuric acid (1-2 drops), stirring at 20 ℃ for 5h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 10: 1) to give red solid Ib, 178mg, 28% yield.m.p.219.9-221.4 ℃.
1H NMR(400MHz，CDCl3)δ8.53(m，2H)，8.41(d，J＝9.0Hz，1H)，8.35(d，J＝8.1Hz，1H)，7.86-7.76(m，1H)，7.71(m，3H)，7.63-7.43(m，9H)，7.39(t，J＝9.3Hz，1H)，7.23(t，J＝7.6Hz，1H)，7.13(m，1H)，7.11(s，1H)，6.05(d，J＝9.4Hz，1H).
13C NMR(101MHz，CDCl3)δ148.83，148.20，143.98，133.52，131.59，129.98，129.74，129.66，128.40，128.34，128.08，128.00，127.84，127.64，127.29，127.20，126.79，126.15，125.68，125.47，125.32，125.29，125.25，125.21，125.18，124.75，124.67，123.23，122.77，120.95，113.60，81.94.
Example 313-phenyl-13-p-trifluoromethylphenyl-13H-
Figure BSA0000240083780000054
And [1, 2-f ]]Preparation of pyran (Ic)
Figure BSA0000240083780000061
Sequentially adding 6-
Figure BSA0000240083780000063
Phenol (0.31g, 1.25mmol), alkynol 2c (0.52g, 1.88mmol), was dissolved in tetrahydrofuran (20mL), followed by dropwise addition of sodium dodecylsulfonate (1-2 drops), stirring at 30 ℃ for 4h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA: 80: 1) to give a dark red solid Ic, 119mg, 19% yield.m.p.185.9-187.6 ℃.
1H NMR(400MHz，CDCl3)δ8.67-8.57(m，1H)，8.50(d，J＝9.0Hz，1H)，8.45(d，J＝8.2Hz，0H)，7.87(d，J＝7.4Hz，1H)，7.77(d，J＝8.9Hz，1H)，7.65(dt，J＝9.8，6.7Hz，3H)，7.55-7.50(m，1H)，7.49-7.42(m，3H)，7.32-7.25(m，2H)，7.20-7.16(m，1H)，6.17(d，J＝9.4Hz，0H).
13C NMR(101MHz，CDCl3)δ148.45，144.72，143.77，140.68，140.46，133.49，131.49，129.80，128.69，128.22，128.19，127.64，127.45，127.34，127.27，127.09，126.90，126.88，126.64，126.04，125.42，125.18，124.94，124.50，123.56，123.12，122.94，120.96，113.62，82.25.
Example 413, 13-bis (4-fluorophenyl) -13H-
Figure BSA0000240083780000064
And [1, 2-f ]]Preparation of pyrans (Id)
Figure BSA0000240083780000062
Sequentially adding 6-
Figure BSA0000240083780000065
Phenol (0.31g, 1.25mmol), alkynol 2d (0.43g, 1.75mmol), dissolved in acetone (20mL), then dodecyl sulfuric acid (1-2 drops) was added dropwise, stirred at 50 ℃ for 5h,and monitoring by TLC. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 30: 1) to give Id as a red solid, 106mg, 18% yield.m.p.197.4-198.6 ℃.
1H NMR(400MHz，CDCl3)δ8.74-8.65(m，1H)，8.65(m，2H)，8.52-8.41(m，1H)，8.01-7.93(m，1H)，7.87(d，J＝9.0Hz，1H)，7.79-7.56(m，8H)，7.56-7.48(m，1H)，7.09-6.96(m，4H)，6.21-6.07(m，1H).
13C NMR(101MHz，CDCl3)δ163.48，161.03，148.09，140.33，133.51，129.74，128.71，128.63，128.32，128.03，127.78，127.33，127.29，126.73，126.12，125.62，125.27，124.74，124.61，123.20，123.11，122.72，120.95，115.21，114.99，113.45，81.61.
Example 513, 13-bis-p-methylphenyl-13H-
Figure BSA0000240083780000072
And [1, 2-f ]]Preparation of pyran (Ie)
Figure BSA0000240083780000071
Sequentially adding 6-
Figure BSA0000240083780000073
Phenol (0.31g, 1.25mmol), alkynol 2e (0.33g, 1.38mmol), was dissolved in dimethyl sulfoxide (20mL), followed by dropwise addition of dodecylsulfonic acid (1-2 drops), stirring at 30 ℃ for 2h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA 60: 1) to give Ie as a pale red solid, 138mg, 24% yield.m.p.225.3-226.8 ℃.
