CN104292151A - Novel viologen compounds and preparation method thereof - Google Patents
Novel viologen compounds and preparation method thereof Download PDFInfo
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- CN104292151A CN104292151A CN201310298443.9A CN201310298443A CN104292151A CN 104292151 A CN104292151 A CN 104292151A CN 201310298443 A CN201310298443 A CN 201310298443A CN 104292151 A CN104292151 A CN 104292151A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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Abstract
The invention relates to novel viologen compounds and a preparation method thereof. Specifically, the invention provides a type of compounds with a structure shown by a formula I. The definitions of the groups are as in the specifications. The compounds of the formula I provided by the invention can be widely applied in the aspects of soft matter material construction, photoelectric materials, and solar cells.
Description
Technical field
The present invention relates to organic synthesis field, particularly, the invention provides the novel viologen compound of a class and preparation thereof.
Background technology
Viologen Compounds is that a class 1,1 '-two replaces 4, the general name of 4 '-bipyridine salt, and they have very strong short of electricity, in organic electronic devices is as solar cell, obtain good application ((a) Zahavy, S. as photoelectron acceptor; Seiler, M.; Marx-Tibbon, S.; Joselevich, E.; Willner, I.; Durr, H.; O ' Connor, D.; Harriman, A.Angew.Chem., Int.Ed.1995,34,1005-1008.; (b) Nishikitani, Y.; Uchida, S.; Asano, T.; Minami, M.; Oshima, S.; Ikai, K.; Kubo, T.J.Phys.Chem.C2008,112,4372.).In addition, Viologen Compounds realizes reversible oxidation-reduction reaction by means such as chemistry, photochemistry and electrochemistry, has good redox property.Can along with the change of color during its generation oxidation-reduction reaction, correspond respectively to the color of its oxidized and reduced, therefore Viologen Compounds is the organic electrochromic material of a class excellent property, in display device, intelligent glass, smart window, there are good application prospect ((a) Cao Liangcheng, Wang Yuechuan, chemical progress in the fields such as automobile anti-dazzle eyepiece, 2008,1353; (b) Sun Yan, Fu Xiangkai, Chen Zhujun, Chen Wei, Jiang Qinglong, fine chemistry industry, 2008,438; (c) Mortimer, R.J.Electrochim.Acta, 1999,44,2971.).
The viologen derivative reported at present is mainly introduced constructed by saturated alkane class substituting group on the nitrogen-atoms of dipyridyl, because saturated alkane group does not produce conjugation with bipyridine group, therefore no matter its length is how for these alkanes substituted radicals, very limited on the impact of the electrochemical properties of constructed viologen derivative, be unfavorable for regulating and controlling the electronics receiving capability of Viologen Compounds and its color change interval.The many viologen polymers introducing multiple purpurine fragment in the polymer also see report, but purpurine fragment is all couple together ((a) Lieder, M. with unconjugated flexible chain such as alkyl chain or polyglycol chain etc. in these systems;
c.W.J.Appl.Electrochem.1997,27,235; (b) Choi, S.; Lee, J.W.; Ko, Y.H.; Kim, K.Macromolecules2002,35,3526; (c) Belitsky, J.M.; Nelson, A.; Stoddart, J.F.Org.Biomol.Chem.2006,4,250.), purpurine primitive is relatively independent each other, and conformation is also uncertain, and what show is the character of independent purpurine individuality.
In sum, this area still lacks a kind of many viologen compound of full conjugate with distinct electrical chemical property.
Summary of the invention
The object of this invention is to provide the novel viologen compound that a class has special redox characteristic and electronic effect, and preparation method thereof.
A first aspect of the present invention, provides a kind of such as formula the compound shown in I:
Wherein,
M is selected from lower group: 1,2,3,4,5;
N is selected from lower group: 1,2,3;
Each R is selected from lower group independently of one another: substituted or unsubstituted C6 ~ C30 aryl, substituted or unsubstituted C1 ~ C30 heteroaryl;
R
1and R
2be selected from lower group independently of one another: the alkyl (straight or branched) of substituted or unsubstituted C1 ~ C30; The aryl of substituted or unsubstituted C6 ~ C30, the heteroaryl of substituted or unsubstituted C1 ~ C30;
Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
X, for compensating negatively charged ion, is preferably selected from lower group: Cl
-, Br
-, I
-, ClO
4 -, CH
3cOO
-, CH
3(C
6h
4) SO
3 -, PF
6 -, AsF
6 -, BF
4 -, NO
3 -, or its combination.
In another preference, described m is selected from lower group: 1,2,3;
Described n is selected from lower group: 1,2;
Described R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C8; Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
Described R is selected from lower group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl,
In another preference, described R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C4; Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30.
In another preference, described R is selected from lower group: substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl,
In another preference, described formula I is selected from lower group:
Above-mentioned various in, R
1and R
2definition as noted before;
R
3be selected from lower group: the alkyl of substituted or unsubstituted C1 ~ C30, the aryl of substituted or unsubstituted C6 ~ C30, or the heteroaryl of substituted or unsubstituted C1 ~ C30.
A second aspect of the present invention, provide a kind of preparation method of formula I as described in the first aspect of the invention, described method comprises step:
(4a) in inert solvent, with formula IIa compound and R-(Y)
n+1reaction, obtains formula Ib compound; With
(4b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained.
