CN104557842A - Novel preparation method of diaryl substituted naphthopyran photochromic compound - Google Patents

Novel preparation method of diaryl substituted naphthopyran photochromic compound Download PDF

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Publication number
CN104557842A
CN104557842A CN201310520303.1A CN201310520303A CN104557842A CN 104557842 A CN104557842 A CN 104557842A CN 201310520303 A CN201310520303 A CN 201310520303A CN 104557842 A CN104557842 A CN 104557842A
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add
synthesis
aphthopyrans
reflux
bis
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Inventor
孟继本
庞美丽
牛彦霞
周岩
吴边鹏
边俊民
张建新
孟庆秘
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Tianjin Fuxin Sunshine Technology Co., Ltd.
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TIANJIN FORESEEN TECHNOLOGY CO LTD
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Abstract

The invention relates to a novel preparation method of a diaryl substituted naphthopyran photochromic compound. One active aldehyde group is introduced onto a substitution aromatic ring, and then other required functional groups are connected to an aldehyde active site, so that photochromic performance of the naphthopyran compound is regulated, absorption wavelength of the naphthopyran compound is controlled to generate red shift or blue shift, and a photochromic wavelength range of the diaryl substituted naphthopyran compound is further expanded.

Description

Novel diaryl replaces aphthopyrans class photochromic compound preparation method
Technical field
Technical scheme of the present invention relates to organic photochromic material, and specifically Novel diaryl replaces aphthopyrans class photochromic compound preparation method.
Background technology
Aryl replaces aphthopyrans class photochromic compound, not only has that performance reasonable light flavescence look, light become orange red, light reddens the character such as look, but also have in solid-state and solution can the characteristic of variable color, has been widely used in people's livelihood field.Such as photochromic sunglasses, photochromic clothing item, ornament etc.For meeting the demand in market, must develop more newly, the photochromic compound new variety of excellent property.From the paper delivered at present and patent, very little by changing the research space that substituting group modifies compound from aromatic ring, the present invention connects an aldehyde radical active group on aromatic ring, connect various functional group by aldehyde radical again, expand scope and the research space of aromatic ring modification.The present invention can regulate and control the photochromic properties of aphthopyrans class photochromic compound, by regulating and controlling the different groups of conjugated system size and connection, makes absorbing wavelength red shift or blue shift, expands the variable color wavelength region that aryl replaces naphthopyran compounds.
Summary of the invention
The object of this invention is to provide Novel diaryl and replace aphthopyrans class photochromic compound preparation method, its synthesis step is as follows:
The first step: the synthesis of benzo lactone
Synthesize by application number 201110275.394.8 patented method;
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
Under nitrogen protection; in 250mL there-necked flask, adding 55mmol magnesium chips, adding anhydrous THF to just not having magnesium chips; add an iodine again; start to stir, warm reaction flask, after initiation reaction; start to drip the 50mmol p-bromobenzaldehyde ethylence acetal being dissolved in the anhydrous THF of 30mL; keep micro-reaction of boiling, after dropwising, continue micro-backflow 1 hour of boiling.Drip the 10mmol naphtho-lactone being dissolved in 40mL THF, after dropwising, continue reflux 5 hours.Steam except THF, in residuum, add the aqueous ammonium chloride solution of 22%, remove unreacted Grignard reagent.With toluene extraction, extraction liquid anhydrous magnesium sulfate drying, filters, toluene solution lucifuge reflux 3 hours, removing toluene.Add 100mL methylene dichloride, instill 5 10% dilute hydrochloric acid and 40g tosic acid, stir lower reflux, detect with TLC, stopped reaction after question response object point disappears, isolates organic phase, and washing, with anhydrous magnesium sulfate drying, filter, removing methylene dichloride, pillar layer separation obtains product.
3rd step: the benzoyl diazanyl phenylnaphthalene of para-orientation the synthesis of pyrylium compound
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20 ~ 30mL dehydrated alcohol; add 20 Glacial acetic acid under stirring, add the benzoyl hydrazine that 0.6 ~ 0.8mmol R replaces, reflux 2 ~ 3 hours; stopped reaction; leach crude product, use distilled water and absolute ethanol washing 2 ~ 4 times respectively, suction filtration; drying, obtains product.
Novel diaryl of the present invention replaces aphthopyrans class photochromic compound preparation method feature and is: on the aromatic ring replaced, connect an aldehyde radical active group, other functional groups or aromatic ring is connected again from aldehyde radical active site, expand the research space carrying out modifying on diaryl naphthopyran class photochromic compound, can its absorbing wavelength of direct regulation and control, make its absorbing wavelength red shift or blue shift, and then expand the variable color wavelength region of diaryl naphthopyran compounds, the photochromic compound kind of more how novel excellent property can be synthesized, meet the demand in market.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
2,2-bis-(benzoyl Hydrazino-phenyl) naphthopyran compounds synthesizes