1H NMR(400MHz，CDCl3)δ8.55(m，1H)，8.43(m，1H)，7.83(d，J＝7.3Hz，1H)，7.71(d，J＝8.9Hz，1H)，7.63-7.55(m，2H)，7.48(d，J＝8.0Hz，5H)，7.39(d，J＝9.4Hz，1H)，7.17-7.09(m，1H)，7.03(d，J＝7.9Hz，4H)，6.08(d，J＝9.4Hz，1H)，2.18(s，6H).
13C NMR(101MHz，CDCl3)δ148.52，142.02，137.19，133.49，131.44，130.73，129.84，128.82，128.27，128.20，127.51，126.86，126.79，126.55，125.98，125.29，125.10，125.02，124.41，123.96，123.07，122.98，120.98，113.62，82.26，21.07.
Example 613, 13-bis-p-methoxyphenyl-13H-
Figure BSA0000240083780000074
And [1, 2-f ]]Preparation of pyran (If)
Figure BSA0000240083780000081
Sequentially adding 6-
Figure BSA0000240083780000082
Phenol (0.31g, 1.25mmol), alkynol 2f (0.43g, 1.63mmol), was dissolved in dichloromethane (20mL), followed by dropwise addition of dodecylbenzenesulfonic acid (1-2 drops), stirring at 20 ℃ for 3h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 30: 1) to give a magenta solid If, 154mg, 25% yield.m.p.237.1-238.3 ℃.
1H NMR(400MHz，CDCl3)δ8.52-8.41(m，2H)，8.38(m，2H)，7.78(d，J＝7.8Hz，1H)，7.65(d，J＝8.9Hz，1H)，7.55-7.49(m，2H)，7.49-7.42(m，5H)，7.38-7.30(m，1H)，7.08(s，1H)，6.70(d，J＝8.8Hz，4H)，6.00(d，J＝9.4Hz，1H)，3.57(s，3H).
13C NMR(101MHz，CDCl3)δ159.01，148.46，137.11，133.52，132.30，132.23，131.46，130.32，129.85，128.30，128.26，127.56，127.48，126.75，126.59，126.03，125.35，125.14，125.01，124.43，124.07，123.13，122.96，122.76，121.02，113.58，113.49，82.07，55.22.
Example 7 testing of photochromic Properties of Compounds Ia, Ib, Ic, Id, Ie and If
Selecting ethyl acetate as ultraviolet testing solvent, 1 × 10-4mol/L is the test concentration. Based on the above standard conditions, UV absorption spectra of Ia, Ib, Ic, Id, Ie and If before light irradiation were tested, as shown in FIG. 1.
Transient absorption spectra after 30s irradiation of Ia, Ib, Ic, Id, Ie and If under UV light (365nm, 260mW) were tested, as shown in FIG. 2. As can be seen from the figure, Ia, Ib, Ic, Id, Ie and If give rise to new absorption peaks at 460nm after illumination.
The ultraviolet light (365nm, 260mW) irradiation is tested,
Figure BSA0000240083780000083
and [1,2, f ]]The time required for the color of the pyran compounds Ia, Ib, Ic, Id, Ie and If to reach saturation is shown in FIG. 3. As can be seen, Ia, Ib, Ic, Id, Ie and If are all relatively saturated at the wavelength of maximum absorption at about 30s or so under continuous UV lamp illumination. In terms of rate of color change, compared to others
Figure BSA0000240083780000084
And [1,2, f ]]The pyran compound, If, has the obvious advantage of reaching saturation in 10 seconds.
Example 8 discoloration Properties testing of Compounds Ia, Ib, Ic, Id, Ie and If
The thermal fading curves of Ia, Ib, Ic, Id, Ie and If after 30s UV irradiation (365nm, 260mW) in dark conditions were tested, as shown in FIG. 4,
Figure BSA0000240083780000093
and [1,2, f ]]The absorbance of the pyran compound is decreased from the maximum value to a steady state within a period of 30 to 96 seconds, wherein the residual color of Ia and If is the lowest and the fading property is good.