Wherein, m=1, n are selected from 1,2,3;
The definition of R, X is described above;
Y is amido.
In another preference, described terminal alkylations reagent is R
1-M
1and R
2-M
2; Wherein, R
1, R
2definition described above;
M
1, M
2be selected from lower group independently of one another: F, Cl, Br, I.
In another preference, in described step (4a), formula IIa compound and R-(Y)
n+1mol ratio be 1 ~ 5:1.
In another preference, described step (4b) is carried out under the existence of supporting electrolyte, and preferably, described supporting electrolyte is tetrabutyl phosphofluoric acid amine (n-Bu
4nPF
6).
In another preference, the reaction times of described step (4b) is 2 ~ 72h.
In another preference, the temperature of reaction of described step (4b) is 50 ~ 150 DEG C.
In another preference, described method also has the one or more features being selected from lower group:
Described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination; And/or
Described step (4a) is carried out at 0 ~ 150 DEG C; And/or
After reaction terminates, with the second solvent, one or many washing is carried out to reaction product, and filter the product obtaining purifying.
In another preference, described second solvent is selected from lower group: methyl alcohol, acetone, tetrahydrofuran (THF), ether, or its combination.
In another preference, described method also comprises: by the second dissolution with solvents reaction product and after the second solvent solution of forming reactions product, to the second solvent solution reflux of described reaction product.
In another preference, described heat-up time is 0.5 ~ 8h.
A third aspect of the present invention, provide a kind of preparation method of formula I as described in the first aspect of the invention, described method comprises step:
(6a) in inert solvent, with formula III compound and the reaction of formula IIb compound, formula Ib compound is obtained; With
(6b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained;
Wherein, m is selected from 1,2, n=1;
The definition of R, X is described above;
Y is amido.
In another preference, described formula III compound and the mol ratio of formula IIb compound are 1:0.1 ~ 10, are preferably 1:0.5 ~ 3.
In another preference, the reaction times of described step (6a) is 1 ~ 7 day, is preferably 2 ~ 4 days.
In another preference, described terminal alkylations reagent is R
1-M
1and R
2-M
2; Wherein, R
1, R
2, M
1, M
2definition described above.
In another preference, ion-exchange is carried out to the reaction product of described step (6b).
In another preference, described method also has the one or more features being selected from lower group:
Described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination; And/or
Described step (6a) is carried out at 0 ~ 150 DEG C; And/or
The reaction times of described step (6a) is 12-120h.
In another preference, described formula III compound is prepared by the following method:
In inert solvent, react with formula IIa compound and Y-R-Y, obtain formula IIa compound;
Above-mentioned various in, Y is amido; The definition of other each groups is described above.
In another preference, the mol ratio of described formula IIa compound and Y-R-Y is 1:1 ~ 10, is preferably 1:2 ~ 4.
In another preference, ion-exchange is carried out to described formula III compound.
In another preference, described inert solvent is ethanol.
In another preference, described reaction is carried out at a reflux temperature, preferably carries out at 50 ~ 150 DEG C.
In another preference, the time of described reaction is 2 ~ 48h, is preferably 6 ~ 24h.
A fourth aspect of the present invention, provides a kind of purposes of compound as described in the first aspect of the invention, the described purposes of formula I for being selected from lower group: electrochromic material, organic solar battery material, or soft material is constructed.
A fifth aspect of the present invention, provide a kind of purposes of compound as described in the first aspect of the invention, described formula I is for the preparation of the goods being selected from lower group: the dimming glass of building energy conservation glass, anti-glare rear-view mirror for automobile, automobile or aircraft, static state display.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Embodiment
The present inventor is through long-term and deep research, be surprised to find that, the full conjugate compound in one class formation with many purpurines unit has chemical property outstanding especially, described compound is owing to containing multiple purpurine unit in these structures, can form multiple valence state in its oxidation-reduction process, therefore single purpurine of all replacing with aforesaid saturated alkane from the viewpoint of electronic effect or redox characteristic of this kind of viologen compound or the non-conjugated many viologen polymers be connected have the difference of essence.
Term
As used herein, term " C6 ~ C30 aryl " refers to the aryl with 6 ~ 30 carbon atoms, comprises monocycle or aryl bicyclic, such as phenyl, naphthyl, or similar group.
Term " C1 ~ C30 heteroaryl " refers to the heteroaryl with 1 ~ 30 carbon atom, such as pyrryl, pyridyl, furyl, or similar group.
Term " C1 ~ C30 alkyl " refers to the straight or branched alkyl with 1 ~ 30 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or similar group.
Term " replacement " refers to that the one or more hydrogen atoms on group are selected from the substituting group replacement of lower group: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30.
The many viologen compound of full conjugate
In order to realize effectively regulating and controlling the electrochemical properties of purpurine, need to introduce the substituting group that can participate in conjugation, due to the conjugation ligation of aromatic ring, multiple purpurine fragment is made to form the system of a full conjugate, in purpurine when positive charge and reduction thereof the free radical that produces can in whole compound structure delocalization, all very large impact will be brought to the colour-change of its oxidation state or reduction attitude.In addition, for the many viologen compound of common bridging, owing to containing multiple purpurine unit in these structures, multiple valence state can be formed in its oxidation-reduction process, therefore single purpurine of all replacing with aforesaid saturated alkane from the viewpoint of electronic effect or redox characteristic of this kind of viologen compound or the non-conjugated many viologen polymers be connected have the difference of essence, there is the specificity of itself, may with serving unique performance.
