CN108250174A - Naphtho-pyrans compounds and preparation method thereof - Google Patents

Naphtho-pyrans compounds and preparation method thereof Download PDF

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CN108250174A
CN108250174A CN201810121584.6A CN201810121584A CN108250174A CN 108250174 A CN108250174 A CN 108250174A CN 201810121584 A CN201810121584 A CN 201810121584A CN 108250174 A CN108250174 A CN 108250174A
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preparation
naphtho
catalyst
reaction
pyrans
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CN108250174B (en
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蒋高喜
张金龙
杨化萌
夏春谷
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Abstract

The invention discloses a kind of naphtho-pyrans compounds and preparation method thereof, which stablizes, and breaches the structure shortcoming of former naphtho-pyrans compounds.Preparation method includes step：(1) diaryl is joined into vinyl compound and naphthol compound is dissolved in solvent, obtain pre-reaction mixed solution；(2) the pre-reaction mixed solution of gained reacts under conditions of temperature is 50 80 DEG C and catalyst in step (1), obtains the naphtho-pyrans compounds.Preparation method step is simple, mild condition, it is easy to accomplish, it is environmentally protective more suitable for industrialized production.

Description

Naphtho-pyrans compounds and preparation method thereof
Technical field
The present invention relates to compound and preparation method thereof more particularly to a kind of novel naphtho-pyrans compounds and its systems Preparation Method.
Background technology
Pyran compounds due to having preferable optical Response, faster fading rate and preferable photostability, And become after spirooxazine compounds, the another kind of photochromic dyes with actual application value.Particularly it is used for light The preparation of the protective materials of mutagens chromoresin glasses and the vehicles.Pyran photochromic compound is broadly divided into naphtho- pyrrole Class of muttering and heteroaromatic and pyran compounds.
Photochromic material is since it is in light energy conversion, optical mirror slip, windshield, optical anti-counterfeiting, decoration material The application of material etc. is more and more universal and its huge dive is shown in fields such as optical information storage, optical recording and photoswitches Before application scape and attract attention.The research and preparation of organic photochromic material have many reports.Aphthopyrans class chemical combination Object is a kind of important organic photochromic material, with preferable optical Response, faster fading rate and preferable light Stability has extensively in non-silver salt photosensitive material, erasable rewritable type CD, organic photochromic resin lens and the fields such as anti-fake Application.
The photosensitive colour-changing phenomenon of photosensitive colour-changing material is changed by compound structure and is generated, by the heterolytic fission of illumination lower key with It reconfigures and realizes, shown in following illumination reaction：
Photo absorption property and anti-fatigue performance are two big important indicators of photosensitive colour-changing substance, and required color can also lead to The allotment of different colours is crossed to realize, therefore synthesis photoresponse is good, anti-fatigue performance is excellent and there are the various light of different color changeable effects Mutagens color substance has important application value.Since the color changeable effect of photosensitive colour-changing compound depends on closed loop body and open loop body The change of absorbing wavelength, and the degree of its molecular structure conjugation generates its absorbing wavelength the influence of blue shift or red shift, therefore often The structure change seen is to be changed on reaction substrate plus appropriate substituent group with changing the conjugated degree of product molecule so as to reach Become the purpose of photosensitive electrochromic substance color changeable effect.
In general, currently used synthetic method mainly has following three kinds：The first is Kabbe synthetic methods, Chang Yilin Hydroxy acetophenone or adjacent hydroxyl acetonaphthone class compound carry out condensation reaction with ketone, and gained intermediate is using reduction and dehydration two It walks successive reaction and completes；Second is to be reacted by aryl grignard reagent with benzo cumarin, is then dehydrated to obtain product；Third Kind is by propargyl alcohol and naphthols or phenol fabricated in situ propargyl aryl ether, then in acid condition, propargyl aryl ether Claisen rearangement occurs and reacts to obtain product.But these methods respectively have its defect, as reaction condition is harsher, intermediate is not easy Preservation, yield are more low, and which limits its industrialized production processes.
Invention content
Goal of the invention：The present invention provides a kind of naphtho-pyrans compounds and preparation method thereof, the compounds property is steady It is fixed, fill up the structure shortcoming of naphtho-pyrans compounds in the prior art；The preparation method solves existing preparation method Condition is harsher, intermediate is not easy to maintain, yield is relatively low, is unsuitable for the problems such as industrialized production.