EXAMPLE 9 fatigue resistance study of Compound Ie
Taking Ie as an example, dissolving it in an organic solvent at a certain concentration, and testing the absorbance of the solution after the solution develops color after being irradiated by ultraviolet light for 20s and the absorbance of the solution after the solution becomes lighter after being shielded from light for 20 s. The fatigue resistance curve was developed after 10 cycles of the test, as shown in fig. 5. The compound is found to have excellent fatigue resistance, and the peak value of the absorbance is hardly changed under the condition of 10-cycle color development test.
For comparison, the naphthopyran molecules Da were measured in the same manner and tested 10 times in cycles to develop a fatigue resistance curve, as shown in FIG. 6. The curve shows that the absorbance peak value of the Da molecule is gradually reduced along with the increase of the color development times, which shows that the color development depth of the Da molecule is continuously reduced along with the increase of the measurement times. Comparing fig. 5, fig. 6, it is evident that the chromaticity of Ie is much higher than Da, thus demonstrating that: with respect to the naphthopyran compounds, there is a need for,
Figure BSA0000240083780000094
the aromatic ring has a larger conjugation degree, and contributes to improvement of fatigue resistance of color development.
Figure BSA0000240083780000091
Example 1013-phenyl-13-p-nitrophenyl-13H-
Figure BSA0000240083780000095
And [1, 2-f ]]Preparation of pyrans (Ig)
Figure BSA0000240083780000092
Sequentially adding 6-
Figure BSA0000240083780000103
Phenol (0.31g, 1.25mmol), alkynol 2g (0.38g, 1.5mmol), dissolved in chloroform (20mL), followed by dropwise addition of sodium dodecylbenzenesulfonate (1-2 drops), stirring at 40 ℃ for 3h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 50: 1) to give Ig as a red oil, 144mg, 24% yield in ms (m/z, ESI +): 480.2[ M + H]+。
Example 1113, 13-bis-p-dimethylaminophenyl-13H-
Figure BSA0000240083780000104
And [1, 2-f ]]Preparation of pyran (Ih)
Figure BSA0000240083780000101
Sequentially adding 6-
Figure BSA0000240083780000105
Phenol (0.31g, 1.25mmol), alkynol 2h (0.44g, 1.5mmol), dissolved in acetonitrile (20mL), followed by dropwise addition of sodium dodecylbenzenesulfonate (1-2 drops), stirring at 30 ℃ for 3h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 90: 1) to give Ih as a red oil, 202mg, 31% yield. ms (m/z, ESI +): 521.7[ M + H]+。
Example 1213-phenyl-13-p-chlorophenyl-13H-
Figure BSA0000240083780000106
And [1, 2-f ]]Preparation of pyran (Ii)
Figure BSA0000240083780000102
Sequentially adding 6-
Figure BSA0000240083780000107
Phenol (0.31g, 1.25mmol), alkynol 2i (0.36g, 1.5mmol), was dissolved in toluene (20mL), followed by dropwise addition of sodium dodecylsulfate (1-2 drops), stirring at 60 ℃ for 3h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 90: 1) to give Ii, 105mg, 18% yield in blue as a red oil (m/z, ESI +): 469.1[ M + H]+。
Example 1313, 13-bis-p-bromophenyl-13H-
Figure BSA0000240083780000113
And [1, 2-f ]]Preparation of pyran (Ij)
Figure BSA0000240083780000111
Sequentially adding 6-
Figure BSA0000240083780000114
Phenol (0.31g, 1.25mmol), alkynol 2j (0.55g, 1.5mmol), dissolved in benzene (20mL), followed by dropwise addition of sodium dodecyl sulfate (1-2 drops), stirring at 60 ℃ for 3h, TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20mL), washed with saturated brine (30mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA ═ 60: 1) to give red oil Ij, 111mg, 5% yield. ms (m/z, ESI +): 593.0[ M + H]+。
Example 1413-phenyl-13-p-iodophenyl-13H-
Figure BSA0000240083780000115
And [1, 2-f ]]Preparation of pyrans (Ik)