The many viologen compound of a class full conjugate provided by the invention, have the structure be shown below:
Wherein,
M is selected from lower group: 1,2,3,4,5;
N is selected from lower group: 1,2,3;
Each R is selected from lower group independently of one another: substituted or unsubstituted C6 ~ C30 aryl, substituted or unsubstituted C1 ~ C30 heteroaryl;
R
1and R
2be selected from lower group independently of one another: the alkyl (straight or branched) of substituted or unsubstituted C1 ~ C30; The aryl of substituted or unsubstituted C6 ~ C30, the heteroaryl of substituted or unsubstituted C1 ~ C30;
Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
X, for compensating negatively charged ion, is preferably selected from lower group: Cl
-, Br
-, I
-, ClO
4 -, CH
3cOO
-, CH
3(C
6h
4) SO
3 -, PF
6 -, AsF
6 -, BF
4 -, NO
3 -, or its combination.
Preferably, described m is selected from lower group: 1,2,3;
Described n is selected from lower group: 1,2;
Described R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C8; Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
Described R is selected from lower group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl,
more preferably, described R is selected from lower group: substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl,
In another preference, described R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C4; Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30.
The present invention's preferred formula I is selected from lower group:
The preparation of the many viologen compound of full conjugate
Present invention also offers the preparation method of the many viologen compound of above-mentioned full conjugate.
In a preference of the present invention, the preparation method of described formula I comprises step:
(4a) in inert solvent, with formula IIa compound and R-(Y)
n+1reaction, obtains formula Ib compound; With
(4b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained.
Wherein, m=1, n are selected from 1,2,3;
The definition of R, X is described above;
Y is amido.
In another preference, described terminal alkylations reagent is R
1-M
1and R
2-M
2; Wherein, R
1, R
2, M
1, M
2definition described above.
In another preference, in described step (4a), formula IIa compound and R-(Y)
n+1mol ratio be 1 ~ 5:1.
Described step (4b) preferably can also be carried out under the existence of supporting electrolyte, and in a preference of the present invention, described supporting electrolyte is tetrabutyl phosphofluoric acid amine (n-Bu
4nPF
6).
The reaction times of above steps is not particularly limited, and whether reaction is carried out completely optionally to use TLC method to judge.In a preference, the reaction times of described step (4b) is 2 ~ 72h.
The temperature of reaction of above steps is not particularly limited, and can carry out at a reflux temperature.In another preference, described step (4a) is carried out at 0 ~ 150 DEG C; The reaction of described step (4b) is carried out at 50 ~ 150 DEG C.
In another preference, described method also has the one or more features being selected from lower group:
Described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination
And/or
After reaction terminates, filter by one or more the second solvent wash reaction product, obtain the product of purifying.
In another preference, described second solvent is selected from lower group: methyl alcohol, acetone, tetrahydrofuran (THF), ether, or its combination.
In another preference, described method also comprises: after adding reaction product with the second solvent, to the second solvent solution reflux of described reaction product.
In another preference, described heat-up time is 0.5 ~ 8h.
In another preference of the present invention, the preparation method of described formula I comprises step:
(6a) in inert solvent, with formula III compound and the reaction of formula IIb compound, formula Ib compound is obtained; With
(6b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained;
Wherein, m is selected from 1,2, n=1;
The definition of R, X is described above;
Y is amido.
In another preference, described formula III compound and the mol ratio of formula IIb compound are 1:0.1 ~ 10, are preferably 1:0.5 ~ 3.
In another preference, described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination.
The reaction times of above steps is not particularly limited, and whether reaction is carried out completely optionally to use TLC method to judge.In another preference, the reaction times of described step (6a) is 1 ~ 7 day, is preferably 2 ~ 4 days.
The temperature of reaction of above steps is not particularly limited, and can carry out at a reflux temperature.In another preference, described step (6a) is carried out at 0 ~ 150 DEG C.
In another preference, described terminal alkylations reagent is R
1-M
1and R
2-M
2; Wherein, R
1, R
2, M
1, M
2definition described above.
In another preference, ion-exchange is carried out to the reaction product of described step (6b), to change the kind compensating negatively charged ion.Described ion-exchange can adopt the ordinary method of any this area, as by compound dissolution in suitable organic solvent, add another kind of negatively charged ion and be precipitated out.
In above-mentioned reaction, each raw material can be obtained by commercially available approach, or is prepared by ordinary method.
In another preference, described formula III compound is prepared by the following method:
In inert solvent, react with formula IIa compound and Y-R-Y, obtain formula IIa compound;
Above-mentioned various in, Y is amido; The definition of other each groups is described above.
In another preference, the mol ratio of described formula IIa compound and Y-R-Y is 1:1 ~ 10, is preferably 1:2 ~ 4.
In another preference, ion-exchange is carried out to described formula III reaction product.
In another preference, described inert solvent is ethanol.
