1. An azulene isoindigo derivative shown as a formula I:

wherein the content of the first and second substances,

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₆-C₂₀Aryl radicals, substituted by one or more R^ASubstituted C₆-C₂₀Aryl radical, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group; said C₂-C₂₀Heteroaryl is C with 1,2, 3 or 4 heteroatoms selected from N, O, Se and S₂-C₂₀A heteroaryl group;

R^Aand R^BEach independently is halogen, C₁-C₄Alkyl, C substituted by one or more halogens₁-C₄Alkyl radical, C₆-C₁₀Aryl radicals or by one or more R^A-1Substituted C₆-C₁₀An aryl group;

R^A-1is halogen, C₁-C₄Alkyl orC substituted by one or more halogens₁-C₄An alkyl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl, by one or more R^ESubstituted C₁-C₄₈Alkyl radical, C₂-C₄₈Alkenyl, by one or more R^FSubstituted C₂-C₄₈Alkenyl radical, C₆-C₂₄Cycloalkyl radicals or substituted by one or more R^GSubstituted C₆-C₂₄A cycloalkyl group;

R^E、R^Fand R^GEach independently is halogen, C₁-C₄Alkyl, aryl, heteroaryl, and heteroaryl,Or C substituted by one or more halogens₁-C₄An alkyl group.

2. The azulene isoindigo derivative according to claim 1, characterized in that,

when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²When each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine, preferably bromine;

and/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently C₆-C₂₀When aryl, said C₆-C₂₀Aryl is C₆-C₁₀Aryl, preferably phenyl, naphthyl or azulenyl, said naphthyl preferably beingThe azulene radical is preferably

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^ASubstituted C₆-C₂₀When aryl, said C₆-C₂₀Aryl is C₆-C₁₀Aryl, preferably phenyl, naphthyl or azulenyl, said naphthyl preferably beingThe azulene radical is preferably

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^ASubstituted C₆-C₂₀When aryl, said plurality is two or three;

and/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently C₂-C₂₀When it is heteroaryl, said C₂-C₂₀Heteroaryl is C₂-C₁₀Heteroaryl, preferably furyl, pyrrolyl, thienyl, pyridyl, imidazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl or pyrazinyl, further preferably thienyl or pyridyl, most preferably thienyl or pyridyl

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^BSubstituted C₂-C₂₀When it is heteroaryl, said C₂-C₂₀Heteroaryl is C₂-C₁₀Heteroaryl, preferably furyl, pyrrolyl, thienyl, pyridyl, imidazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl or pyrazinyl, further preferably thienyl or pyridyl, most preferably thienyl or pyridyl

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^BSubstituted C₂-C₂₀When heteroaryl, said plurality is two or three;

and/or when R^AAnd R^BWhen each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R^AAnd R^BAre each independently C₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^AAnd R^BEach independently is C substituted by one or more halogen₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^AAnd R^BEach independently is C substituted by one or more halogen₁-C₄When alkyl, said plurality is two or three;

and/or when R^AAnd R^BEach independently is C substituted by one or more halogen₁-C₄When it is alkyl, said halogenThe element is fluorine, chlorine, bromine or iodine;

and/or when R^AAnd R^BAre each independently C₆-C₁₀When aryl, said C₆-C₁₀Aryl is phenyl, naphthyl or azulenyl, the naphthyl is preferredThe azulene radical is preferably

And/or when R^AAnd R^BEach independently by one or more R^A-1Substituted C₆-C₁₀When aryl, said C₆-C₁₀Aryl is phenyl, naphthyl, said naphthyl is preferredThe azulene radical is preferably

And/or when R^AAnd R^BEach independently by one or more R^A-1Substituted C₆-C₁₀When aryl, said plurality is two or three;

and/or when R^A-1When the halogen is fluorine, chlorine, bromine or iodine;

and/or when R^A-1Is C₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^A-1Is C substituted by one or more halogens₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^A-1Is substituted by one or more halogensSubstituted by elements C₁-C₄When alkyl, said plurality is two or three;

and/or when R^A-1Is C substituted by one or more halogens₁-C₄Alkyl, said halogen being fluorine, chlorine, bromine or iodine, preferably fluorine;

and/or when R¹And R²Are each independently C₁-C₄₈When alkyl, said C₁-C₄₈Alkyl is C₆-C₂₀Alkyl, preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl;

and/or when R¹And R²Each independently by one or more R^ESubstituted C₁-C₄₈When alkyl, said C₁-C₄₈Alkyl is C₆-C₂₀Alkyl, preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl;

and/or when R¹And R²Each independently by one or more R^ESubstituted C₁-C₄₈When alkyl, said plurality is two or three;

and/or when R¹And R²Are each independently C₂-C₄₈When alkenyl, said C₂-C₄₈Alkenyl is C₂-C₂₀An alkenyl group;

and/or when R¹And R²Each independently by one or more R^FSubstituted C₂-C₄₈When alkenyl, said C₂-C₄₈Alkenyl is C₂-C₂₀An alkenyl group;

and/or when R¹And R²Each independently by one or more R^FSubstituted C₂-C₄₈When alkenyl, said plurality is two or three;

and/or when R^E、R^FAnd R^GWhen each is independently halogen, the halogen is fluorine, chlorine, bromine or iodine;

and/or when R^E、R^FAnd R^GAre each independently C₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^E、R^FAnd R^GAre each independentlyWhen, C is said₁-C₄Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;

and/or when R^E、R^FAnd R^GEach independently is C substituted by one or more halogen₁-C₄When alkyl, said C₁-C₄Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or when R^E、R^FAnd R^GEach independently is C substituted by one or more halogen₁-C₄When alkyl, said plurality is two or three;

and/or when R^E、R^FAnd R^GEach independently is C substituted by one or more halogen₁-C₄When the alkyl is used, the halogen is fluorine, chlorine, bromine or iodine.

3. The azulene isoindigo derivative according to claim 2, characterized in that,

when R is^AAnd R^BEach independently being C substituted by more than one halogen₁-C₄When alkyl, said C substituted by more than one halogen₁-C₄Alkyl is trifluoromethyl;

and/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently by an R^ASubstituted C₆-C₂₀Aryl radicalsWhen said is replaced by an R^ASubstituted C₆-C₂₀Aryl is

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently a plurality of R^ASubstituted C₆-C₂₀When aryl, said is substituted by a plurality of R^ASubstituted C₆-C₂₀Aryl is

And/or, when X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently by an R^BSubstituted C₂-C₂₀When it is heteroaryl, said is substituted by one R^BSubstituted C₂-C₂₀Heteroaryl is

And/or when R^A-1Is C substituted by more than one halogen₁-C₄Alkyl, said C substituted by multiple halogens₁-C₄Alkyl is trifluoromethyl;

and/or when R^E、R^FAnd R^GEach independently being C substituted by more than one halogen₁-C₄When alkyl, said C substituted by more than one halogen₁-C₄The alkyl group is trifluoromethyl.

4. The azulene isoindigo derivative according to claim 1, characterized in that,

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹and X¹⁰Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, preferably H or C₂-C₂₀A heteroaryl group; preferably, X¹、X²、X⁴、X⁵、X⁶、X⁷、X⁹And X¹⁰Is H;

and/or, X¹And X¹⁰Identical or different, preferably identical;

and/or, X²And X⁹Identical or different, preferably identical;

and/or, X³And X⁸Identical or different, preferably identical;

and/or, X⁴And X⁷Identical or different, preferably identical;

and/or, X⁵And X⁶Identical or different, preferably identical;

and/or, Y¹And Y²Identical or different, preferably identical;

and/or, Y¹And Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, preferably H, bromo,

And/or, R^AAnd R^BEach independently is halogen, C₁-C₄Alkyl or C substituted by one or more halogens₁-C₄Alkyl, preferably halogen;

and/or, R¹And R²Identical or different, preferably identical;

and/or, R¹And R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈Alkyl, preferably C₁-C₄₈Alkyl radical, morePreferably C₆-C₂₀Alkyl, most preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl.

5. The azulene isoindigo derivative according to claim 1, characterized in that the compound according to formula I is according to any of the following schemes:

the first scheme is as follows:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

scheme II:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Bis halogen, C₁-C₄Alkyl or C substituted by one or more halogens₁-C₄An alkyl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

X¹and X¹⁰The same;

X²and X⁹The same;

X³and X⁸The same;

X⁴and X⁷The same;

X⁵and X⁶The same;

Y¹and Y²The same;

R¹and R²The same;

the third scheme is as follows:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹and X¹⁰Each independently is H or C₂-C₂₀A heteroaryl group;

Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Bis halogen;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

X¹and X¹⁰The same;

X²and X⁹The same;

X³and X⁸The same;

X⁴and X⁷The same;

X⁵and X⁶The same;

Y¹and Y²The same;

R¹and R²The same;

and the scheme is as follows:

X¹、X²、X⁴、X⁵、X⁶、X⁷、X⁹and X¹⁰Is H;

X³and X⁸Each independently is H or C₂-C₂₀A heteroaryl group;

Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Aand R^BIs halogen;

R¹and R²The same;

R¹and R²Are each independently C₁-C₄₈Alkyl, preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl.