The first step: the synthesis of benzo lactone
Synthesize by application number 201110275.394.8 patented method.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
Under nitrogen protection; in 250mL there-necked flask, adding 55mmol magnesium chips, adding anhydrous THF to just not having magnesium chips; add an iodine again; start to stir, warm reaction flask, after initiation reaction; start to drip the 50mmol p-bromobenzaldehyde ethylence acetal being dissolved in the anhydrous THF of 30mL; keep micro-reaction of boiling, after dropwising, continue micro-backflow 1 hour of boiling.Drip the 10mmol naphtho-lactone being dissolved in 40mL THF, after dropwising, continue reflux 5 hours.Steam except THF, in residuum, add the aqueous ammonium chloride solution of 22%, remove unreacted Grignard reagent.With toluene extraction, extraction liquid anhydrous magnesium sulfate drying, filters, toluene solution lucifuge reflux 3 hours, removing toluene.Add 100mL methylene dichloride, instill 5 10% dilute hydrochloric acid and 40g tosic acid, stir lower reflux, detect with TLC, stopped reaction after question response object point disappears, isolates organic phase, and washing, with anhydrous magnesium sulfate drying, filter, removing methylene dichloride, pillar layer separation obtains product.Productive rate 62%, m.p.173 ~ 176 DEG C.
1H NMR(300MHz,CDCl 3):6.25(d,1H),7.21-7.98(m,5H),9.98(s,2H)
3rd step: 2,2-bis-(benzoyl Hydrazino-phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 2 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 51%, m.p.215-218 DEG C.
1H NMR(300MHz DMSO-d 6):8.45(s,2H),7.35-8.14(m,25H),6.66(d,J=9.9Hz,1H).
13C NMR(75MHz DMSO-d 6):81.50,113.93,118.06,119.91,121.56,123.97,124.65,126.71,127.04,127.59,128.08,128.40,129.04,129.21,130.04,131.70,133.34,133.39,133.71,146.07,147.25,149.75,163.15.
HRMS:[M+H] +649.2205.C 41H 29O 3N 4,requires[M+H] +649.2210
Embodiment 2
The first step: the synthesis of benzo lactone
With embodiment 1.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
With embodiment 1.
3rd step: 2,2-bis-(4-Bromophenacyl diazanyl phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 25mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 2.5 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 86%, m.p.187-189 DEG C.
1H NMR(300MHz DMSO-d 6):8.42(s,2H)7.36-8.14(m,25H),6.67(d,J=10.5Hz,1H).
13C NMR(75MHz DMSO-d 6):81.48,113.93,118.05,119.93,121.55,123.98125.53,26.72,127.10,127.54,128.39,129.04,129.20,129.68,130.04,131.46,132.41,133.58,146.16,147.60,147.60,149.73,162.20.
HRMS:[M+H] +783.0608,C 41H 28O 3N 4Br 2,requires.[M+H] +783.0601.
Embodiment 3
The first step: the synthesis of benzo lactone
With embodiment 1.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
With embodiment 1.
3rd step: 2,2-bis-(4-chlorobenzoyl Hydrazino-phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 2.5 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 93%, m.p.183-185 DEG C.
1H NMR(300MHz DMSO-d 6):8.40(s,2H),7.33-8.11(m,25H),6.64(d,J=10.0Hz,1H).
13C NMR(75MHz DMSO-d 6):81.50,113.94，118.06，119.93，121.56，123.97，126.72，126.99，127.09，127.55，128.39，128.52，129.05，129.21，129.52，130.04，132.01，133.59，136.61，146.15，147.57，149.74,162.07.
HRMS:[M+H] +695.1603.C 41H 28O 3N 4Cl 2.requires[M+H] +695.1611
Embodiment 4
The first step: the synthesis of benzo lactone
With embodiment 1.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
With embodiment 1.
3rd step: 2,2-bis-(4-nitrobenzoyl hydrazide group phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 25mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 1.5 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 93%, m.p.189-192 DEG C.
1H NMR(300MHz DMSO-d 6):8.42(s,2H),7.34-8.35(m,25H),6.65(d,J=10.4Hz,1H).
13C NMR(75MHz DMSO-d 6):81.48,113.94,118.04,119.97,121.55,122.80,123.55,123.98,126.99,126.74,127.23,127.50,128.38,129.12,130.05,130.69,133.42,138.99,146.35,148.38,149.24,149.72,161.50.
HRMS:[M+H] +717.2099.C 41H 28O 7N 6.requires[M+H] +717.2092
Embodiment 5
The first step: the synthesis of benzo lactone
With embodiment 1.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
With embodiment 1.
3rd step: 2,2-bis-(4-methoxybenzoyl Hydrazino-phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 2.5 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 93%, m.p.189-192 DEG C.
1H NMR(300MHz DMSO-d 6):8.42(s,2H),7.04-8.14(m,25H),6.66(d,J=9.9Hz,1H),3.83(s,6H).
13CNMR(75MHz DMSO-d 6):55.36,81.51,113.66,113.93,118.07,119.88,121.55,123.96,125.39,125.43,126.70,126.93,127.60,128.38,129.04,129.22,129.55,130.02,133.83,145.93,146.62,149.76,161.99,162.56.
HRMS:[M+H] +687.2604.C 42H 34O 5N 4.requires[M+H] +687.2602
Embodiment 6
The first step: the synthesis of benzo lactone
With embodiment 1.
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
With embodiment 1.
3rd step: 2,2-bis-(4-toluyl Hydrazino-phenyl) naphthopyran compounds synthesis
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20mL dehydrated alcohol, under stirring, add 20 Glacial acetic acid; add 0.6mmol benzoyl hydrazine; reflux 2 hours, stopped reaction, leaches product; use distilled water and absolute ethanol washing 2 ~ 4 times respectively; obtain product, productive rate 78%, m.p.194-196 DEG C.
1H NMR(300MHz DMSO-d 6):8.44(s,2H),7.31-8.13(m,25H),6.65(d,J=9.9Hz,1H),2.37(s,6H).
13C NMR(300MHz DMSO-d 6):20.97,81.51,113.93,118.06,119.89,121.56,123.97,126.71,126.98,127.61,128.39,128.93,129.04,129.22,130.03,130.47,133.77,141.77,146.00,146.94,149.75,161.83,162.87,162.97.
HRMS:[M+H] +655.2709.C 42H 34O 3N 4requires[M+H] +655.2704
The foregoing is only preferred embodiment of the present invention, be not limited to the present invention, within the spirit and principles in the present invention all, any amendment made and equivalent replacement, all should be included within protection scope of the present invention.