In another preference, described reaction is carried out at a reflux temperature, preferably carries out at 50 ~ 150 DEG C.
In another preference, the time of described reaction is 2 ~ 48h, is preferably 6 ~ 24h.
Electrochromic material
Electrochromism refers to that material produces stable reversible change phenomenon at the optical properties (transmissivity, reflectivity or specific absorption) of ultraviolet-visible light or near infrared region under DC Electric Field, shows as the reversible change of color and transparency in appearance.The material with electrochromic property is then called electrochromic material.Off-color material is the core of Electrochromic device, and organic electrochromic material is the feature such as molecular structure can design, color diversity, good processability, low cost of manufacture owing to having, and is subject to paying close attention to more and more widely.
Purpurine is the very special organism of a class, and it has excellent redox property, by method generation redox reactions such as chemistry, electrochemistry and photochemistry, and is attended by significant colour-change, thus can as electrochromism or photochromic material.In addition, its different redox state can provide electronics or receive electronics.Especially, the many viologen compound of full conjugate provided by the invention have special chemical property, the single purpurine reported with previous literature or many viologen polymers of non-conjugated connection all compared with, due to the conjugation ligation of aromatic ring, multiple purpurine fragment is made to form the system of a full conjugate, because its reduction potential of existence of conjugation reduces, under lower current potential, namely variable color can be there is.Therefore be suitable for very much in organic reaction as excellent electron acceptor(EA) or as oxide species.Also good application prospect is had in fields such as chemical catalysis, supramolecule, weedicide and photovoltaic cells.
Described compound also can be used for preparation Electrochromic composite material or as electrochromic material, for the preparation of electrochromic device.Preferred electrochromic device comprises (but being not limited to): the dimming glass, static state display etc. of building energy conservation glass, anti-glare rear-view mirror for automobile, automobile or aircraft.
Major advantage of the present invention
(1) the full conjugate compound in a series of structure with many purpurines unit has been prepared.Owing to containing multiple purpurine unit in these structures, multiple valence state can be formed in its oxidation-reduction process, therefore single purpurine of all replacing with aforesaid saturated alkane from the viewpoint of electronic effect or redox characteristic of this kind of viologen compound or the non-conjugated many viologen polymers be connected have the difference of essence, have chemical property outstanding especially.
(2) the many viologen compound of a series of aromatic ring bridgings of the designed synthesis of the present invention, the single purpurine reported with previous literature or many viologen polymers of non-conjugated connection all compared with, due to the conjugation ligation of aromatic ring, multiple purpurine fragment is made to form the system of a full conjugate, because its reduction potential of existence of conjugation reduces, can issue at lower current potential the look that changes.
(3) in the many viologen compound of full conjugate of the present invention, the free radical produced when the positive charge of purpurine unit and reduction thereof can in whole compound structure delocalization, can further improve the stability of material.
(4) owing to containing multiple purpurine unit in the compounds of this invention structure, multiple valence state can be formed in its oxidation-reduction process, there is multiple oxidation-reduction energy level, be that the used time will more horn of plenty in colour-change as off-color material, when using as photoelectron acceptor material in photovoltaic cell, energy level more easily mates.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
Universal method
The synthesis of Zincke salt
The synthesis of DNFB: in 2000mL single port bottle, add p-Nitrophenyl chloride (63.64g, 402mmol), nitrosonitric acid (150mL), stirred at ambient temperature forms yellow solution.Add 30mL sulfuric acid, the rapid heat release of system also generates brown gas.After reacting half an hour, no longer heat release is also cooled to room temperature gradually, and system is yellow solution, and TLC shows raw material point and disappears, add 1000mL shrend to go out reaction, separate out a large amount of yellow solid, after filtration drying, obtain 2,4-dinitrochlorobenzene (yellow solid, 80.19g, productive rate 96%).
1H?NMR(400MHz,DMSO-d
6):8.91(d,1H);8.51-8.48(dd,1H),8.08(d,1H)。
In Zincke salt 1:1000mL single port bottle, add 4,4'-Bipyridine (50g, 321mmol), DNFB (54g, 267mmol), acetone (500mL).Be heated to back flow reaction 24 hours, generate a large amount of gray solid, stop heating, be cooled to room temperature, to filter and with a large amount of washing with acetone gained solid, then solid is added in a large amount of acetone, be heated to the 2-3 hour that refluxes.Filtered while hot, obtains product 60.34g after drying, productive rate 70%.
1H?NMR(400MHz,D
2O)δ9.37(d,1H),9.24(d,2H),8.93-8.90(dd,1H),8.81-8.80(dd,2H),8.67(d,2H),8.26(d,1H),8.02-8.01(dd,2H)。
In Zincke salt 2:250mL single port bottle, add 4,4'-Bipyridine (3.63g, 23mmol), DNFB (16.46g, 81mmol) and acetonitrile (70mL), stir and form yellow solution, be heated to back flow reaction 72 hours.Generate a large amount of white precipitate, filtered while hot, gained solid adds in 150mL acetone, refluxes 1 hour.Filter, solid, through washing with acetone, obtains pale solid (6g, productive rate 50%) after drying.