Figure BSA0000240083780000112
Referring to the procedure of example 1, a red oil, Ik, 63mg, 9% yield. ms (m/z, ESI +): 561.1[ M + H]+。
Example 1513-phenyl-13-p-diethylaminophenyl-13H-
Figure BSA0000240083780000116
And [1, 2-f ]]Preparation of pyran (Il)
Figure BSA0000240083780000121
Referring to the procedure of example 2, a red oil, Il, 177mg, 28% yield. ms (m/z, ESI +): 506.3[ M + H]+。
Example 1613-phenyl-13-p-ethylphenyl-13H-
Figure BSA0000240083780000124
And [1, 2-f ]]Preparation of pyran (Im)
Figure BSA0000240083780000122
Referring to the procedure of example 3, a red oil Im, 116mg, 20% yield. ms (m/z, ESI +): 463.2[ M + H]+。
Example 1713-phenyl-13-n-propoxyphenyl-13H-
Figure BSA0000240083780000125
And [1, 2-f ]]Preparation of pyran (In)
Figure BSA0000240083780000123
Referring to the procedure of example 4, a red oil, In, was prepared, 92mg, 15% yield. ms (m/z, ESI +): 493.2[ M + H]+。
Example 1813-p-methylphenyl-13-p-nitrophenyl-13H-
Figure BSA0000240083780000134
And [1, 2-f ]]Preparation of pyran (Io)
Figure BSA0000240083780000131
Referring to the procedure of example 5, a red oil, Io, 136mg, 22% yield. ms (m/z, ESI +): 494.2[ M + H]+。
Example 1913-p-Biphenyl-13-p-trifluoromethylphenyl-13H-
Figure BSA0000240083780000135
And [1, 2-f ]]Preparation of pyrans (Ip)
Figure BSA0000240083780000132
Referring to the procedure of example 6, a red oil Ip, 130mg, 18% yield.ms (m/z, ESI +): 579.2[ M + H]+。
Example 2013-p-methoxy-phenyl-13-p-ethylphenyl-13H-
Figure BSA0000240083780000136
And [1, 2-f ]]Preparation of pyran (Iq)
Figure BSA0000240083780000133
Referring to the procedure of example 10, a red oil, Iq, 154mg, 25% yield.ms (m/z, ESI +): 493.2[ M + H]+。
Example 2113-p-methoxy-13-p-dimethylaminophenyl-13H-
Figure BSA0000240083780000143
And [1, 2-f ]]Preparation of pyran (Ir)
Figure BSA0000240083780000141
Referring to the procedure of example 11, a red oil Ir, 114mg, 18% yield.ms (m/z, ESI +): 508.2[ M + H ]]+。
Example 2213-p-chlorophenyl-13-p-trifluoromethylphenyl-13H-
Figure BSA0000240083780000144
And [1, 2-f ]]Preparation of pyrans (Is)
Figure BSA0000240083780000142
Referring to the procedure of example 12, a red oil Is prepared, 134mg, 20% yield.ms (m/z, ESI +): 537.1[ M + H]+。
Example 2313, 13-Biphenyl-13H-
Figure BSA0000240083780000145
And [1, 2-f ]]Preparation of pyran (It)
Figure BSA0000240083780000151
Referring to the procedure of example 13, It was prepared as a red oil, 220mg, 30% yield.ms (m/z, ESI +): 587.2[ M + H]+。
Example 2413-phenyl-13-p-piperidinylphenyl-13H-
Figure BSA0000240083780000154
And [1, 2-f ]]Preparation of pyrans (Iu)
Figure BSA0000240083780000152
Referring to the procedure of example 1, a red oil Iu, 162mg, 25% yield.ms (m/z, ESI +): 518.3[ M + H]+。
Example 2513-phenyl-13-p-morpholinophenyl-13H-
Figure BSA0000240083780000155
And [1, 2-f ]]Preparation of pyran (Iv)
Figure BSA0000240083780000153
Referring to the procedure of example 1, a red oil Iv, 123mg, 19% yield.ms (m/z, ESI +): 520.2[ M + H ]]+。
Example 26 contains 13, 13-bis-p-methylphenyl-13H-
Figure BSA0000240083780000161
And [1, 2-f ]]Preparation of pyran (Ie) color-changing spectacle lens Prepare for
Taking one kilogram of color changing spectacle lens resin as an example, 1 gram of 13, 13-bis-p-methylphenyl-13H-
Figure BSA0000240083780000162
And [1, 2-f ]]Uniformly mixing 50-55% of pyran (Ie) and (fluorosilicone) acrylate, 35-40% of styrene, 10% of cross-linking agent, 1-2 g of initiator and 5-10 g of light stabilizer, injecting the mixture into a mold, and heating and polymerizing for 24 hours at 95-100 ℃ until the resin is hardened to obtain the spectacle lens. And soaking the lens in deionized water to obtain the photochromic contact lens.