Technical solution：The naphtho-pyrans compounds of the present invention, just like the general structure of formula (III)：
In the general structure, R1、R2And R3Separately selected from H, halogen, cyano, alkyl, alkoxy, formoxyl, Formamido, benzoyl and group-4 ethyl formate.
Wherein, R1Independently selected from H, cyano, halogen, alkoxy, formoxyl, formamido, benzoyl and formic acid second Ester group.
The halogen is one or more of for F, Cl and Br, preferably Br.
The alkoxy is one or more of C1-C4 alkoxies, preferably methoxyl group.
And R2And R3Separately it is selected from H, halogen, alkyl and alkoxy.
The halogen is one or more of F, Cl and Br.
The alkyl is one or more of C1-C4 alkyl, preferably methyl.
The alkoxy is one or more of C1-C4 alkoxies, preferably methoxyl group.
The preparation method of above-mentioned naphtho-pyrans compounds, includes the following steps：
(1) naphthol compound that the diaryl of formula (I) is joined to vinyl compound and formula (II) is dissolved in solvent, is obtained pre- Reaction mixture.
(2) the pre-reaction mixed solution of gained reacts under conditions of temperature is 50-80 DEG C and catalyst in step (1), Obtain the naphtho-pyrans compounds.
Reaction route is as follows：
R1、R2And R3Separately selected from H, halogen, cyano, alkyl, alkoxy, formoxyl, formamido, benzoyl Base and group-4 ethyl formate.
Wherein, R1Independently selected from H, cyano, halogen, alkoxy, formoxyl, formamido, benzoyl and formic acid second Ester group.
The halogen is one or more of for F, Cl and Br, preferably Br.
The alkoxy is one or more of for C1-C4 alkoxies, preferably methoxyl group and ethyoxyl, further preferred first Oxygroup.
And R2And R3Separately it is selected from H, halogen, alkyl and alkoxy.
The halogen is one or more of F, Cl and Br.
The alkyl is one or more of for C1-C4 alkyl, preferably methyl, ethyl, further preferred methyl.
The alkoxy is one or more of for C1-C4 alkoxies, preferably methoxyl group, preferably methoxyl group and ethyoxyl, Further preferred methoxyl group.
In step (1), a concentration of 0.1-0.2mol/L, preferably 0.13- of the diaryl connection vinyl compound 0.17mol/L, further preferred 0.15mol/L.
The molar ratio of the diaryl connection vinyl compound and naphthol compound is 1-2:1, preferably 1.3-1.7:1, into One step preferably 1.5:1.
The preferable organic solvent of solvent Selective dissolution is in dichloromethane, dichloroethanes, chloroform and toluene One or more, preferred dichloroethanes.
In step (2), preferably 80 DEG C of reaction temperature.
The catalyst is phosphonic acids catalyst.The preferred diphenyl phosphate of phosphonic acids catalyst, dosage are catalyst amount, tool Body dosage is the 5%mol of naphthol compound amount.
In the poor reaction of substrate active, step is additionally added co-catalyst in (2).
The co-catalyst is acidic promotor.Acidic promotor is benzoic acid, trifluoro-benzoic acid, p-methyl benzenesulfonic acid One or more of with three fluosulfonic acid, dosage is catalyst amount, and specific dosage is less than naphthol compound amount 5mmol%.But in the preferable reaction substrate of reactivity, co-catalyst can not be added.
The specific preparation method of above-mentioned naphtho-pyrans compounds, includes the following steps：
(1) the diaryl connection vinyl compound of formula (I) and the naphthol compound of formula (II) are dissolved in dichloroethanes, are obtained Pre-reaction mixed solution.
(2) the pre-reaction mixed solution obtained into step (1) adds in catalyst (relative to naphthol compound 5mmol%), normal-temperature reaction 20-40min, preferably 30min；50-80 DEG C is then heated to continue to be stirred to react 7-9h, it is preferably warm 80 DEG C of degree, is stirred to react 8h, is cooled to room temperature, co-catalyst (relative to the 5mmol% of naphthol compound) is added in, in 70- 80 DEG C of stirring 20-40min, preferably stir 30min under the conditions of 80 DEG C, obtain reaction mixture under the conditions of 90 DEG C.
(3) reaction mixture is cooled to room temperature after the reaction was complete, with the isolated product aphthopyrans class of silicagel column Compound.