1H?NMR(400MHz,CD
3OD)δ9.67(d,2H),9.34(d,1H),9.11(d,2H),9.00-8.97(dd,2H),8.41(d,1H)。
Embodiment 1: the synthesis of compound P12
Step 1:Zincke salt 1(5.37g, 15mmol), Ursol D (0.542,5mmol) adds in 60mL ethanol, is heated to back flow reaction 48 hours, is cooled to room temperature, and filter, solid is dissolved in methyl alcohol.Drop in a large amount of acetone by above-mentioned methanol solution again, separate out precipitation, filter, washing with acetone solid, obtains product after drying.Gray solid (0.352g, productive rate 15%).
1H?NMR(400MHz,CD
3OD)δ9.52(d,4H),8.92(d,4H),8.80(d,4H),8.35(s,4H),8.14(d,4H)。MS(ESI):m/z194.1[M-2Cl]
2+
Step 2: by step 1 gained compound (0.233g, 0.5mmol), methyl iodide (1mL, 160mmol) adds in 60mL acetonitrile.Be heated to backflow 72 hours, separate out a large amount of red solid.Stop heating, after being cooled to room temperature, uncovered stirring is spent the night, and filters, gained solid after washing with acetone, dry target compound P12(0.308g, productive rate 63%).
1HNMR(400MHz,CD
3CN):9.05(d,4H),8.87(d,4H),9.49-8.42(dd,8H),7.47(d,4H),6.89-6.87(dd,4H),4.41(s,6H)。
13CNMR(100MHz,CD
3CN):152.47,149.95,147.44,146.81,145.22,128.51,128.25,128.00,127.96,127.82and49.45。HRMS (MALDI-DHB) calculated value C
28h
26n
4 +[M-4Cl]: 418.2161, experimental value: 418.2152.
Embodiment 2: the synthesis of compound P14
Step 1:Zincke salt 1(1.95g, 5.5mmol), 4,4 '-benzidine (0.3g, 1.6mmol) add in 120mL ethanol, be heated to back flow reaction 12 hours, filter, after gained solids washed with acetone, then add in 100mL anhydrous methanol dissolve obtain orange solution, add NH
4pF
6carry out ion-exchange, filter, solid product drying after washing with acetone obtains hexafluorophosphate 0.192g, productive rate 75%.
1HNMR(400MHz,DMSO-d
6):9.58(d,4H),8.93(d,4H),8.84(d,4H),8.25(d,4H),8.18(d,4H),8.12(d,4H)。
13CNMR(100MHz,DMSO-d
6):153.42,152.05,150.29,146.45,145.53,145.23,144.35,142.28,140.87,140.63,129.92,128.83,128.63,127.52,126.91,126.19,125.76,125.49,124.51,123.31,122.21,and120.94。MS(ESI):m/z[M-2Cl]
2+232.1。HRMS (MALDI-DHB) calculated value C
32h
24n
4[M-2PF
6]: 464.20, experimental value: C
32h
23n
4 +463.1917.
Step 2: step 1 gained compound (0.825g, 1.55mmol), methyl iodide (3mL, 480mmol) adds in 80mL acetonitrile, is heated to backflow, reacts 48 hours.Stop heating, after being cooled to room temperature, uncovered stirred for several hour.Filter, solid is through washing with acetone, and obtain 1.25g solid after drying, crude product is all dissolved in 300mL water, adds NH
4pF
6(7.5g, 46mmol, 30eq) carries out ion-exchange, stirred at ambient temperature 6 hours.Filter, wash solid with water, after drying, obtain target compound P14(1.5g, productive rate 91%).
1HNMR(400MHz,CD
3CN):9.26(d,4H),8.94(d,4H),8.63(d,4H),8.50(d,4H),8.16(d,4H),7.97(d,4H),4.48(s,6H)。
13CNMR(100MHz,CD
3CN):150.86,149.32,146.62,145.56,142.39,142.15,129.52,127.29,126.97,125.31and48.65。HRMS (MALDI-DHB) calculated value C
34h
30n
4[M-4PF
6]: 494.2472, experimental value: 494.2465
Embodiment 3: the synthesis of compound P15
Step 1:Zincke salt 1(3.64g, 10mmol), Ursol D (3.26g, 30mmol) adds in dehydrated alcohol (100mL), is heated to backflow 12 hours.Filter, solid, through washing with acetone, obtains compound b-1(brown-red solid, 2.75g, productive rate 97% after drying), then it is obtained hexafluorophosphate by ion-exchange.
1HNMR(400MHz,CD
3CN):9.33(d,2H),8.89-8.88(dd,2H),8.67(d,2H),8.12-8.10(dd,2H),7.57-7.50(dd,2H),6.79-6.77(dd,2H),5.97(s,2H).
13CNMR(100MHz,CD
3CN):154.22,152.26,152.14,145.05,142.02,126.69,126.07,122.72,118.26,115.54。MS(ESI):m/z248.0[M-Cl]
+。HRMS (ESI) calculated value C
16h
14n
3[M-Cl]: 248.12, experimental value: 248.11822.
Step 2: by step 1 gained compound (0.455g, 0.81mmol) and Zincke salt 2(0.576g, 2mmol), add in dehydrated alcohol (60mL), be heated to backflow, react 84 hours.Be cooled to room temperature, filter to obtain gray solid, washing with acetone, after drying, obtain intermediate compound (0.31g, productive rate 50%).