6. The azulene isoindigo derivative according to claim 1, characterized in that the compound according to formula I is any one of the following compounds:

7. a preparation method of azulene isoindigo derivative shown in formula I is characterized by comprising any one of the following schemes:

scheme A:

when the azulene isoindigo derivative shown as the formula I is described in any one of claims 1 to 6, and Y is¹And Y²Are each independently C₆-C₂₀Aryl or C₂-C₂₀When it is heteroaryl;

a compound of formula II with Y¹-B and Y²Carrying out coupling reaction as described below on the B to obtain a compound shown as a formula I;

a is halogen or OTf;

b isPotassium trifluoroborate or

The coupling reaction preferably comprises the steps of: in a solvent, in the presence of alkali, a palladium catalyst and a ligand, reacting a compound shown as a formula II with Y¹-B and Y²Carrying out the coupling reaction on the B to obtain a compound shown as a formula I;

scheme B:

when the azulene isoindigo derivative shown in the formula I is as shown in any one of claims 1 to 6, and Y is¹And Y²When is bromine;

carrying out bromination reaction on the compound shown in the formula III to obtain a compound shown in the formula I;

the bromination reaction preferably comprises the following steps: carrying out bromination reaction on the compound shown in the formula III in a solvent in the presence of NBS and alkali to obtain the compound shown in the formula I;

scheme C:

when the azulene isoindigo derivative shown in the formula I is as in any one of claims 1-6,

carrying out coupling reaction shown as the following on the compound shown as the formula IV and the compound shown as the formula V to obtain the compound shown as the formula I,

the coupling reaction preferably comprises the steps of:

in a solvent, in the presence of a Lawson reagent, carrying out the coupling reaction on the compound shown in the formula IV and the compound shown in the formula V to obtain the compound shown in the formula I.

8. The process for the preparation of azulene isoindigo derivative according to formula I in claim 7, characterized in that:

in the coupling reaction, Y is¹And Y²The same;

and/or, in the coupling reaction, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹And X¹⁰Are each independently H, C₆-C₂₀Aryl radicals, substituted by one or more R^ASubstituted C₆-C₂₀Aryl radical, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, preferably H, C₆-C₂₀Aryl or C₂-C₂₀A heteroaryl group; preferably, in the coupling reaction, the compound shown in the formula I isThe compound shown as the formula II is

And/or, in said coupling reaction, R^AAnd R^BAre each independently C₁-C₄Alkyl radical, C₆-C₁₀Aryl radicals or by one or more R^A-1Substituted C₆-C₁₀Aryl radical, R^A-1Preferably C₁-C₄An alkyl group;

and/or, in said coupling reaction, R^E、R^FAnd R^GIs C₁-C₄Alkyl or

And/or, in the coupling reaction, when a is halogen, the halogen is fluorine, chlorine, bromine or iodine, preferably bromine;

and/or, in the coupling reaction, the coupling reaction is carried out under the protection of inert gas, and the inert gas is preferably nitrogen and/or argon;

and/or, in the coupling reaction, the coupling reaction is carried out under anaerobic conditions;

and/or, in the coupling reaction, the palladium catalyst is Pd (PPh)₃)₄、Pd(PPh₃)₂Cl₂And Pd (dppf) Cl₂One or more of;

and/or, in the coupling reaction, the molar ratio of the palladium catalyst to the compound shown in the formula II is 0.01: 1-5:1, preferably 0.03:1 to 1.65:1, more preferably 0.03:1 to 0.3: 1;

and/or, in the coupling reaction, the solvent is water and/or an organic solvent, more preferably water and an organic solvent; the organic solvent is preferably C₁-C₄One or more of an alcohol solvent, an aromatic hydrocarbon solvent and an ether solvent, more preferably tetrahydrofuran; when the organic solvent is water and the organic solvent, the volume ratio of the water to the organic solvent may be 1: 3-1: 5;

and/or, in the coupling reaction, the volume-mass ratio of the solvent to the compound shown in the formula II is 1mL/g-100mL/g, preferably 35mL/g-98 mL/g;

and/or, in the coupling reaction, the base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, silver carbonate and sodium bicarbonate, preferably potassium carbonate;

and/or in the coupling reaction, the molar ratio of the alkali to the compound shown as the formula II is 5: 1-7: 1, preferably 6: 1;

and/or, in the coupling reaction, the ligand is S-phos;

and/or, in the coupling reaction, the ratio of the ligand to the palladium catalyst is 4: 1-6: 1, preferably 5: 1;

and/or, in the coupling reaction, the reaction temperature is 50-120 ℃, preferably 80-110 ℃;

and/or, in the coupling reaction, the reaction time is from 30 minutes to 10 hours, preferably from 5 to 9 hours;

and/or, in the bromination reaction, the solvent is a halogenated alkane solvent, preferably dichloromethane;

and/or, in the bromination reaction, the alkali is sodium acetate and/or potassium acetate;

and/or in the bromination reaction, the compound shown as the formula I isCorrespondingly, the compound shown as the formula III is

And/or, in the coupling reaction, the compound shown in the formula IV is the same as the compound shown in the formula V;

and/or, in the coupling reaction, the compound shown in the formula IV and the compound shown in the formula V are respectively and independentlyPreferably, the compound shown in the formula I is

And/or, in the coupling reaction, the solvent is an aromatic hydrocarbon solvent, preferably one or more of toluene, benzene and xylene;

and/or, in the coupling reaction, the molar ratio of the Lawson reagent to the compound shown in the formula IV is 0.5:1-5:1, preferably 0.5:1-1:1, more preferably 0.5:1-0.8: 1;

and/or in the coupling reaction, the reaction temperature is 60-80 ℃;

and/or, in the coupling reaction, the volume-to-mass ratio of the solvent to the compound shown in the formula IV is 20 mL/g-80 mL/g, preferably 56 mL/g;

and/or in the coupling reaction, the reaction time is 0.5-5 hours, preferably 0.5-1 hour.

9. The process for the preparation of azulene isoindigo derivative according to formula I according to claim 7 or 8, characterized in that the process for the preparation of the compound according to formula I further comprises the following steps:

performing cyclization reaction on the compound shown in the formula VI as shown in the specification to obtain a compound shown in the formula IV;

wherein, X¹、X²、X³、X⁴、X⁵And R²Are as defined in any one of claims 1 to 6;

the cyclization reaction preferably comprises the following steps:

in a solvent, in the presence of alkali and oxalyl chloride, carrying out the cyclization reaction on the compound shown as the formula VI to obtain the compound shown as the formula IV.

10. The process for the preparation of azulene isoindigo derivative according to formula I according to claim 9, characterized in that:

in the cyclization reaction, the compound shown as the formula VI is Correspondingly, the compound shown as the formula IV is

And/or, in the cyclization reaction, the solvent is a halogenated hydrocarbon solvent, preferably dichloromethane;

and/or, in the cyclization reaction, the volume-mass ratio of the solvent to the compound shown in the formula VI is 50 mL/g-100mL/g, preferably 72 mL/g;

and/or, in the cyclization reaction, the base is triethylamine;

and/or in the cyclization reaction, the molar ratio of the compound shown as the formula VI to the oxalyl chloride is 1: 1-1: 3, and more preferably 1: 1.2-1: 1.5;

and/or in the cyclization reaction, the reaction temperature is 0-50 ℃, and preferably 0-30 ℃;

and/or in the cyclization reaction, the reaction time is 6-18 hours, preferably 8-12 hours, and more preferably 10 hours.

11. The process for the preparation of azulene isoindigo derivative according to formula I according to claim 9, characterized in that the process for the preparation of the compound according to formula I further comprises the following steps:

carrying out the Buhward-Hartvisch coupling reaction on the compound shown in the formula VII to obtain a compound shown in the formula VI;

b is halogen or-OTf;

wherein, X¹、X²、X³、X⁴、X⁵And R²Are as defined in any one of claims 1 to 6;

the said Buhward-Hartvich coupling reaction preferably comprises the following steps:

in a solvent, in a base, a palladium catalyst, a ligand and R²-NH₂In the presence of a compound of formula VIIThe compound is subjected to the Buhward-Hartvisch coupling reaction to obtain the compound shown in the formula VI.