Naphtho-pyrans compounds obtained nearly more than 30 are planted in aforementioned manners, and which part product structure formula is as follows：
The corresponding compound name of more than structural formula is：
1st, 3- diphenylmethylenes aphthopyrans；2nd, 6- methoxyl groups -3- diphenylmethylene aphthopyrans；3rd, 10- methoxies Base -3- diphenylmethylene aphthopyrans；4th, the bromo- 3- diphenylmethylenes aphthopyrans of 7-；5th, the bromo- 3- diphenylmethylenes of 6- Aphthopyrans；6th, the bromo- 3- diphenylmethylenes aphthopyrans of 10-；7th, 7- cyano -3- diphenylmethylene aphthopyrans；8、7- Benzoyl -3- diphenylmethylene aphthopyrans；9th, 7- formic acid esters -3- diphenylmethylene aphthopyrans；10th, 3- diphenyl Methylene anthra pyrans；11st, 3- diphenylmethylenes pyrene and pyrans；12nd, N- benzoyls -3- diphenylmethylenes indoles and pyrrole It mutters；13rd, 3,5- dimethoxys -3- diphenylmethylene chromenes；14th, 3- diphenylmethylenes chromene；15、3,10- Bis- two pyrans of (diphenyl methyl)-naphtho-；16th, bis- two pyrans of (diphenylmethylene)-naphtho- of 3,11-；17th, the bis- (hexichol of 2,8- Ylmethyl) two pyrans of-naphtho-；18th, bis- (3- diphenylmethylenes) naphtho-s of 1,2- and pyrans crosses thioether；19th, bis- (the 4- fluorophenyls of 3- Methylene) aphthopyrans；20th, bis- (the 4- bromobenzenes methylene) aphthopyrans of 3-；21st, bis- (4- chlorobenzenes methylene) the naphtho- pyrroles of 3- It mutters；22nd, (E) -3- (4- chlorphenyls) phenylmethylene-aphthopyrans；23rd, (E) -3- (4- aminomethyl phenyls) phenylmethylene-naphthalene And pyrans；24th, (E) -3- (naphthalene) phenylmethylene-aphthopyrans；25th, (E) -3- tolylthiophenes methylene-aphthopyrans； 26th, (Z)-[(1.3- diphenylmethylene aphthopyrans base) phenylmethylene] aphthopyrans.
Advantageous effect：1st, novel naphthopyran class compounds property provided by the invention is stablized, and purity is higher；2nd, it breaches The structure shortcoming of naphtho-pyrans compounds in the past；3rd, completely new big pi bond delocalized electron body, conducive to the photochromism of the structure The exploitation of energy；4th, preparation method step of the invention is simple, can be prepared by naphtho-pyrans compounds by single step reaction；5、 Mild condition, it is easy to accomplish；6th, the new three wastes are not generated in preparation process, environmental-friendly, the development to adapt to the epoch provides one The environmentally protective synthetic method of item；7th, raw material is less compared with type in preparation method, and consersion unit is less, and preparation process is less, into This is relatively low, more suitable for industrialized production.
Description of the drawings
Fig. 1 is the 3- diphenylmethylene aphthopyrans prepared in the embodiment of the present invention 11H-NMR spectrum；
Fig. 2 is the 3- diphenylmethylene aphthopyrans prepared in the embodiment of the present invention 113C-NMR spectrograms.
Specific embodiment
Embodiment 1
The preparation of 1,3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and beta naphthal (0.5mmol) It is added in dichloroethanes DCE (5mL), stirs to two kinds of substrates and dissolve.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.Postcooling that the reaction was complete is to room temperature, with the isolated product 1 of silicagel column, 3- hexichol Methylene aphthopyrans, yield 93%.
Structural characterization data：1H-NMR(400MHz,CDCl3) δ 7.90 (d, J=8.5Hz, 1H), 7.72 (dd, J=8.2, 1.3Hz, 1H), 7.64 (d, J=8.9Hz, 1H), 7.47 (ddd, J=8.5,7.4,1.4Hz, 3H), 7.41-7.25 (m, 8H), 7.23-7.14 (m, 1H), 7.10-7.05 (m, 1H), 7.02 (d, J=10.3Hz, 1H), 6.46 (d, J=10.3Hz, 1H).