1HNMR(400MHz,CD
3OD):9.75(d,4H),9.55(d,4H),9.08(d,4H),8.92(d,4H),8.81(d,4H),8.44-8.37(m,8H),8.16(d,4H)。
13CNMR(100MHz,D
2O):164.68,155.63,151.36,149.92,145.86,144.98,144.52,144.17,142.46,127.52,126.91,126.31and122.79.
MS(ESI):m/z206.5[M-4Cl]
3+。HRMS (MALDI-DHB) calculated value C
42h
32n
6[M-4PF
6]: 620.27, experimental value: 620.2683.
Step 3: by above products therefrom (0.338g, 0.28mmol), (1mL, (160mmol) adds in acetonitrile (80mL) methyl iodide, is heated to backflow, reacts 48 hours.Stop heating, after being cooled to room temperature, uncovered stirred for several hour.Filter, solid, through washing with acetone, obtains solid crude product and is all dissolved in 25mL water, add 1.5g (9.2mmol, 33eq) NH after drying
4pF
6carry out ion-exchange, stirred at ambient temperature 6 hours.Filter, wash solid with water, after drying, obtain target compound P15(0.2g, productive rate 90%).
1HNMR(400MHz,CD
3CN):9.34(d,4H),9.29(d,4H),8.96(d,4H),8.79(d,4H),8.68(d,4H),8.52(d,4H),8.21(s,8H),4.46(s,6H)。
13CNMR(100MHz,D
2O):151.88,151.36,149.38,146.44,145.84,145.68,144.40,144.35,127.52,127.26,126.98,126.89and48.46。HRMS (MALDI-DHB) calculated value C
44h
38n
6[M-6PF
6]: 650.3158, experimental value: 650.3153.
Embodiment 4: the synthesis of compound P16
4,4-diamino terphenyl (0.7g, 2.69mmol) and Zincke salt 1(3.38g, 9.41mmol is added in step 1:50mL tube sealing), then add ethanol (20mL), be warming up to backflow.Climb board monitoring reaction, question response terminates, stopped reaction, is cooled to room temperature.Solution is transferred to 500mL single port bottle, then in bottle, adds acetone (300mL), reflux 2 hours, suction filtration obtains 1.21g solid product, productive rate: 74%.
1H?NMR(400MHz,DMSO)δ9.58(d,J=6.8Hz,4H),8.94(d,J=5.7Hz,4H),8.83(d,J=6.8Hz,4H),8.19(d,J=8.8Hz,8H),8.12–8.00(m,8H)。MS(ESI):m/z270.3[M-2Cl]
2+。
Add product (400mg, 0.65mmol) and the anhydrous acetonitrile (3mL) of step 1 in step 2:30mL tube sealing, then add methyl iodide (0.8mL).Oil bath is heated to 90 DEG C, and two days later, stopped reaction, is cooled to room temperature in reaction.In system, add acetone, suction filtration obtains brown-red solid.The a small amount of water dissolution of red solid, adds phosphofluoric acid aqueous ammonium, produces precipitation immediately under stirring, filter to obtain solid.Solid adds tetrabutylammonium chloride solution, produces precipitation immediately, filter to obtain target compound P16 (brown solid, 415mg, productive rate 71%) after dissolving with a small amount of Nitromethane 99Min. again.
1H?NMR(400MHz,DMSO)δ9.75(d,J=6.8Hz,4H),9.34(d,J=6.9Hz,4H),8.99(d,J=7.0Hz,4H),8.91(d,J=6.8Hz,4H),8.23(d,J=8.7Hz,4H),8.11(d,J=8.7Hz,4H),8.06(d,J=7.7Hz,4H),8.03–8.02(m,4H),4.48(s,6H)。
Embodiment 5: the synthesis of compound P17
Step 1:Zincke salt 1(3.62g, 10mmol), p-diaminodiphenyl (7.61g, 40mmol) adds in 350mL ethanol, is heated to back flow reaction 12 hours, has a large amount of red solid to generate.Filtered while hot, gained solid adds in 500mL acetone, and reflux 2 hours, filtered while hot, obtains red solid 2.82g after drying, productive rate 80%.Hexafluorophosphate can be obtained after ion-exchange.
1HNMR(400MHz,CD
3CN):9.06(d,2H),8.87(d,2H),8.88(d,2H),8.48(d,2H),7.90(t,4H),7.75(d,2H),7.53(d,2H),6.77(d,2H)。
13CNMR(100MHz,CD
3CN):152.83,151.09,149.59,144.99,143.48,140.61,139.72,127.72,126.36,125.25,124.95,124.80,122.00,121.89and114.24。
MS(ESI):m/z[M-Cl]
+324.1。HRMS (ESI) calculated value C
22h
18n
3 +[M-Cl]: 324.15, experimental value: 324.1495.
Step 2: step 1 gained compound (0.41g, 1.14mmol), Zincke salt 2(0.28g, 0.5mmol) add in 50mL dehydrated alcohol, be heated to backflow, react 72 hours.Filtration obtains beige solid, after washing with acetone drying, obtains product 0.341g, productive rate 91%.Hexafluorophosphate can be obtained after ion-exchange.