12. The process for the preparation of azulene isoindigo derivative according to formula I according to claim 11, characterized in that:

in said coupling reaction between said B and B, wherein B is halogen, said halogen is fluorine, chlorine, bromine or iodine, preferably chlorine;

and/or, in the Buhward-Hartvehg coupling reaction, the compound shown in the formula VI isCorrespondingly, the compound shown as the formula VII is

And/or, in the Buhward-Hartvisch coupling reaction, the solvent is one or more of aromatic hydrocarbon solvent, halogenated aromatic hydrocarbon solvent, ether solvent and amide solvent, preferably one or more of toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, dimethoxyethane, N-dimethylformamide and N, N-dimethylacetamide;

and/or, in the Buhward-Hartvich coupling reaction, the base is one or more of sodium tert-butoxide, potassium tert-butoxide, sodium carbonate and potassium carbonate;

and/or, in said coupling reaction between said base and said compound of formula VII in a molar ratio of 1: 1-5:1, preferably 2: 1-4: 1;

and/or, in the Buhward-Hartvich coupling reaction, the palladium catalyst is Pd₂(dba)₃、Pd(PPh₃)₄、Pd(PPh₃)₂Cl₂、Pd(dppf)Cl₂And Pd (OAc)₂One or more of;

and/or, in said coupling reaction between said palladium catalyst and said compound of formula VII in a molar ratio of 0.01: 1-5:1, preferably 0.01: 1-1.65: 1, more preferably 0.02:1 to 0.2: 1;

and/or, in the Buhward-Hart-Virgiz coupling reaction, the ligand is Xantphos, BINAP, P (o-tol)₃And P (t-Bu)₃One or more of;

and/or, in said Buhward-Hartvich coupling reaction, said R²-NH₂The molar ratio of the compound to the compound shown as the formula VII is 1: 1-5:1, preferably 2: 1-4: 1;

and/or in the Buhward-Hartvisch coupling reaction, the reaction temperature is 80-150 ℃, preferably 100-120 ℃;

and/or in the Buhward-Hartvich coupling reaction, the reaction time is 8 to 18 hours, preferably 9 to 12 hours.

13. A compound, compound 3a or compound 3b according to formula IV:

X¹、X²、X³、X⁴、X⁵and R²Is as defined in any one of claims 1 to 6,

the compound shown in the formula IV is preferably

14. A method for preparing a compound shown in a formula VIII from azulene isoindigo derivative shown in a formula I is characterized by comprising the following steps:

when the azulene isoindigo derivative shown as the formula I is shown in any one of claims 1 to 6Is as described in (1), and Y¹And Y²In the case of halogen or-OTf,

carrying out polymerization reaction as shown in the specification on a compound shown in a formula I and a compound shown in a formula IX to obtain a polymer shown in a formula VIII,

n is 2 to 40;

c isPotassium trifluoroborate or

The polymerization reaction preferably comprises the steps of:

in a solvent, in the presence of a palladium catalyst, a ligand and alkali, carrying out the polymerization reaction on a compound shown as a formula I and a compound shown as a formula IX to obtain a polymer shown as a formula VIII.

15. The process of claim 14 for the preparation of a compound of formula VIII:

in said polymerization, at Y¹And Y²When halogen, said halogen is fluorine, chlorine, bromine or iodine, preferably bromine;

and/or, in the polymerization reaction, the C is

And/or, in the polymerization reaction, the compound shown as the formula I is

And/or, in said polymerization, a compound of formula IXThe object isPreferably, the polymer of formula VIII is

And/or in the polymerization reaction, n is 4-26, preferably 6-16;

and/or, in the polymerization reaction, the polymerization reaction is carried out under the protection of inert gas, and the inert gas is nitrogen and/or argon;

and/or, in said polymerization reaction, said polymerization reaction is carried out under oxygen-free conditions;

and/or, in the polymerization reaction, the palladium catalyst is Pd (PPh)₃)₄、Pd(PPh₃)₂Cl₂And Pd (dppf) Cl₂One or more of;

and/or, in the polymerization reaction, the molar ratio of the palladium catalyst to the compound shown in the formula I is 0.01: 1-5:1, preferably 0.01:1 to 1.65:1, more preferably 0.01:1 to 0.3: 1;

and/or, in the polymerization reaction, the solvent is water and/or an organic solvent, preferably water and an organic solvent; the organic solvent is preferably C₁-C₄One or more of an alcohol solvent, an aromatic hydrocarbon solvent and an ether solvent, more preferably tetrahydrofuran; when the organic solvent is water and the organic solvent, the volume ratio of the water to the organic solvent is 1: 3-1: 5;

and/or, in the polymerization reaction, the volume-mass ratio of the solvent to the compound shown in the formula I is 2mL/g-40mL/g, preferably 20mL/g-40 mL/g;

and/or, in the polymerization reaction, the alkali is one or more of sodium carbonate, potassium carbonate, cesium carbonate, silver carbonate and sodium bicarbonate, preferably potassium carbonate;

and/or in the polymerization reaction, the molar ratio of the alkali to the compound shown in the formula I is 5: 1-7: 1, preferably 6: 1;

and/or, in said polymerization, said ligand is S-phos;

and/or, in the polymerization reaction, the molar ratio of the ligand to the palladium catalyst is 4: 1-6: 1, preferably 5: 1;

and/or, in the polymerization reaction, the reaction temperature is 50-120 ℃, preferably 80-110 ℃;

and/or in the polymerization reaction, the reaction time is 10-40 hours, preferably 15-24 hours.

16. A polymer of formula VIII:

n is 2-40, preferably 4-26, and more preferably 6-16;

wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、R¹And R²Are as defined in any one of claims 1 to 6.

17. The application of the azulene isoindigo derivative shown in the formula I and/or the polymer shown in the formula VIII in the preparation of a response material is disclosed in any one of claims 1 to 6, and the polymer shown in the formula VIII is disclosed in claim 16, and is preferably applied to the preparation of a color developing agent, a color developing material or a proton sensor.

Background

The stimulus response material is a molecular system with an intelligent behavior, and is sensitive to external stimulus, and the molecular structure of the stimulus response material is reversibly or irreversibly changed under the action of an external stimulus signal (such as pH value, light, temperature, voltage, redox agent, gas and the like), so that the physicochemical property or the functional state of the stimulus response material is greatly changed, and the corresponding function is further embodied. At present, the stimuli-responsive material has important application values in the fields of controlled drug release, nano catalysis, chemical sensing, biotechnology and the like (Paspaakis G.et al.Polym.chem.2011,2, 1234-1248; Stuart M.A.C.et al.Nat.Mater.2010,9, 101-113; Bajpai A.K.et al.prog.Polym.Sci.2008,33, 1088-1118; York A.W.et al.Adv.Drug Delivery Rev.2008,60, 1018-1036; Alarocon C.D.H.et al.chem.Soc.Rev.2005,34,276-285; Discher D.E.et al.science 2002,297, 967-973.).

The acid-induced color-changing material is an important component of a stimulus response material, and the material has reversible color change due to different pH values or contact with acidic/alkaline gases, so that the material is widely applied to the fields of pH test paper or sensors and the like, and for example, components such as methyl red, bromocresol green, thymol blue and the like in the pH test paper are the most common acid-induced color-changing materials. The acid-induced color-changing material is used as a core component of the pH test paper or the sensor, and the sensitivity of the acid-induced color-changing material determines the detection limit and the responsiveness of the device. In recent years, the development of highly sensitive and highly responsive acid-induced color-changing materials has been one of the major points of research in this field.

Disclosure of Invention

The technical problem to be solved by the invention is that the acid-induced discoloration compound in the prior art has a single structure. Therefore, the invention provides an azulene isoindigo derivative, a preparation method and an application thereof. The azulene isoindigo derivative has a large pi conjugated system, reversible redox property, an adjustable dissolution promoting alkyl chain and reversible proton response property, and can be polymerized to form a novel organic functional material; in addition, the azulene isoindigo derivative has a plurality of chemical active sites, can be subjected to modification connection of different sites, and has the advantages of simple preparation method, cheap and easily-obtained raw materials and high purity of a target compound.

The invention provides an azulene isoindigo derivative shown as a formula I:

wherein the content of the first and second substances,

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₆-C₂₀Aryl radicals, substituted by one or more R^ASubstituted C₆-C₂₀Aryl radical, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group; said C₂-C₂₀Heteroaryl is C with 1,2, 3 or 4 heteroatoms selected from N, O, Se and S₂-C₂₀A heteroaryl group;

R^Aand R^BEach independently is halogen, C₁-C₄Alkyl, C substituted by one or more halogens₁-C₄Alkyl radical, C₆-C₁₀Aryl radicals or by one or more R^A-1Substituted C₆-C₁₀An aryl group;

R^A-1is halogen, C₁-C₄Alkyl or C substituted by one or more halogens₁-C₄An alkyl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl, by one or more R^ESubstituted C₁-C₄₈Alkyl radical, C₂-C₄₈Alkenyl, by one or more R^FSubstituted C₂-C₄₈Alkenyl radical, C₆-C₂₄Cycloalkyl radicals or substituted by one or more R^GSubstituted C₆-C₂₄A cycloalkyl group;

R^E、R^Fand R^GEach independently is halogen, C₁-C₄Alkyl, aryl, heteroaryl, and heteroaryl,Or C substituted by one or more halogens₁-C₄An alkyl group.