13C-NMR(101MHz,CDCl3)δ151.74,146.86,140.31,139.39,131.30,130.03, 129.87,129.66,128.84,128.58,128.57,127.71,126.98,126.87,126.03,124.32,121.80, 121.14,120.41,116.75,116.27,114.30。
HRMS(ESI+):m/z Calcd.for C26H19O[M+H]+:347.1436.Found:347.1421；for C26H18NaO[M+Na]+:369.1255.Found:369.1283。
Embodiment 2
The preparation of 6- methoxyl group -3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 7- methoxynaphthols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 8h.Reaction intermediate is isolated, is added to dichloroethanes DCE (5mL) again, and add in catalyst phosphonic acids (5mmol%) is warming up to 80 DEG C, stirs 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirrings 30min.Postcooling that the reaction was complete is to room temperature, with the isolated product 6- methoxyl groups -3- diphenylmethylenes naphtho- pyrrole of silicagel column It mutters, yield 73%.
1H-NMR(400MHz,CDCl3) δ 7.60 (d, J=8.9Hz, 1H), 7.55 (d, J=8.8Hz, 1H), 7.50-7.43 (m, 2H), 7.40-7.33 (m, 2H), 7.29 (tdd, J=7.9,5.2,2.4Hz, 6H), 7.23-7.15 (m, 2H), 7.01 (dd, J=8.9,2.4Hz, 1H), 6.94 (t, J=8.9Hz, 2H), 6.44 (d, J=10.3Hz, 1H), 3.88 (s, 3H).
13C-NMR(101MHz,CDCl3)δ158.74,152.37,146.84,140.37,139.41,131.32, 130.23,130.12,129.84,129.66,128.53,127.69,126.82,125.98,125.24,121.19,120.51, 116.33,116.12,114.25,113.43,100.43,77.32,77.00,76.68,55.22。
HRMS(ESI+):m/z Calcd.for C27H21O2[M+H]+:377.1542.Found:377.1526； C27H20NaO2[M+Na]+:399.1361.Found:399.1360。
Embodiment 3
The preparation of 10- methoxyl group -3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 3- methoxynaphthols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 8h.Reaction intermediate is isolated, is added to dichloroethanes DCE (5mL) again, and add in catalyst phosphonic acids (5mmol%) is warming up to 80 DEG C, stirs 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirrings 30min.Postcooling that the reaction was complete is to room temperature, with the isolated product 10- methoxyl groups -3- diphenylmethylenes naphtho- pyrrole of silicagel column It mutters, yield 60%.
1H-NMR(400MHz,CDCl3)δ7.90–7.81(m,1H),7.73–7.62(m,3H),7.44–7.38(m,2H), 7.38-7.33 (m, 3H), 7.33-7.28 (m, 4H), 7.20-7.14 (m, 1H), 7.08 (s, 1H), 6.99 (d, J=10.3Hz, 1H), 6.40 (d, J=10.3Hz, 1H), 3.97 (s, 3H)
13C-NMR(101MHz,CDCl3)δ147.32,146.70,140.08,138.75,131.56,130.07, 129.49,128.71,128.17,127.76,127.56,127.24,126.96,125.90,124.87,124.65,124.08, 122.36,120.99,120.18,115.04,108.02,77.32,77.00,76.68,56.02.
HRMS(ESI+):m/z Calcd.for C27H21O2[M+H]+:377.1542.Found:377.1533； C27H20NaO2[M+Na]+:399.1361.Found:399.1354.
Embodiment 4
The preparation of the bromo- 3- diphenylmethylenes aphthopyrans of 7-, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 6- bromide naphthols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C stirring 30min.Postcooling that the reaction was complete is to room temperature, with the bromo- 3- diphenylmethylenes naphtho-s of the isolated product 7- of silicagel column Pyrans, yield 79%.
1H-NMR(400MHz,CDCl3) δ 7.82 (d, J=2.1Hz, 1H), 7.69 (d, J=9.0Hz, 1H), 7.52-7.40 (m, 4H), 7.40-7.33 (m, 2H), 7.33-7.23 (m, 5H), 7.22-7.16 (m, 1H), 7.03 (d, J=8.9Hz, 1H), 6.88 (d, J=10.3Hz, 1H), 6.44 (d, J=10.3Hz, 1H)
13C-NMR(101MHz,CDCl3)δ151.82,146.49,140.08,139.17,131.20,130.94, 130.44,130.10,129.65,128.91,128.58,127.72,127.26,126.97,126.18,122.94,122.35, 119.80,118.06,117.80,116.90,114.56,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H17BrNaO[M+Na]+:447.0360.Found:447.0365.