1HNMR(400MHz,CD
3CN):9.31(s,4H),9.12(d,4H),8.90(d,4H),8.73(d,4H),8.55(d,4H),8.13(t,8H),7.99-7.93(dd,12H)。
13CNMR(100MHz,CD
3CN):153.43,151.17,149.07,145.95,145.39,142.30,140.60,128.72,126.68,125.68,125.32and122.09。MS(ESI):m/3z257.4[M-4Cl]
3+。HRMS (MALDI-DHB) calculated value C
54h
40n
6[M-4PF
6]: 772.33, experimental value: 772.3309.
Step 3: step 2 gained compound (0.51g, 0.56mmol), methyl iodide (3mL, 480mmol) adds in 80mL acetonitrile, is heated to back flow reaction 48 hours.Stop heating, after being cooled to room temperature, uncovered stirred for several hour.Filter, solid is through washing with acetone, and obtain 0.689g solid after drying, crude product is all dissolved in 200mL water, adds NH
4pF
6(6.37g, 39mmol, 68eq) carries out ion-exchange, and reflux 3 hours, is cooled to room temperature, filters, obtains target compound P17(0.60g, productive rate 90% after washing and drying).
1HNMR(400MHz,CD
3CN):9.30(d,4H),9.25(d,4H),8.91(d,4H),8.74(d,4H),8.63(d,4H),8.49(d,4H),8.18(t,8H),7.99(t,8H),4.45(s,6H)。
13CNMR(100MHz,CD
3CN):150.89,150.56,149.33,146.61,145.69,145.58,142.43,142.40,142.24,142.19,129.58,129.56,127.49,127.31,127.01,125.36,125.33and48.69。HRMS (MALDI-DHB) calculated value C
56h
46n
6 +[M-6PF
6]: 802.3774, experimental value: 802.3770.
Embodiment 6: the synthesis of compound P18
Step 1:Zincke salt 1(3.4g, 9.48mmol), 1,5-diaminonaphthalene (0.5g, 3.16mmol) add in 20mL ethanol, be heated to back flow reaction 24 hours, filter, gained solid after 2 hours, filters to obtain light yellow solid 1.18g, productive rate 74% with 100ml acetone reflux.
1H?NMR(400MHz,MeOD)δ9.45(d,J=5.8Hz,4H),8.94(d,J=4.8Hz,4H),8.86(d,J=5.9Hz,4H),8.23(d,J=6.4Hz,2H),8.17(d,J=4.8Hz,4H),8.02(q,J=8.8Hz,4H)。MS(ESI):m/z438.2[M-2Cl]
+。
Step 2: step 1 gained compound (0.4g, 0.78mmol), methyl iodide (0.5mL, 7.9mmol) adds in 15mL acetonitrile, is heated to backflow, reacts 48 hours.Stop heating, filter after being cooled to room temperature, solid with methylene chloride washs, and obtains target compound P18 (solid 0.69g, productive rate 90%) after drying.
1HNMR(400MHz,MeOD)δ9.55(d,J=5.8Hz,4H),9.10(d,J=4.8Hz,4H),8.86(d,J=5.9Hz,4H),8.23(d,J=6.4Hz,2H),8.17(d,J=4.8Hz,4H),8.02(q,J=8.8Hz,4H)，4.48(s,6H)。MS(ESI):m/z468.1[M-4I]
+。
Embodiment 7: the synthesis of compound P19
Step 1: by 1,3,5-tri-(4-aminophenyl) benzene (1.06g, 3.02mmol) with Zincke salt 1 (4.89g, 13.6mmol) be dissolved in 20mL DMSO, under 80 ° of C, reaction separates out a large amount of solid in three days, stops heating naturally cooling to room temperature, is poured into 100mL THF:Et
2in O/1:1, filter, collect solid, wash solid collection filtrate with 600mL, removal of solvent under reduced pressure, obtains faint yellow solid, again dissolves with 300mL methyl alcohol, adds 2.00g NH
4pF
6separate out a large amount of solid, solid collected by filtration.Rapid column chromatography, dry method loading, eluent is followed successively by (MeCOMe:CH
2cl
2/ 9:1, MeCOMe, MeCOMe:NH
4pF
6/ 500mL:50mg, 500mL:150mg).By the 60mL water washing of gained solid, vacuum-drying, obtains faint yellow solid 0.76g, productive rate 21%.
1H?NMR(400MHz,CD
3CN)δ(ppm):9.13(d,J=6.8Hz,6H),8.90(d,J=6.0Hz,6H),8.54(d,J=6.4Hz,6H),8.28(d,J=8.8Hz,6H),8.23(s,3H),7.96(d,J=8.4Hz,6H),7.91(d,J=6.0Hz,6H)。
13CNMR(100MHz,CD
3CN)δ(ppm):156.12,152.33,145.91,144.35,143.06,141.97,141.5,130.50,127.60,127.37,127.09,126.04,122.99。MS (ESI) m/z:257.4 [M-3PF
6 -]
3+.HRMS (ESI): Calcd for C
54h
39n
63 3+[M-3PF
6 -]
3+: 257.1073. experimental value: 257.1083.