In one embodiment, in the compounds of formula I, certain groups may be defined as follows, and the remaining groups may be defined as in any of the above embodiments: (for this expression, hereinafter, referred to as a certain embodiment)

When X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²When each is independently a halogen, the halogen is preferably fluorine, chlorine, bromine or iodine, more preferably bromine.

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently C₆-C₂₀When aryl, said C₆-C₂₀Aryl is preferably C₆-C₁₀Aryl, more preferably phenyl, naphthyl (preferably) Or azulenyl (preferably))。

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^ASubstituted C₆-C₂₀When aryl, said C₆-C₂₀Aryl is preferably C₆-C₁₀Aryl, more preferably phenyl, naphthyl (preferably) Or azulenyl (preferably)) Preferably, said plurality is two or three.

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently C₂-C₂₀When it is heteroaryl, said C₂-C₂₀Heteroaryl is preferably C₂-C₁₀Heteroaryl, more preferably furyl, pyrrolyl, thienyl, pyridyl, imidazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl or pyrazinyl, further preferably thienyl or pyridyl, most preferably thienyl or pyridyl

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Each independently by one or more R^BSubstituted C₂-C₂₀When it is heteroaryl, said C₂-C₂₀Heteroaryl is preferably C₂-C₁₀Heteroaryl, more preferably furyl, pyrrolyl, thienyl, pyridyl, imidazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl or pyrazinyl, further preferably thienyl or pyridyl, most preferably thienyl or pyridylSaid plurality is preferably two or three.

In one aspect: when R is^AAnd R^BWhen each is independently a halogen, the halogen is preferably fluorine, chlorine, bromine or iodine.

In one aspect: when R is^AAnd R^BAre each independently C₁-C₄When alkyl, said C₁-C₄The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.

In one aspect: when R is^AAnd R^BEach independently by one or more halogensSubstituted C₁-C₄When alkyl, said C₁-C₄The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group, and the plural is preferably two or three.

In one aspect: when R is^AAnd R^BEach independently is C substituted by one or more halogen₁-C₄In the case of alkyl, the halogen is preferably fluorine, chlorine, bromine or iodine, and the plurality is preferably two or three.

In one aspect: when R is^AAnd R^BEach independently being C substituted by more than one halogen₁-C₄When alkyl, said C substituted by more than one halogen₁-C₄The alkyl group is trifluoromethyl.

In one aspect: when R is^AAnd R^BAre each independently C₆-C₁₀When aryl, said C₆-C₁₀Aryl is preferably phenyl, naphthyl (preferably) Or azulenyl (preferably))。

In one aspect: when R is^AAnd R^BEach independently by one or more R^A-1Substituted C₆-C₁₀When aryl, said C₆-C₁₀Aryl is preferably phenyl, naphthyl (preferably) Or azulenyl (preferably)) Preferably, said plurality is two or three.

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently by an R^ASubstituted C₆-C₂₀When aryl, said is substituted by one R^ASubstituted C₆-C₂₀Aryl is

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently a plurality of R^ASubstituted C₆-C₂₀When aryl, said is substituted by a plurality of R^ASubstituted C₆-C₂₀Aryl is

In one aspect: when X is present¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹And Y²Are each independently by an R^BSubstituted C₂-C₂₀When it is heteroaryl, said is substituted by one R^BSubstituted C₂-C₂₀Heteroaryl is

In one aspect: when R is^A-1When halogen is used, the halogen is preferably fluorine, chlorine, bromine or iodine.

In one aspect: when R is^A-1Is C₁-C₄When alkyl, said C₁-C₄The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.

In one aspect: when R is^A-1Is C substituted by one or more halogens₁-C₄Alkyl radical, said C₁-C₄The alkyl is preferably methyl, ethyl, n-propyl, isopropylAn alkyl group, an n-butyl group, an isobutyl group or a tert-butyl group, said plurality preferably being two or three.

In one aspect: when R is^A-1Is C substituted by one or more halogens₁-C₄Alkyl, said halogen is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, said plurality is preferably two or three.

In one aspect: when R is^A-1Is C substituted by more than one halogen₁-C₄Alkyl, said C substituted by multiple halogens₁-C₄The alkyl group is trifluoromethyl.

In one aspect: when R is¹And R²Are each independently C₁-C₄₈When alkyl, said C₁-C₄₈Alkyl is preferably C₆-C₂₀Alkyl, more preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl.

In one aspect: when R is¹And R²Each independently by one or more R^ESubstituted C₁-C₄₈When alkyl, said C₁-C₄₈Alkyl is preferably C₆-C₂₀Alkyl, more preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl, said plurality preferably being two or three.

In one aspect: when R is¹And R²Are each independently C₂-C₄₈When alkenyl, said C₂-C₄₈Alkenyl is preferably C₂-C₂₀An alkenyl group.

In one aspect: when R is¹And R²Each independently by one or more R^FSubstituted C₂-C₄₈When alkenyl, said C₂-C₄₈Alkenyl is preferably C₂-C₂₀Alkenyl, said plurality being preferably two or three.

In one aspect: when R is^E、R^FAnd R^GWhen each is independently a halogen, the halogen is preferably fluorine, chlorine, bromine or iodine.

In one aspect: when R is^E、R^FAnd R^GAre each independently C₁-C₄When alkyl, said C₁-C₄The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group.

In one aspect: when R is^E、R^FAnd R^GAre each independentlyWhen, C is said₁-C₄Alkyl is independently preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

In one aspect: when R is^E、R^FAnd R^GEach independently is C substituted by one or more halogen₁-C₄When alkyl, said C₁-C₄The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group, and the plural is preferably two or three.

In one aspect: when R is^E、R^FAnd R^GEach independently is C substituted by one or more halogen₁-C₄In the case of alkyl, the halogen is preferably fluorine, chlorine, bromine or iodine.

In one aspect: when R is^E、R^FAnd R^GEach independently being C substituted by more than one halogen₁-C₄When alkyl, said C substituted by more than one halogen₁-C₄The alkyl group is trifluoromethyl.

In one aspect: x¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹And X¹⁰Independently of one another, preferably H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, more preferably H or C₂-C₂₀A heteroaryl group.

In one aspect: x¹And X¹⁰Identical or different, preferablyThe same is selected.

In one aspect: x²And X⁹Identical or different, preferably identical.

In one aspect: x³And X⁸Identical or different, preferably identical.

In one aspect: x⁴And X⁷Identical or different, preferably identical.

In one aspect: x⁵And X⁶Identical or different, preferably identical.

In one aspect: x¹、X²、X⁴、X⁵、X⁶、X⁷、X⁹And X¹⁰Is H.

In one aspect: x³And X⁸Each independently is H or C₂-C₂₀A heteroaryl group.

In one aspect: y is¹And Y²Identical or different, preferably identical.

In one aspect: y is¹And Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, more preferably H, bromo,

In one aspect: r^AAnd R^BEach independently is halogen, C₁-C₄Alkyl or C substituted by one or more halogens₁-C₄Alkyl, more preferably halogen.

In one aspect: r¹And R²Identical or different, preferably identical.

In one aspect: r¹And R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈Alkyl, preferably C₁-C₄₈Alkyl, more preferably C₆-C₂₀Alkyl, most preferably n-hexyl, n-heptyl, n-octylNonyl, n-quinyl or 2-hexyl-1-quinyl.

In one embodiment, the compound of formula I is any one of the following:

the first scheme is as follows:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

scheme II:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Bis halogen, C₁-C₄Alkyl or C substituted by one or more halogens₁-C₄An alkyl group;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

X¹and X¹⁰The same;

X²and X⁹The same;

X³and X⁸The same;

X⁴and X⁷The same;

X⁵and X⁶The same;

Y¹and Y²The same;

R¹and R²The same;

the third scheme is as follows:

X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹and X¹⁰Each independently is H or C₂-C₂₀A heteroaryl group;

Y¹and Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Bis halogen;

R¹and R²Are each independently H, C₁-C₄₈Alkyl or by one or more R^ESubstituted C₁-C₄₈An alkyl group;

X¹and X¹⁰The same;

X²and X⁹The same;

X³and X⁸The same;

X⁴and X⁷The same;

X⁵and X⁶The same;

Y¹and Y²The same;

R¹and R²The same;

and the scheme is as follows:

X¹、X²、X⁴、X⁵、X⁶、X⁷、X⁹and X¹⁰Is H;

X³and X⁸Each independently is H or C₂-C₂₀Heteroaryl radical

Y¹And Y²Each independently is H, halogen, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀A heteroaryl group;

R^Aand R^BIs halogen;

R¹and R²The same;

R¹and R²Are each independently C₁-C₄₈Alkyl, preferably n-hexyl, n-heptyl, n-octyl, n-nonyl, n-quinyl or 2-hexyl-1-quinyl.