Embodiment 5
The preparation of the bromo- 3- diphenylmethylenes aphthopyrans of 6-, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 7- methoxynaphthols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C stirring 30min.Postcooling that the reaction was complete is to room temperature, with the bromo- 3- diphenylmethylenes naphtho-s of the isolated product 6- of silicagel column Pyrans, yield 69%.
1H-NMR (400MHz, CDCl3) δ 8.04 (d, J=1.9Hz, 1H), 7.58 (t, J=8.5Hz, 2H), 7.49- 7.42 (m, 2H), 7.42-7.34 (m, 2H), 7.34-7.25 (m, 5H), 7.23-7.16 (m, 1H), 7.07 (d, J=8.9Hz, 1H), 6.90 (d, J=10.3Hz, 1H), 6.48 (d, J=10.3Hz, 1H)
13C-NMR(101MHz,CDCl3)δ152.38,146.50,140.08,139.22,131.21,130.15, 130.02,129.86,129.69,128.60,128.25,127.74,127.66,127.01,126.21,123.76,116.98, 122.28,121.61,119.81,117.19,113.74,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H17BrNaO[M+Na]+:447.0360.Found:447.0334.
Embodiment 6
The preparation of the bromo- 3- diphenylmethylenes aphthopyrans of 10-, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 3- bromide naphthols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C stirring 30min.Postcooling that the reaction was complete is to room temperature, with the bromo- 3- diphenylmethylenes naphtho-s of the isolated product 10- of silicagel column Pyrans, yield 63%.
1H-NMR(400MHz,CDCl3) δ 7.91 (s, 1H), 7.86 (d, J=8.5Hz, 1H), 7.67-7.54 (m, 3H), 7.53-7.44 (m, 1H), 7.42-7.35 (m, 3H), 7.35-7.26 (m, 6H), 7.25-7.16 (m, 1H), 6.95 (d, J= 10.3Hz, 1H), 6.47 (d, J=10.3Hz, 1H)
13C-NMR(101MHz,CDCl3)δ148.33,146.36,140.03,138.40,132.45,131.26, 130.41,130.19,128.63,127.84,127.66,127.60,127.18,127.10,126.41,125.24,122.75, 121.29,119.67,117.89,116.10,110.39,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H18BrO[M+H]+:425.0541.Found:425.0539； C26H17BrNaO[M+Na]+:447.0360.Found:447.0364.
Embodiment 7
The preparation of 7- cyano -3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 6- cyano naphthols 2 (0.5mmol) is added in dichloroethanes DCE (5mL), stirring to connection alkene dissolving, it is impossible to which the naphthols of dissolving is stirred to no solid Particle.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 8h.Reaction intermediate is isolated, is added to dichloroethanes again DCE (5mL), and catalyst phosphonic acids (5mmol%) is added in, 80 DEG C are warming up to, stirs 8h.It is cooled to room temperature, adds in toluene sulphur Sour TsOH (5mmol%), 80 DEG C of stirring 30min.Postcooling that the reaction was complete is spin-dried for after adding in a little silica gel to room temperature, uses silica gel Post separation obtains product 7- cyano -3- diphenylmethylene aphthopyrans, yield 72%.
1H-NMR(400MHz,CDCl3) δ 8.05 (d, J=1.7Hz, 1H), 7.92 (d, J=8.8Hz, 1H), 7.65 (d, J =8.9Hz, 1H), 7.59-7.52 (m, 1H), 7.48-7.40 (m, 2H), 7.41-7.34 (m, 2H), 7.32 (t, J=7.5Hz, 3H), 7.29-7.19 (m, 4H), 7.12 (d, J=8.9Hz, 1H), 6.91 (d, J=10.4Hz, 1H), 6.50 (d, J= 10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ153.90,146.03,139.72,138.86,134.50,131.05, 130.37,130.23,129.67,128.68,128.61,127.77,127.47,127.18,126.48,122.91,122.45, 119.25,119.08,118.58,117.95,114.80,107.61,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C27H18NO[M+H]+:372.1388.Found:372.1380； C27H17NNaO[M+Na]+:394.1208.Found:394.1202.
Embodiment 8
The preparation of 7- benzoyl -3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 6- benzoyls naphthols 2 (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 8h.Reaction intermediate is isolated, is added to dichloroethanes DCE (5mL) again, and add in catalyst phosphonic acids (5mmol%) is warming up to 80 DEG C, stirs 8h.It is cooled to room temperature, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirrings 30min.Postcooling that the reaction was complete is spin-dried for after adding in a little silica gel to room temperature, with the isolated product 7- benzoyls of silicagel column- 3- diphenylmethylene aphthopyrans, yield 84%.