Claims (1)

1. Novel diaryl replaces aphthopyrans class photochromic compound preparation method, it is characterized in that: step is as follows:
The first step: the synthesis of benzo lactone: with the synthesis of application number 201110275.394.8 patented method;
The synthesis of second step: 2,2-bis-(4-Fonnylphenyl) aphthopyrans
Under nitrogen protection, in 250mL there-necked flask, adding 55mmol magnesium chips, adding anhydrous THF to just not having magnesium chips, add an iodine again, start to stir, warm reaction flask, after initiation reaction, start to drip the 50mmol p-bromobenzaldehyde ethylence acetal being dissolved in the anhydrous THF of 30mL, keep micro-reaction of boiling, after dropwising, continue micro-backflow 1 hour of boiling; Drip the 10mmol naphtho-lactone being dissolved in 40mL THF, after dropwising, continue reflux 5 hours; Steam except THF, in residuum, add the aqueous ammonium chloride solution of 22%, remove unreacted Grignard reagent; With toluene extraction, extraction liquid anhydrous magnesium sulfate drying, filters, toluene solution lucifuge reflux 3 hours, removing toluene; Add 100mL methylene dichloride, instill 5 10% dilute hydrochloric acid and 40g tosic acid, stir lower reflux, detect with TLC, stopped reaction after question response object point disappears, isolates organic phase, and washing, with anhydrous magnesium sulfate drying, filter, removing methylene dichloride, pillar layer separation obtains product;
3rd step: the benzoyl diazanyl phenylnaphthalene of para-orientation the synthesis of pyrylium compound
In 50mL there-necked flask, add 0.3mmol2,2-bis-(4-Fonnylphenyl) aphthopyrans; add 20 ~ 30mL dehydrated alcohol; add 20 Glacial acetic acid under stirring, add the benzoyl hydrazine that 0.6 ~ 0.8mmol R replaces, reflux 2 ~ 3 hours; stopped reaction; leach crude product, use distilled water and absolute ethanol washing 2 ~ 4 times respectively, suction filtration; drying, obtains product.
CN201310520303.1A 2013-10-29 2013-10-29 Novel preparation method of diaryl substituted naphthopyran photochromic compound Pending CN104557842A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250174A (en) * 2018-02-07 2018-07-06 中国科学院兰州化学物理研究所苏州研究院 Naphtho-pyrans compounds and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993156A (en) * 2011-09-19 2013-03-27 天津孚信科技有限公司 Preparation method of aryl-substituted-naphthopyran photochromic compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993156A (en) * 2011-09-19 2013-03-27 天津孚信科技有限公司 Preparation method of aryl-substituted-naphthopyran photochromic compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PANG, MEILI 等: "Synthesis, Characterization and Photochromic Properties ofNovel Naphthopyrans with Hydrazone Unit Residue", 《CHIN. J. CHEM.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250174A (en) * 2018-02-07 2018-07-06 中国科学院兰州化学物理研究所苏州研究院 Naphtho-pyrans compounds and preparation method thereof
CN108250174B (en) * 2018-02-07 2021-09-10 中国科学院兰州化学物理研究所苏州研究院 Naphthopyran compounds and preparation method thereof

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