In one embodiment, the compound of formula I is any one of the following compounds:

the application also provides a preparation method of the compound shown in the formula I, which comprises the following steps:

when Y is¹And Y²Are each independently C₆-C₂₀Aryl or C₂-C₂₀When it is heteroaryl;

a compound of formula II with Y¹-B and Y²Carrying out coupling reaction as described below on the B to obtain a compound shown as a formula I;

a is halogen or OTf;

b isPotassium trifluoroborate or

Wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、R¹And R²The definition of (1) is as described in any of the above schemes.

The coupling reaction preferably comprises the steps of: in a solvent in the presence of a base, a palladium catalyst and a ligandThen, the compound shown as the formula II and Y are reacted¹-B and Y²And (4) carrying out the coupling reaction on the B to obtain the compound shown in the formula I.

In the coupling reaction, Y is¹And Y²Preferably the same.

In the coupling reaction, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹And X¹⁰Preferably H, C₆-C₂₀Aryl radicals, substituted by one or more R^ASubstituted C₆-C₂₀Aryl radical, C₂-C₂₀Heteroaryl or substituted by one or more R^BSubstituted C₂-C₂₀Heteroaryl, more preferably H, C₆-C₂₀Aryl or C₂-C₂₀A heteroaryl group.

In the coupling reaction, R^AAnd R^BPreferably C₁-C₄Alkyl radical, C₆-C₁₀Aryl radicals or by one or more R^A-1Substituted C₆-C₁₀Aryl radical, R^A-1Preferably C₁-C₄An alkyl group.

In the coupling reaction, R^E、R^FAnd R^GPreferably C₁-C₄Alkyl or

In the coupling reaction, when a is halogen, the halogen is preferably fluorine, chlorine, bromine or iodine, more preferably bromine.

In the coupling reaction, the compound shown as the formula I is preferablyThe compound shown in the formula II is preferably

In the coupling reaction, the coupling reaction is preferably carried out under the protection of an inert gas, and the inert gas is preferably nitrogen and/or argon.

In the coupling reaction, the coupling reaction is preferably carried out under anaerobic conditions.

In the coupling reaction, the palladium catalyst may be Pd (PPh)₃)₄、Pd(PPh₃)₂Cl₂And Pd (dppf) Cl₂One or more of (a).

In the coupling reaction, the molar ratio of the palladium catalyst to the compound of formula II may be a ratio conventional in the art for such coupling reactions, preferably 0.01: 1-5:1, more preferably 0.03:1 to 1.65:1, most preferably 0.03:1 to 0.3:1, for example 0.05: 1.

in the coupling reaction, the solvent may be a solvent conventional in the art for such coupling reactions, preferably water and/or an organic solvent, more preferably water and an organic solvent; the organic solvent is preferably C₁-C₄One or more of an alcohol solvent (preferably ethanol), an aromatic hydrocarbon solvent (preferably toluene and/or chlorobenzene), and an ether solvent (preferably 1, 4-dioxane and/or tetrahydrofuran), more preferably tetrahydrofuran. When the organic solvent is water and the organic solvent, the volume ratio of the water to the organic solvent is 1: 3-1: 5.

in the coupling reaction, the volume-to-mass ratio of the solvent to the compound shown in the formula II can be a ratio which is conventional in the coupling reaction in the field, and is preferably 1mL/g-100mL/g, and is preferably 35mL/g-98 mL/g.

In the coupling reaction, the base may be a base conventional in the art for such coupling reactions, preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate, silver carbonate and sodium bicarbonate, more preferably potassium carbonate.

In the coupling reaction, the molar ratio of the alkali to the compound shown in the formula II can be a conventional ratio of the coupling reaction in the field, preferably 5: 1-7: 1, and more preferably 6: 1.

In the coupling reaction, the ligand may be a ligand conventional in such coupling reactions of the art, preferably S-phos (2-dicyclohexylphosphine-2 ', 6' -dimethoxy-biphenyl).

In the coupling reaction, the ratio of the ligand to the palladium catalyst can be 4: 1-6: 1, preferably 5: 1.

In the coupling reaction, the reaction temperature may be a temperature conventional in the art for such coupling reactions, preferably from 50 ℃ to 120 ℃, more preferably from 80 ℃ to 110 ℃.

In the coupling reaction, the progress of the coupling reaction can be detected by a detection method (such as TLC, GC, etc.),¹H NMR or GC, etc.) and the end point of the reaction is generally determined as the time when the compound represented by formula II disappears or does not react any more, the reaction time is preferably 30 minutes to 10 hours, more preferably 5 to 9 hours.

The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:

when Y is¹And Y²When is bromine;

carrying out bromination reaction on the compound shown in the formula III to obtain a compound shown in the formula I;

wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、R¹And R²The definition of (1) is as described in any of the above schemes;

the bromination reaction preferably comprises the following steps: in a solvent, under the existence of NBS and alkali, carrying out bromination reaction on the compound shown in the formula III to obtain the compound shown in the formula I.

The conditions and procedures of the bromination reaction described may be those conventional in this type of bromination reaction in the art, with the following being particularly preferred in the present invention:

in the bromination reaction, the solvent can be a halogenated alkane solvent, preferably dichloromethane.

In the bromination reaction, the alkali can be sodium acetate and/or potassium acetate.

In the bromination reaction, the compound shown as the formula I is preferably selectedAccordingly, the compound represented by the formula III is preferably

The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:

carrying out coupling reaction shown as the following on the compound shown as the formula IV and the compound shown as the formula V to obtain the compound shown as the formula I,

wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、Y¹、Y²、R¹And R²The definition of (1) is as described in any of the above schemes;

the coupling reaction preferably comprises the steps of:

in a solvent, in the presence of a Lawson reagent, carrying out the coupling reaction on the compound shown in the formula IV and the compound shown in the formula V to obtain the compound shown in the formula I.

In the coupling reaction, the compound shown in the formula IV and the compound shown in the formula V are preferably the same; more preferablyAccordingly, the compound of formula I is preferred

In the coupling reaction, the solvent may be a solvent conventional in the art for such coupling reactions, preferably an aromatic hydrocarbon solvent, more preferably one or more of toluene, benzene and xylene.

In the coupling reaction, the molar ratio of the lawson reagent to the compound represented by formula IV may be 0.5:1 to 5:1, preferably 0.5:1 to 1:1, more preferably 0.5:1 to 0.8: 1.

In the coupling reaction, the reaction temperature can be the conventional temperature of the coupling reaction in the field of organic synthesis, and preferably is 60-80 ℃.

In the coupling reaction, the volume-to-mass ratio of the solvent to the compound shown in formula IV can be a ratio which is conventional in the coupling reaction in the field, and is preferably 20 mL/g-80 mL/g, and more preferably 56 mL/g.

In the coupling reaction, the progress of the reaction can be detected by a detection method (such as TLC, GC, etc.) which is conventional in the field of organic synthesis,¹H NMR or GC, etc.), the reaction time may be 0.5 to 5 hours, preferably 0.5 to 1 hour, with the end point of the reaction generally being the time when the compound shown in formula IV disappears.

The preparation method of the compound shown in the formula I can further comprise the following steps:

performing cyclization reaction on the compound shown in the formula VI as shown in the specification to obtain a compound shown in the formula IV;

wherein, X¹、X²、X³、X⁴、X⁵And R²The definition of (1) is as described in any of the above schemes;

the cyclization reaction preferably comprises the following steps:

in a solvent, in the presence of alkali and oxalyl chloride, carrying out the cyclization reaction on the compound shown as the formula VI to obtain the compound shown as the formula IV.

The conditions and procedures of the ring closure reaction may be those conventional in the art for such ring closure reactions, and the following are particularly preferred in the present invention:

in the cyclization reaction, the compound shown as the formula VI is preferably selected Accordingly, the compound of formula IV is preferred

In the cyclization reaction, the solvent can be a solvent conventional in the cyclization reaction in the field, preferably a halogenated hydrocarbon solvent, and more preferably dichloromethane.

In the cyclization reaction, the amount of the solvent is not particularly limited as long as the reaction is not affected, and the volume-to-mass ratio of the solvent to the compound shown in the formula VI can be 50mL/g to 100mL/g, preferably 72 mL/g.

In the ring closure reaction, the base may be a base conventional in the art for such ring closure reactions, preferably triethylamine.

In the cyclization reaction, the molar ratio of the compound shown as the formula VI to the oxalyl chloride can be 1: 1-1: 3, and is more preferably 1: 1.2-1: 1.5.

In the cyclization reaction, the reaction temperature can be a temperature conventional in the cyclization reaction in the field, preferably 0-50 ℃, and more preferably 0-30 ℃.