1H-NMR(400MHz,CDCl3) δ 8.15 (d, J=1.6Hz, 1H), 8.03-7.92 (m, 2H), 7.87-7.80 (m, 2H), 7.71 (d, J=8.8Hz, 1H), 7.64-7.57 (m, 1H), 7.52-7.44 (m, 4H), 7.42-7.35 (m, 2H), 7.34- 7.26 (m, 5H), 7.24-7.17 (m, 1H), 7.12 (d, J=8.9Hz, 1H), 7.02 (d, J=10.3Hz, 1H), 6.51 (d, J =10.3Hz, 1H)
13C-NMR(101MHz,CDCl3)δ196.15,153.61,146.38,139.96,139.08,137.83, 133.19,132.62,132.27,131.56,131.15,130.83,129.92,129.68,128.63,128.60,128.31, 127.74,127.06,127.00,126.29,122.38,121.56,119.95,117.73,117.31,114.62,77.32, 77.00,76.68.
HRMS(ESI+):m/z Calcd.for C33H23O2[M+H]+:451.1698.Found:451.1690； C33H22NaO2[M+Na]+:473.1517.Found:473.1514.
Embodiment 9
The preparation of 7- formic acid esters -3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 6- cyano naphthols 2 (0.5mmol) is added in dichloroethanes DCE (5mL), stirring to connection alkene dissolving, it is impossible to which the naphthols of dissolving is stirred to no solid Particle.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 8h.Reaction intermediate is isolated, is added to dichloroethanes again DCE (5mL), and catalyst phosphonic acids (5mmol%) is added in, 80 DEG C are warming up to, stirs 8h.It is cooled to room temperature, adds in toluene sulphur Sour TsOH (5mmol%), 80 DEG C of stirring 30min.Postcooling that the reaction was complete is spin-dried for after adding in a little silica gel to room temperature, uses silica gel Post separation obtains product 7- formic acid esters -3- diphenylmethylene aphthopyrans, yield 64%.
1H-NMR(400MHz,CDCl3) δ 8.46 (d, J=1.7Hz, 1H), 8.04 (dd, J=8.9,1.7Hz, 1H), 7.91 (dd, J=8.8,2.4Hz, 1H), 7.77-7.68 (m, 1H), 7.45 (dd, J=8.3,1.4Hz, 2H), 7.40-7.34 (m, 2H),7.34–7.25(m,5H),7.25–7.18(m,1H),7.14–7.09(m,1H),7.05–6.95(m,1H),6.48(d,J =10.3Hz, 1H), 3.95 (s, 3H)
13C-NMR(101MHz,CDCl3)δ166.98,153.52,146.42,140.02,139.13,131.61, 131.44,131.18,131.09,129.69,128.94,128.60,127.75,127.04,126.41,126.28,125.88, 122.30,121.40,119.99,117.65,114.55,77.32,77.00,76.68,52.16.
HRMS(ESI+):m/z Calcd.for C28H21O3[M+H]+:405.1491.Found:405.1479； C28H20NaO3[M+Na]+:427.1310.Found:427.1258.
Embodiment 10
The preparation of 3- diphenylmethylene aphthopyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 9- anthrols (0.5mmol) It is added in dichloroethanes DCE (5mL), stirs to two kinds of substrates and dissolve.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.Room temperature is cooled to, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirrings 30min.Postcooling that the reaction was complete is to room temperature, with the isolated product 3- diphenylmethylenes anthra pyrans of silicagel column, yield 85%.
1H-NMR(400MHz,CDCl3) δ 8.60-8.45 (m, 2H), 8.17 (dd, J=8.2,1.4Hz, 1H), 7.94 (dd, J=8.2,1.5Hz, 1H), 7.66-7.45 (m, 6H), 7.44-7.23 (m, 8H), 7.04 (d, J=10.3Hz, 1H), 6.58 (d, J=10.3Hz, 1H)
13C-NMR(101MHz,CDCl3)δ148.02,146.75,140.35,139.71,131.18,131.03, 129.66,128.53,127.88,127.70,127.65,127.18,127.00,126.93,126.83,126.35,124.94, 123.68,123.03,122.46,122.23,121.69,121.56,120.96,116.40,110.93,77.32,77.00, 76.68.