Step 2: by step 1 gained compound (0.10g, 0.083mmol) and n-Bu
4nPF
6(0.48g, 1.25mmol) is dissolved in acetonitrile (6mL), adds methyl iodide (0.483g, 1.25mmol), and reflux added methyl iodide (0.483g, 1.25mmol) after 12 hours, continues back flow reaction 24 hours, stops heating naturally cooling to room temperature.Filter, collect solid, with a small amount of acetonitrile wash solid.Gained solid is dissolved in DMSO(5mL), be heated to 80 ° of C, add n-Bu
4nPF
6(1.0g), 30 minutes at this temperature, separate out solid, add 30mL THF:Et
2o/2:1, filters, and collects solid, washs solid respectively with 20mL THF and MeCOMe.Vacuum-drying obtains target compound P19(faint yellow solid, 60mg, productive rate 70.2%).
1H?NMR(D
2O,400MHz)δ:9.43(d,J=6.8Hz,6H),9.05(d,J=6.4Hz,6H),8.71(d,J=6.8Hz,6H),8.58(d,J=6.4Hz,6H),8.21(s,3H),8.18(d,J=8.4Hz,6H),7.97(d,J=8.8Hz,6H),4.48(s,9H)。
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. one kind such as formula the compound shown in I:
Wherein,
M is selected from lower group: 1,2,3,4,5;
N is selected from lower group: 1,2,3;
Each R is selected from lower group independently of one another: substituted or unsubstituted C6 ~ C30 aryl, substituted or unsubstituted C1 ~ C30 heteroaryl;
R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C30, the aryl of substituted or unsubstituted C6 ~ C30, or the heteroaryl of substituted or unsubstituted C1 ~ C30;
Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
X, for compensating negatively charged ion, is preferably selected from lower group: Cl
-, Br
-, I
-, ClO
4 -, CH
3cOO
-, CH
3(C
6h
4) SO
3 -, PF
6 -, AsF
6 -, BF
4 -, NO
3 -, or its combination.
2. compound as claimed in claim 1, it is characterized in that, described m is selected from lower group: 1,2,3;
Described n is selected from lower group: 1,2;
Described R
1and R
2be selected from lower group independently of one another: the alkyl of substituted or unsubstituted C1 ~ C8; Wherein, described replacement refers to that the group being selected from lower group replaces: the aryl of halogen, hydroxyl, carboxyl, carbonyl, C6 ~ C30, the heteroaryl of C1 ~ C30;
Described R is selected from lower group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl,
3. compound as claimed in claim 1, it is characterized in that, described formula I is selected from lower group:
Above-mentioned various in, R
1and R
2definition as described in the appended claim 1;
R
3be selected from lower group: the alkyl of substituted or unsubstituted C1 ~ C30, the aryl of substituted or unsubstituted C6 ~ C30, or the heteroaryl of substituted or unsubstituted C1 ~ C30.
4. the preparation method of formula I as claimed in claim 1, it is characterized in that, described method comprises step:
(4a) in inert solvent, with formula IIa compound and R-(Y)
n+1reaction, obtains formula Ib compound; With
(4b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained;
Wherein, m=1, n are selected from 1,2,3;
The definition of R, X is described above;
Y is amido.
5. preparation method as claimed in claim 4, it is characterized in that, described method also has the one or more features being selected from lower group:
Described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination; And/or
Described step (4a) is carried out at 0 ~ 150 DEG C; And/or
After reaction terminates, with the second solvent, one or many washing is carried out to reaction product, and filter the product obtaining purifying.
6. the preparation method of formula I as claimed in claim 1, it is characterized in that, described method comprises step:
(6a) in inert solvent, with formula III compound and the reaction of formula IIb compound, formula Ib compound is obtained; With
(6b) with formula Ib compound and terminal alkylations reagent react, formula I is obtained;
Wherein, m is selected from 1,2, n=1;
The definition of R, X is described above;
Y is amido.
7. method as claimed in claim 6, it is characterized in that, described method also has the one or more features being selected from lower group:
Described inert solvent is be selected from the solvent of lower group: water, methyl alcohol, ethanol, propyl alcohol, acetonitrile, DMF, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-dioxane, or N,N-dimethylacetamide, or its combination; And/or
Described step (6a) is carried out at 0 ~ 150 DEG C; And/or
The reaction times of described step (6a) is 12-120h.
8. method as claimed in claim 6, it is characterized in that, described formula III compound is prepared by the following method:
In inert solvent, react with formula IIa compound and Y-R-Y, obtain formula IIa compound;
Above-mentioned various in, Y is amido; The definition of other each groups is described above.
9. a purposes for compound as claimed in claim 1, is characterized in that, the described purposes of formula I for being selected from lower group: electrochromic material, organic solar battery material, or soft material is constructed.
10. a purposes for compound as claimed in claim 1, is characterized in that, described formula I is for the preparation of the goods being selected from lower group: the dimming glass of building energy conservation glass, anti-glare rear-view mirror for automobile, automobile or aircraft, static state display.
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| CN107353242A (en) * | 2017-07-12 | 2017-11-17 | 中国科学院上海有机化学研究所 | Two-dimentional supermolecule porous polymer, monomer compound and preparation method |
| CN107353242B (en) * | 2017-07-12 | 2019-11-12 | 中国科学院上海有机化学研究所 | Two-dimentional supermolecule porous polymer, monomer compound and preparation method |
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