In the cyclization reaction, the progress of the cyclization reaction can be detected by a detection method (such as TLC, GC, etc.),¹H NMR or GC, etc.) and is generally carried out when the compound of formula VI disappearsIs the end point of the reaction; the reaction time may be 6 to 18 hours, preferably 8 to 12 hours, and more preferably 10 hours.

The invention also provides a preparation method of the compound shown in the formula IV, which comprises the following steps:

performing cyclization reaction on the compound shown in the formula VI as shown in the specification to obtain a compound shown in the formula IV;

wherein, X¹、X²、X³、X⁴、X⁵And R²The definition of (1) is as described in any of the above schemes;

the conditions and procedures of the ring closure reaction may be as described above.

The present invention also provides a compound 3a or a compound 3 b:

the invention also provides a compound shown in the formula IV:

X¹、X²、X³、X⁴、X⁵and R²The definition of (a) is as described above,

the compound shown in the formula IV is preferably

The preparation method of the compound shown in the formula I can further comprise the following steps:

carrying out the Buhward-Hartvisch coupling reaction on the compound shown in the formula VII to obtain a compound shown in the formula VI;

b is halogen or-OTf;

wherein, X¹、X²、X³、X⁴、X⁵And R²The definition of (1) is as described in any of the above schemes;

the said Buhward-Hartvich coupling reaction preferably comprises the following steps:

in a solvent, in a base, a palladium catalyst, a ligand and R²-NH₂In the presence of the compound shown in the formula VII, the Buhward-Hartvisch coupling reaction is carried out to obtain the compound shown in the formula VI.

The conditions and steps of the Buhward-Hartvehg coupling reaction described may be those conventional in the art for such reactions, and the following are particularly preferred in the present invention:

in the said Buhward-Hartvisch coupling reaction, in the case where B is halogen, the said halogen is preferably fluorine, chlorine, bromine or iodine, more preferably chlorine.

In the Buhward-Hartvisc coupling reaction, the compound represented by the formula VI is preferably usedThe compound of formula VII is preferably

In the coupling reaction of the bravad-hartweichi type, the solvent may be a solvent conventional in the art, preferably one or more of aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, ether solvents and amide solvents, more preferably one or more of toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, dimethoxyethane, N-dimethylformamide and N, N-dimethylacetamide.

In the Buhward-Hartvisch coupling reaction, the base may be a base conventional in the art for such reactions, preferably one or more of sodium tert-butoxide, potassium tert-butoxide, sodium carbonate and potassium carbonate.

In the said Buhward-Hartvich coupling reaction, the molar ratio of the said base to the said compound of formula VII may be in the proportions conventional in the art for such reactions, preferably 1: 1-5:1, more preferably 2: 1-4: 1.

in the Buhward-Hartvich coupling reaction, the palladium catalyst may be Pd₂(dba)₃、Pd(PPh₃)₄、Pd(PPh₃)₂Cl₂、Pd(dppf)Cl₂And Pd (OAc)₂One or more of (a).

In the said Buhward-Hartvich coupling reaction, the molar ratio of the said palladium catalyst to the said compound of formula VII may be in the proportion conventional in this type of reaction, preferably 0.01: 1-5:1, more preferably 0.01: 1-1.65: 1, more preferably 0.02:1 to 0.2:1, for example 0.025: 1.

in the Buhward-Hartvisch coupling reaction, the ligand is preferably Xantphos (4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene), BINAP ((+ -) -2,2 '-bis- (diphenylphosphino) -1,1' -binaphthyl), P (o-tol)₃(tris (o-methylphenyl) phosphorus) and P (t-Bu)₃(tri-tert-butylphosphine).

In said Buhward-Hartvich coupling reaction, said R²-NH₂The molar ratio of the compound shown as the formula VII to the compound shown as the formula VII can be a conventional ratio of the reaction in the field, and is preferably 1: 1-5:1, and more preferably 2: 1-4: 1.

In the Buhward-Hartvisch coupling reaction, the reaction temperature may be a temperature conventional in the art, preferably 80-150 ℃, more preferably 100-120 ℃.

In the Buhward-Hartvisc coupling reaction, the progress of the reaction can be detected by methods conventional in the art (e.g., TLC, GC, etc.),¹H NMR or GC, etc.), generally as in the formula(VII) end point of reaction when compound VII disappears; the reaction time may be 8 to 18 hours, preferably 9 to 12 hours.

The invention also provides a preparation method of the compound shown in the formula VI, which comprises the following steps:

carrying out the Buhward-Hartvisch coupling reaction on the compound shown in the formula VII to obtain a compound shown in the formula VI;

b is halogen or-OTf;

wherein, X¹、X²、X³、X⁴、X⁵And R²The definition of (1) is as described in any of the above schemes;

the conditions and steps of the Buhward-Hartvehg coupling reaction can be as described above.

The invention also provides a method for preparing the compound shown in the formula VIII from the compound shown in the formula I, which comprises the following steps:

when Y is¹And Y²In the case of halogen or-OTf,

carrying out polymerization reaction as shown in the specification on a compound shown in a formula I and a compound shown in a formula IX to obtain a polymer shown in a formula VIII,

n is 2 to 40;

c isPotassium trifluoroborate or

Wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、R¹And R²The definition of (1) is as described in any of the above schemes;

the polymerization reaction preferably comprises the steps of:

in a solvent, in the presence of a palladium catalyst, a ligand and alkali, carrying out the polymerization reaction on a compound shown as a formula I and a compound shown as a formula IX to obtain a polymer shown as a formula VIII.

In said polymerization, at Y¹And Y²In the case of halogen, the halogen is fluorine, chlorine, bromine or iodine, preferably bromine.

In the polymerization, the C is preferably

In the polymerization reaction, the compound represented by the formula I is preferablyThe compound of formula IX is preferablyAccordingly, the polymer of formula VIII is

In the polymerization reaction, n is preferably 4 to 26, and more preferably 6 to 16.

In the polymerization reaction, the polymerization reaction is preferably carried out under the protection of inert gas, and the inert gas is preferably nitrogen and/or argon.

In the polymerization, the polymerization is preferably carried out under oxygen-free conditions.

In the polymerization, the palladium catalyst may be Pd (PPh)₃)₄、Pd(PPh₃)₂Cl₂And Pd (dppf) Cl₂One or more of (a).

The molar ratio of the palladium catalyst to the compound of formula I in the polymerization reaction may be in a ratio conventional in the art for such reactions, preferably 0.01: 1-5:1, more preferably 0.01:1 to 1.65:1, most preferably 0.01:1 to 0.3:1, for example 0.03: 1.

in the polymerization reaction, the solvent may be a solvent conventional in the art such reaction, preferably water and/or an organic solvent, more preferably water and an organic solvent; the organic solvent is preferably C₁-C₄One or more of an alcohol solvent (preferably ethanol), an aromatic hydrocarbon solvent (preferably toluene and/or chlorobenzene), and an ether solvent (preferably 1, 4-dioxane and/or tetrahydrofuran), more preferably tetrahydrofuran. When the organic solvent is water and the organic solvent, the volume ratio of the water to the organic solvent is 1: 3-1: 5.

in the polymerization reaction, the volume-to-mass ratio of the solvent to the compound shown in formula I can be a ratio which is conventional in the polymerization reaction in the field, and is preferably 2mL/g-40mL/g, more preferably 20mL/g-40mL/g, such as 36.7 mL/g.

In the polymerization, the base may be a base conventionally used in such polymerization in the art, preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate, silver carbonate and sodium hydrogen carbonate, more preferably potassium carbonate.

In the polymerization reaction, the molar ratio of the alkali to the compound shown in the formula I can be a conventional ratio in the polymerization reaction in the field, and is preferably 5: 1-7: 1, and more preferably 6: 1.

In the polymerization, the ligand may be a ligand conventional in the art for such polymerizations, preferably S-phos (2-dicyclohexylphosphine-2 ', 6' -dimethoxy-biphenyl).

In the polymerization reaction, the ratio of the ligand to the palladium catalyst can be 4:1 to 6:1, preferably 5: 1.

In the polymerization reaction, the reaction temperature may be a temperature conventional in such polymerization reactions in the art, preferably 50 to 120 ℃, more preferably 80 to 110 ℃.

In the polymerization, the progress of the polymerization can be detected by a detection method (such as TLC, GC, etc.) which is conventional in the field of organic synthesis,¹H NMR or GC, etc.), wherein the disappearance or no longer reaction of the compound shown as the formula I is generally used as the end point of the reaction, and the reaction time is preferably 10 to 40 hours, more preferably 15 to 24 hours.

The invention also provides a polymer shown as the formula VIII:

n is 2-40, preferably 4-26, and more preferably 6-16;

wherein, X¹、X²、X³、X⁴、X⁵、X⁶、X⁷、X⁸、X⁹、X¹⁰、R¹And R²The definition of (1) is as described in any of the above schemes.