HRMS(ESI+):m/z Calcd.for C30H21O[M+H]+:397.1592.Found:397.1572； C30H20NaO[M+Na]+:419.1412.Found:419.1311.
Embodiment 11
The preparation of 3- diphenylmethylenes pyrene and pyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 4- pyrenes phenol (0.5mmol) It is added in dichloroethanes DCE (5mL), stirs to two kinds of substrates and dissolve.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 30 minutes.80 DEG C are warming up to continue to stir 8h.Room temperature is cooled to, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirrings 30min.Postcooling that the reaction was complete is to room temperature, with the isolated product 3- diphenylmethylenes pyrene of silicagel column and pyrans, yield 50%.
1H-NMR(400MHz,CDCl3) δ 8.13 (d, J=9.2Hz, 1H), 8.06-7.95 (m, 2H), 7.93-7.85 (m, 2H), 7.82 (d, J=1.4Hz, 2H), 7.66 (s, 1H), 7.64-7.59 (m, 2H), 7.49-7.37 (m, 5H), 7.37-7.30 (m, 4H), 6.70 (d, J=10.0Hz, 1H), 6.57 (d, J=10.0Hz, 1H)
13C-NMR(101MHz,CDCl3)δ147.11,146.69,140.12,139.53,131.67,131.49, 131.19,129.90,128.54,127.87,127.32,127.05,126.83,126.62,126.46,126.28,125.88, 125.72,125.67,124.85,124.78,124.51,122.41,121.76,120.40,118.90,118.61,117.87, 77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C30H21O[M+H]+:397.1592.Found:397.1572； C30H20NaO[M+Na]+:419.1412.Found:419.1311.
Embodiment 12
The preparation of N- benzoyls -3- diphenylmethylenes indoles and pyrans, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and N- benzoyls indoles - 7- phenol (0.5mmol) is added in dichloroethanes DCE (5mL), stir to the dissolving of two kinds of substrates (undissolvable naphthols stir to There is no solid particle, 3g, 3i).Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 8h.Reaction intermediate is isolated, again Dichloroethanes DCE (5mL) is added to, and adds in catalyst phosphonic acids (5mmol%), is warming up to 80 DEG C, stirs 8h.It is cooled to often Temperature adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirring 30min.Postcooling that the reaction was complete adds in a little silicon to room temperature It is spin-dried for after glue, with the isolated product N- benzoyls -3- diphenylmethylenes indoles of silicagel column and pyrans, yield 55%.
1H-NMR(400MHz,CDCl3) δ 8.21 (d, J=8.9Hz, 1H), 7.75-7.68 (m, 2H), 7.64-7.57 (m, 1H),7.56–7.46(m,4H),7.43–7.34(m,2H),7.34–7.24(m,6H),7.23–7.15(m,1H),6.92(d,J =8.9Hz, 1H), 6.66 (d, J=10.1Hz, 1H), 6.61 (d, J=3.8Hz, 1H), 6.44 (d, J=10.1Hz, 1H)
13C-NMR(101MHz,CDCl3)δ168.45,150.06,146.93,140.36,139.35,134.25, 131.96,131.67,131.36,129.73,129.13,128.81,128.60,128.53,127.69,127.01,126.86, 126.09,122.24,121.21,117.15,117.02,112.98,112.93,105.47,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C31H22NO2[M+H]+:440.1651.Found:440.1638； C31H21NNaO2[M+Na]+:462.1470.Found:462.1477.
Embodiment 13
The preparation of 3,5- dimethoxy -3- diphenylmethylene chromenes, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 3,5- dimethoxy benzenes Phenol (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Add in catalyst phosphonic acids (5mmol%), normal-temperature reaction 8h.Reaction intermediate is isolated, dichloroethanes DCE (5mL) is added to again, adds in toluene sulphur Sour TsOH (20mmol%), 80 DEG C of stirring 8h.Postcooling that the reaction was complete is spin-dried for after adding in a little silica gel to room temperature, uses silicagel column Isolated product 3,5- dimethoxy -3- diphenylmethylene chromenes, yield 40%.
1H-NMR(400MHz,CDCl3)δ7.44–7.38(m,2H),7.36–7.30(m,2H),7.30–7.20(m,5H), 6.64 (d, J=10.2Hz, 1H), 6.15 (d, J=10.2Hz, 1H), 6.05 (q, J=2.3Hz, 2H), 3.77 (s, 3H), 3.76 (s,3H).