Example 27 contains 13, 13-bis-p-methoxyphenyl-13H-
Figure BSA0000240083780000163
And [1, 2-f ]]Pyran (If) color-changing raincoat plastic Preparation of
15g of stearic acid, 1g of glyceryl monostearate, 0.5g of hexadecanol and 6g of glycerol are uniformly mixed, heated to 90 ℃, and then added with 13, 13-di-p-methoxyphenyl-13H-
Figure BSA0000240083780000164
And [1, 2-f ]]0.1g of the pyran (If) photochromic compound was stirred for 5 hours to allow the color-changing dye to be completely dissolved in the mixture. Adding 80g of distilled water at the temperature of 80-90 ℃, accelerating the stirring until complete emulsification, reducing the temperature to 40-45, adding 0.1g of a mixture of methyl paraben, ethyl paraben and propyl paraben, uniformly mixing, and cooling to room temperature. And preparing the photochromic plastic. The plastic can be used for preparing photochromic raincoats.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications derived from the technical solutions of the present invention are within the scope of the present invention.

Claims (10)

1. One kind
Figure FSA0000240083770000013
And [1,2, f ]]The pyran photochromic compound is characterized by having a structure shown as a formula I:
Figure FSA0000240083770000011
wherein R is1，R2Each independently selected from CH3O，CH3CH2O，CH3CH2CH2O，CH3，CH3CH2，CH3CH2CH2，(CH3)2N，(CH3CH2)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperidinyl, morpholinyl.
2. The compound of claim 1 having the structure of formula I
Figure FSA0000240083770000014
And [1,2, f ]]A pyran photochromic compound characterized in that R1，R2Each independently selected from CH3O，CH3，(CH3)2N，H，F，Cl，Br，I，CF3，NO2Ph, piperidinyl.
3. The compound of claim 2 having the structure of formula I
Figure FSA0000240083770000015
And [1,2, f ]]A pyran photochromic compound characterized in that R1，R2Each independently selected from CH3O，CH3，H，F，Cl，Br，CF3And Ph.
4. The method of claim 3Having the structure of formula I
Figure FSA0000240083770000016
And [1,2, f ]]A pyran photochromic compound selected from:
Figure FSA0000240083770000012
Figure FSA0000240083770000021
5. the compound of any one of claims 1-4 having the structure of formula I
Figure FSA0000240083770000023
And [1,2, f ]]A method for preparing a pyran photochromic compound, characterized by comprising the steps of:
Figure FSA0000240083770000022
dissolving the compound 1 and the compound 2 in an aprotic organic solvent, reacting in the presence of an acid catalyst, extracting, washing, drying, concentrating under reduced pressure to obtain a crude product, and performing silica gel column chromatography on the crude product to obtain the compound I.
6. The process of claim 5, wherein the aprotic organic solvent is selected from one or more of toluene, benzene, dimethyl sulfoxide, acetone, tetrahydrofuran, and acetonitrile. The acid catalyst is selected from one or more of dodecyl benzene sulfonic acid, dodecyl sulfuric acid and dodecyl sulfonic acid.
7. The method for preparing the compound of formula I according to claim 5, wherein the molar ratio of the compound 1 to the compound 2 is 1: 1-1: 1.5.
8. The preparation method of the compound of formula I according to claim 5, wherein the reaction temperature is 20-60 ℃ and the reaction time is 2-5 h.
9. The preparation method of claim 5, wherein the detergent for silica gel column chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 10-100: 1.
10. The method according to any one of claims 1 to 4
Figure FSA0000240083770000031
And [1,2, f ]]The pyran photochromic compound is applied to preparing photochromic glasses, photochromic glass, photochromic decorative articles, photochromic clothes, photochromic paint ink and anti-counterfeiting materials.
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