The invention provides a polymer shown as a formula VIII, and a preparation method thereof is as described above.

The invention also provides application of the compound shown in the formula I and/or the polymer shown in the formula VIII in preparation of a response material, preferably application in preparation of a color developing agent, a color developing material or a proton sensor.

The term "halogen" refers to fluorine, chlorine, bromine or iodine.

The term "alkyl" refers to a saturated straight or branched chain hydrocarbon radical having from one to twelve carbon atoms (e.g., C)₁-C₆Alkyl radicals, also e.g. C₁-C₄Alkyl groups). Examples of alkyl groups include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-butyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-2-pentyl, 2-methyl-1-butyl, 2-pentyl, 2-methyl-2-pentyl, and the like, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-Butyl, 1-heptyl and 1-octyl.

The term "alkenyl" refers to a group having at least one site of unsaturation, i.e., a carbon-carbon sp²Straight or branched hydrocarbon radicals of two to forty-eight carbon atoms of a double bond (e.g. C)₂-C₂₀Alkenyl) and includes groups having "cis" and "trans" orientations or "E" and "Z" orientations.

The term "aryl" refers to any stable monocyclic or polycyclic carbocyclic ring of up to 20 atoms in each ring, wherein all rings are aromatic. Examples of the above aryl unit include phenyl, naphthyl, phenanthryl or anthryl.

The term "heteroaryl" refers to an aryl (or aromatic ring) containing 1,2, 3 or 4 heteroatoms independently selected from N, O, S and Se, which may be a monocyclic or polycyclic aromatic system, such as furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, isoxazolyl, oxazolyl, oxadiazolyl, imidazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, thiadiazolyl, benzimidazolyl, indolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, quinolinyl, isoquinolinyl, and the like.

The term "cycloalkyl" refers to a saturated monocyclic or polycyclic cycloalkyl group having six to twenty-four carbon atoms. Cycloalkyl groups contain 6 to 24 carbon atoms.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

In the present invention, room temperature means 10 to 40 ℃.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: the azulene isoindigo derivative has a large pi conjugated system, reversible redox property, adjustable dissolution promoting alkyl chain and reversible proton response property, and is a novel organic functional material which can be processed through solution; in addition, the azulene isoindigo derivative has a plurality of chemical active sites, can be subjected to modification connection of different sites, and has the advantages of simple preparation method, cheap and easily-obtained raw materials and high purity of a target compound.

Drawings

FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of Compound 1 a.

FIG. 2 is a cyclic voltammogram of Compound 1 a.

FIG. 3 shows the color change of the solution of the compound 1a after trifluoroacetic acid is added and the color change of the solution after triethylamine is added to adjust the system to be neutral.

FIG. 4 shows NMR spectra of Compound 1a before protonation, after protonation and after neutralization with base.

FIG. 5 is a gel permeation chromatography test chart of Polymer P1.

FIG. 6 is a compoundThe color of the solution after trifluoroacetic acid addition was changed, and triethylamine was added to adjust the color of the solution after the system was neutral.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

In the following examples, room temperature means 10-40 ℃. Overnight means 10-12 hours. Reflux refers to the reflux temperature of the solvent at atmospheric pressure.

Example 1 Synthesis of azulene isoindigo (1)

1.1, N-hexyl-2-aminoazulene (3a)

The compound 2(1.0g,6.1mmol), tris (dibenzylideneacetone) dipalladium (141mg,0.15mmol), (+ -) -2,2 '-bis- (diphenylphosphino) -1,1' -Binaphthyl (BINAP) (287mg,0.46mmol) and sodium tert-butoxide (1.18g,12.3mmol) were taken in a 100ml Schlenk tube and N was aspirated₂Three times in N₂Under the protection of (1.62ml,12.3mmol) and 30ml toluene are added, the reaction is heated at 100 ℃, the solution gradually turns to reddish brown, after 9h, the heating is stopped, ethyl acetate is extracted, anhydrous sodium sulfate is dried, concentration and column chromatography (petroleum ether: ethyl acetate 10: 1) are carried out, and orange-red oily liquid (1.3g, 99%) is obtained.

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃) δ 7.87(d, J ═ 9.4Hz,2H),7.18(m,3H),6.62(s,2H),4.65(s,1H),3.37(t, J ═ 7.1Hz,2H),1.87 to 1.64(m,2H),1.54 to 1.25(m,6H),0.98(t, J ═ 6.6Hz,3H), nuclear magnetic resonance carbon spectrum:¹³C NMR(101MHz,CDCl₃) δ 158.65,142.11,128.49,127.26,124.58,100.85,45.16,31.72,29.91,26.84,22.75,14.18. low resolution mass spectrum: MS (ESI) M/z 228.2[ M + H ]]⁺High resolution mass spectrometry: HRMS (ESI) M/z [ M + H ]]⁺Calculated values: c₁₆H₂₂228.1747, found: 228.1747.

1.2 azulene isatin (4a)

A50 ml Schlenk tube was taken, nitrogen gas was purged three times, oxalyl chloride (62. mu.L, 0.73mmol) and 10ml dichloromethane were added, the mixture was placed in an ice-water bath, a 10ml dichloromethane solution of 3(138.8mg,0.61mmol) was slowly added dropwise thereto, the solution turned yellow first and gradually turned green-black, after 30min, a 0.5ml dichloromethane solution of triethylamine (0.38ml,4.5eq) was slowly added dropwise thereto, white smoke was generated in the reaction tube, the reaction was allowed to react at room temperature for 10 hours, then water was added thereto to quench the reaction, dichloromethane was extracted, dried over anhydrous sodium sulfate, concentrated, and column-chromatographed (petroleum ether: ethyl acetate: 3: 1) to obtain an orange-red solid (53mg, 31%).

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃) δ 8.54-8.47 (m,1H),8.12(d, J ═ 9.0Hz,1H), 7.62-7.42 (m,3H),6.49(s,1H),3.73(t, J ═ 7.2Hz,2H), 1.90-1.66 (m,2H), 1.47-1.16 (m,6H),0.88(t, J ═ 6.9Hz,3H), nuclear magnetic resonance carbon spectrum:¹³C NMR(101MHz,CDCl₃) δ 174.2,165.4,162.7,153.0,138.6,136.3,135.5,133.3,133.1,132.8,110.5,98.8,42.1,31.5,28.1,26.6,22.6,14.1. low resolution mass spectrometry: MS (ESI) M/z 282.0[ M + H ]]⁺High resolution mass spectrometry: HRMS (ESI) M/z [ M + H ]]⁺Calculated values: c₁₈H₂₀O₂282.1489, found: 282.1488.

1.3 azulene isoindigo (1a)

A dry Schlenk tube was taken, 4(0.445g,1.58mmol) was added, and N was replaced by suction₂After three times, the mixture was dissolved in 25ml of toluene, lawson's reagent (0.320g,0.79mmol) was added under nitrogen protection, the reaction was heated at 60 ℃ to gradually turn blue-black, and after 1 hour, the TLC assay starting material disappeared, heating was stopped, and column chromatography was performed directly (petroleum ether: ethyl acetate 15: 1) to obtain a blue-black solid (122mg, 29%).

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃) δ 8.22(d, J ═ 10.2Hz,2H),7.91(d, J ═ 9.4Hz,2H),7.37(t, J ═ 9.7Hz,2H),7.29 to 7.14(m,4H),6.59(s,2H),3.86(t, J ═ 7.2Hz,4H),1.86 to 1.76(m,4H),1.50 to 1.17(m,12H),0.88(t, J ═ 6.9Hz,6H), nuclear magnetic resonance carbon spectrum:¹³C NMR(101MHz,CDCl₃) δ 172.28,156.42,151.41,135.01,134.54,134.12,132.28,128.64,126.90,121.19,117.57,97.61,41.89,31.67,28.56,26.82,22.66,14.16. low resolution mass spectrometry: MS (MALDI) M/z 530.1[ M ]]⁺High resolution mass spectrometry: HRMS (MALDI) M/z [ M]⁺Calculated values: c₃₆H₃₈O₂N₂530.2928, found: 530.2942. elemental analysis: the molecular formula is as follows: c₃₆H₃₈N₂O₂(ii) a Calculated values: c, 81.47; h, 7.22; n,5.28. found: c, 81.18; h, 7.28; n, 5.11.

1.4, N- (2-hexyl-1-decyl) -2-aminoazulene (3b)

The synthesis was performed as in example 1, step 1.1, using 2-hexyl-1-decylamine instead of n-hexylamine, with a yield of 99%.

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ7.83(d,J＝9.3Hz,2H),7.19–7.08(m,3H),6.61(s,1H),4.68(s,1H),3.29(d,J＝6.1Hz,2H),1.72–1.69(m,1H),1.51–1.07(m,24H),0.92(t,J＝6.6Hz,6H).