13C-NMR(101MHz,CDCl3)δ161.55,155.59,154.93,146.90,140.56,139.71, 131.34,129.72,128.42,127.65,126.64,125.77,119.62,117.29,115.64,104.79,92.94, 92.81,77.32,77.00,76.68,55.59,55.52.
HRMS(ESI+):m/z Calcd.for C24H21O3[M+H]+:357.1491.Found:357.1483； C24H20NaO3[M+Na]+:379.1310.Found:379.1305.
Embodiment 14
The preparation of 3,10- bis- two pyrans of (diphenyl methyl)-naphtho-, includes the following steps：
By 2- benzyloxy -1,1- diphenyl -2,3- connection enols (0.75mmol, 1.5equiv.) and 2,7- naphthalenediols (0.5mmol) is added in dichloroethanes DCE (5mL), is stirred to two kinds of substrates and is dissolved.Catalyst phosphonic acids (5mmol%) is added in, Normal-temperature reaction 30 minutes.80 DEG C are warming up to, continues to stir 8h.Room temperature is cooled to, adds in p-methyl benzenesulfonic acid TsOH (5mmol%), 80 DEG C of stirring 30min.Postcooling that the reaction was complete is spin-dried for after adding in a little silica gel to room temperature, isolated comprising miscellaneous with silicagel column Then the product of matter crystallizes in the volatilization of the in the mixed solvent of DCM/MeOH and obtains clean product 3, and 10- bis- (diphenyl methyls)- Two pyrans of naphtho-, yield 73%.
1H-NMR(400MHz,CDCl3)δ7.88–7.82(m,2H),7.48–7.33(m,12H),7.31–7.27(m,4H), 7.02-6.92 (m, 2H), 6.89-6.71 (m, 6H), 6.46 (d, J=10.3Hz, 2H)
13C-NMR(101MHz,CDCl3)δ146.28,140.80,140.68,138.05,131.59,129.54, 128.67,127.33,127.00,126.36,125.49,124.87,123.72,121.69,119.24,118.60,116.80, 77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C42H29O2[M+H]+:565.2168.Found:565.2155； C42H28NaO2[M+Na]+:587.1987.Found:587.1979.
The amount of catalyst and co-catalyst in above-described embodiment 1-14 is to rub relative to the percentage of naphthol compound You measure.

Claims (10)

1. a kind of naphtho-pyrans compounds, which is characterized in that the compound is the general structure of formula (III)：
Wherein, in the general structure, R1、R2And R3Separately selected from H, halogen, cyano, alkyl, alkoxy, formoxyl, Formamido, benzoyl and group-4 ethyl formate.
2. naphtho-pyrans compounds according to claim 1, it is characterised in that：The R1Independently selected from H, cyano, halogen Element, alkoxy, formoxyl, formamido, benzoyl and group-4 ethyl formate.
3. naphtho-pyrans compounds according to claim 1, it is characterised in that：The R2And R3Separately it is selected from H, halogen, alkyl and alkoxy.
4. the preparation method of any naphtho-pyrans compounds of a kind of claim 1-3, which is characterized in that including following Step：
(1) naphthol compound that the diaryl of formula (I) is joined to vinyl compound and formula (II) is dissolved in solvent, obtains pre-reaction Mixed solution；
(2) the pre-reaction mixed solution of gained reacts under conditions of temperature is 50-80 DEG C and catalyst in step (1), obtains The naphtho-pyrans compounds；
Reaction route is as follows：
Wherein, R1、R2And R3Separately selected from H, halogen, cyano, alkyl, alkoxy, formoxyl, formamido, benzoyl Base and group-4 ethyl formate.
5. preparation method according to claim 4, it is characterised in that：In step (1), the diaryl joins vinyl compound A concentration of 0.1-0.2mol/L.
6. preparation method according to claim 4, it is characterised in that：The diaryl connection vinyl compound and aphthols The molar ratio for closing object is 1-2:1.
7. preparation method according to claim 4, it is characterised in that：In step (2), the catalyst is catalyzed for phosphonic acids Agent.
8. preparation method according to claim 4, it is characterised in that：Step is additionally added co-catalyst in (2).
9. preparation method according to claim 8, it is characterised in that：The co-catalyst is acidic promotor.
10. preparation method according to claim 4, it is characterised in that：The solvent is dichloromethane, dichloroethanes, three One or more of chloromethanes and toluene.
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