1.5 azulene isatin (4b)

N- (2-hexyl-1-decyl) -2-aminoazulene (3b) was used instead of N-hexyl-2-aminoazulene (3a), and was synthesized in the same manner as in example 1, step 1.2 with a yield of 20%.

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ8.55–8.46(m,1H),8.11(d,J＝9.1Hz,1H),7.62–7.45(m,3H),6.46(s,1H),3.61(d,J＝7.1Hz,2H),1.95–1.92(m,1H),1.47–1.13(m,24H),0.85(t,J＝6.7Hz,6H).

1.6 azulene isoindigo (1b)

The synthesis was performed as in step 1.2 of example 1, using azulene isatin (4b) instead of azulene isatin (4a), in 17% yield.

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ8.19(d,J＝10.1Hz,2H),7.90(d,J＝9.3Hz,2H),7.35(t,J＝9.7Hz,2H),7.22(t,J＝9.9Hz,2H),7.18(t,J＝9.7Hz,2H),6.56(s,2H),3.74(d,J＝7.2Hz,4H),2.05–1.96(m,2H),1.48–1.12(m,48H),0.89–0.79(m,12H).

example Synthesis of 23, 3' -bis (thien 2-yl) azulene isoindigo (6)

2.1, 3' -dibromoazulene isoindigo (5)

Weighing 1b (118mg, 0.15mmol) and sodium acetate (24mg, 0.29mmol) into a 25ml sealed tube, adding 5ml dichloromethane under nitrogen protection for dissolution, cooling in ice bath, adding N-bromosuccinimide (NBS) (52mg, 0.29mmol), slowly raising the reaction liquid to room temperature, and after 12h, directly carrying out column chromatography (petroleum ether: dichloromethane ═ 3: 1) to obtain a blue-black solid (106mg, 76%).

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ8.04(t,J＝10.5Hz,4H),7.43(t,J＝9.8Hz,2H),7.45–7.34(m,4H),3.99(d,J＝7.6Hz,4H),2.17–2.08(m,2H),1.45–1.17(m,48H),0.89–0.82(m,12H).

2.2, 3' -bis (thien 2-yl) azulene isoindigo (6)

Compound 5(61mg, 0.063mmol), 2-thiopheneboronic acid (32mg, 0.25mmol), tris (dibenzylideneacetone) dipalladium (3mg,0.0031mmol), Sphos (6mg, 0.016mmol) and K were weighed out₂CO₃(53mg, 0.38mmol) to 50mL lock. 6mL of a mixture of deoxygenated tetrahydrofuran and water (5:1) was added under nitrogen. Then the temperature is increased to 80 ℃, and the reflux reaction is carried out for 5 hours under the condition of pipe sealing. After the reaction is finished, a small amount of water and dichloromethane are addedAlkane extraction, combined organic phases, spin-dried and column chromatographed (petroleum ether: dichloromethane ═ 2:1) to afford a blue-black oily liquid (52mg, 84%).

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ8.12(d,J＝10.2Hz,2H),7.83(d,J＝9.5Hz,2H),7.48(d,J＝5.2Hz,2H),7.37(t,J＝9.7Hz,2H),7.23–7.08(m,8H),3.74(d,J＝7.5Hz,4H),1.51–1.40(m,2H),1.34–0.93(m,48H),0.88–0.82(m,12H).

example 3 Synthesis of example Polymer P1

Compounds 5(49mg, 0.05mmol), 7(21mg, 0.05mmol), tris (dibenzylideneacetone) dipalladium (1.4mg,0.0015mmol), Sphos (3.1mg, 0.0075mmol) and K were weighed out₂CO₃(41mg, 0.3mmol) to 10mL lock. 1.8mL of a mixture of deoxygenated tetrahydrofuran and water (5:1) was added under nitrogen. Then the temperature is increased to 110 ℃, and the reaction is carried out for 24 hours under the condition of tube sealing and refluxing. The solution was thickened, cooled to room temperature, the reaction was dropped into 200mL of methanol, filtered, extracted with a Soxhlet extractor and the dichloromethane phase gave a dark green polymer (23mg, 47%).

Gel permeation chromatography: mn: 8287, PDI: 1.55.

example 43 Synthesis of 3, 3' -dibromoisatin (8)

Weighing 4b (84mg, 0.30mmol) into a 25ml sealed tube, adding 5ml dichloromethane under nitrogen protection for dissolution, cooling in ice bath, adding N-bromosuccinimide (53mg, 0.30mmol), slowly raising the reaction solution to room temperature, after 5h, directly carrying out column chromatography (petroleum ether: ethyl acetate 3: 1) to obtain a red solid (100mg, 93%).

Hydrogen nuclear magnetic resonance spectroscopy:¹H NMR(400MHz,CDCl₃):δ8.51(d,J＝9.3Hz,1H),8.28–8.16(m,1H),7.69–7.48(m,3H),3.98(t,J＝7.6Hz,2H),1.81(p,J＝7.5Hz,2H),1.49–1.21(m,6H),0.89(t,J＝7.0Hz,3H).

effect example 1 ultraviolet absorption Spectroscopy and electrochemical Properties of Compound 1a

Ultraviolet absorption spectroscopy is carried out on a U-3900 spectrometer, and the sample solution is chloroform (the molar concentration is 2 multiplied by 10)^{- 5}M), the scanning range is 1000-300nm, and the optical band gap of the compound is calculated by the following formula:

E_gap ^opt＝1240nm/λ_onset (1)

the cyclic voltammetry test was performed on a computer-controlled CHI610D electrochemical analyzer using a conventional three-electrode test system with a platinum electrode as the working electrode, a Saturated Calomel Electrode (SCE) as the reference electrode, a platinum wire as the counter electrode, and a sample dissolved in freshly evaporated dichloromethane (molar concentration 1X 10^-3M)，Bu₄NPF₆(0.1M) as a supporting electrolyte, the scanning speed is 100mV/s, the saturated calomel is used as a reference, the saturated calomel energy level is-4.36 eV relative to the vacuum energy level, and the HOMO and LUMO energy levels of the material can be calculated by the following formula:

HOMO/LUMO＝–4.36–E_red1 ^1/2/E_ox1 ^1/2 (2)

FIG. 1 shows an ultraviolet-visible absorption spectrum of compound 1a, wherein the initial absorption peak is located at about 774nm, and the optical band gap is 1.60eV as calculated by formula (1). FIG. 2 is a cyclic voltammogram of compound 1a, from which the HOMO and LUMO energy levels of compound 1a can be calculated to be-4.89 eV and-3.38 eV, respectively, according to the cyclic voltammogram and equation (2).

Effect example 2 detection of trifluoroacetic acid in organic solvent by Compound 1a as responsive Material

FIG. 3 is a graph showing the visible color change of trifluoroacetic acid detected by using compound 1a as a responsive material. The operation process comprises the following steps: dissolving the compound 1a in a dichloromethane solution, wherein the solution is blue; when 3% by volume of trifluoroacetic acid was added thereto, a grayish green color of the solution was clearly observed; after triethylamine was added to neutralize the trifluoroacetic acid, the solution returned to the original color. FIG. 4 is the NMR spectrum of compound 1a before protonation, after protonation and neutralization with alkali, which shows that compound 1a has reversible proton response, can be reused and reduces cost.

Effect example 3 gel permeation chromatography testing of Polymer P1

FIG. 5 is a gel permeation chromatography test chart of Polymer P1. The gel permeation chromatography test method comprises the following steps: normal temperature gel permeation chromatograph, chloroform as eluting agent. The polymer P1 was found to have a number average molecular weight of 8287, a weight average molecular weight of 12884, a peak molecular weight of 9508 and a polydispersity index of 1.55.

The compounds in the present application (taking compound 1a as an example) have the following advantages over the compounds reported in the prior literature:

(1) the compounds of the present application show more pronounced color change under acidic conditions

Compound 1a in the present application changes from blue to grayish green under acidic conditions in Effect example 2 (see FIG. 3 for details), and(Hou, B.et al.acta Chim.Sinica 2020,78,788-796.) turns purple under acidic conditions under the same conditions (see FIG. 6 for details). It is understood that the compounds of the present application are related toHas more obvious color development effect.

(2) The compounds of the present application have a more sensitive proton response

Reported in the literature (Gao, H.et al. ACS Macro Lett.2019,8,1360-Saturation is achieved with 5% to 10% by volume trifluoroacetic acid, whereas the protonation state of compound 1a in this application is saturated with 3% by volume trifluoroacetic acid. In contrast, the compounds of the present application have a more sensitive proton response effect.

(3) The compounds in the present application have better redox behaviour

Relative to the reports in the literature (Lu, Y.et al.chem.Asian J.2017,12,302-307.)Compound 1a in the present application has a better redox potential.

Relative to the literature (Li, C.et al. org. chem. Front.2018,5, 442-446)Compound 1a in the present application has a better redox potential.