# US 10,870,655 B2 · Indacen-4-one derivatives, process for their preparation and polymers containing them

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- Number: US 10,870,655 B2
- Document ID: US10870655B2
- Status: Granted
- Kind: B2
- Application number: 15/573,865
- Filed: 2016-05-16
- Published: 2018-08-30
- Granted: 2020-12-22
- Earliest claimed: 2015-05-14
- Assignees: ENI S.p.A.
- Applicants: Eni S.p.A.
- Inventors: Riccardo Po; Gabriele Bianchi
- Web page: https://patentgrep.com/patent/US10870655B2

## CPC

- C07D 495/04: Ortho-condensed systems
- C08G 61/124: {with a five-membered ring containing one nitrogen atom in the ring}
- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- C08G 2261/11: Homopolymers
- C08G 2261/122: statistical
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3243: containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
- C08G 2261/3246: containing nitrogen and sulfur as heteroatoms
- C08G 2261/514: Electron transport
- C08G 2261/91: Photovoltaic applications
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/50: Photovoltaic [PV] devices
- H10K 85/215: {comprising substituents, e.g. PCBM}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Indacen-4-one derivative having general formula (I) in which: —W and W1, which are the same or different, preferably the same, represent an oxygen atom; a sulfur atom; an N—R3 group in which R3 represents a hydrogen atom, or is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups; —Z and Y, which are the same or different, preferably the same, represent a nitrogen atom; or a C—R4 group in which R4 represents a hydrogen atom, or is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, linear or branched C1-C20, preferably C2-C10, alkoxyl groups, R5—O—[CH2—CH2—O]n— polyethyleneoxyl groups in which R5 is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups, and n is an integer ranging from 1 to 4; —R6—OR7 groups in which R6 is selected from linear or branched C1-C20, preferably C2-C10, alkylene groups and R7 represents a hydrogen atom or is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups, or is selected from R5—[—OCH2—CH2—]n— polyethyleneoxyl groups in which R5 has the same meanings as above reported and n is an integer ranging from 1 to 4, —COR8 groups in which R8 is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups, —COOR9 groups in which R9 is selected from linear or branched C1-C20, preferably C2-C10, alkyl groups, or represent a —CHO group, or a cyano group (—CN); —R1 and R2, which are the same or different, preferably the same, are selected from linear or branched C1-C10, preferably C2-C10, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, linear or branched C1-C20, preferably C2-C10, alkoxyl groups, R5—O—[CH2—CH2—O]n— polyethyleneoxyl groups in which R5 has the same meanings as above reported and n is an integer ranging from 1 to 4, —R6—OR7 groups in which R6 and R7 have the same meanings as above reported, —COR8 groups in which R8 has the same meanings as above reported, —COOR9 groups in which R9 has the same meanings as above reported, or represent a —CHO group, or a cyano group (—CN). Said indacen-4-one derivative may advantageously be used in the synthesis of electron-donor polymers, said polymers being a further object of the present invention. Said polymers may advantageously be used in the construction of photovoltaic devices (or solar devices) such as, for example, photovoltaic cells (or solar cells), photovoltaic modules (or solar modules), on either a rigid or flexible support.

## Claims

### Claim 1

Process for the preparation of an indacen-4-one derivative having general formula (I):
in which:
W and W1, which are the same or different, represent an oxygen atom; a sulfur atom; an N—R3 group in which R3 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups;
Z and Y, which are the same or different, represent a nitrogen atom; or a C—R4 group in which R4 represents a hydrogen atom, or is selected from groups including linear or branched C1-C20 alkyl groups; optionally substituted cycloalkyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, linear or branched C1-C20 alkoxyl groups, R5—O—[CH2—CH2—O]n— polyethyleneoxyl groups in which R5 is selected from linear or branched C1-C20 alkyl groups, and n is an integer ranging from 1 to 4, —R6—OR7 groups in which R6 is selected from linear or branched C1-C20 alkylene groups and R7 represents a hydrogen atom or is selected from linear or branched C1-C20 alkyl groups, or is selected from groups including R5—[OCH2—CH2—]n— polyethyleneoxyl groups in which R5 has the same meanings as listed above and n is an integer ranging from 1 to 4, —COR8 groups in which R8 is selected from linear or branched C1-C20 alkyl groups, —COOR9 groups in which R9 is selected from linear or branched C1-C20 alkyl groups; or represent a —CHO group, or a cyano group (—CN); and
R1 and R2 represent a linear or branched C1-C20 alkyl group, comprising the following stages:
(a) causing at least one heteroaryl compound incorporating a terminal alkyne group having general formula (II):
in which W and Z have the same meanings as listed above, to react with at least one halogenated heteroaryl compound having general formula (III):
in which W1 and Y have the same meanings as listed above and X represents a halogen atom to obtain a compound having general formula (IV):
in which W, Z, W1 and Y have the same meanings as listed above;
(b) causing at least one compound having general formula (IV) obtained in stage (a) to react in the presence of at least one palladium-containing catalyst and of at least one copper-containing catalyst to obtain a compound having general formula (V):
in which W, Z, W1 and Y have the same meanings as listed above;
(c) causing at least one compound having general formula (V) obtained in stage (b) to react with at least one iron salt to obtain a compound having general formula (VI):
in which W, Z, W1 and Y have the same meanings as listed above;
(d) causing at least one compound having general formula (VI) obtained in stage (c) to react with at least one alkyl-magnesium bromide having general formula (VII):
R—MgBr (VII)
in which R represents a linear or branched C1-C20 alkyl group, to obtain a compound having general formula (VIII):
in which R, W, Z, W1 and Y have the same meanings as listed above;
(e) causing at least one compound having general formula (VIII) obtained in stage (d) to react with at least one strong organic acid, to obtain a indacen-4-one derivative having general formula (I).

### Claim 2 (depends on 1)

Process according to claim 1, in which:
in said stage (a) said heteroaryl compound containing a terminal alkyne group having general formula (II) and said halogenated heteroaryl compound having general formula (III), are used in molar ratios ranging from 1:2 to 1:10; and/or
said stage (a) is carried out in the presence of at least one palladium-containing catalyst selected from compounds of palladium in oxidation state (0) or (II) including: palladium(II)chloride [PdCl2], palladium(II)acetate [Pd(OAc)2], tris(dibenzylidene)dipalladium(0) [Pd2(dba)3 where dba=C6H5CH═CHCOCH═CHC6H5], bis(acetonitrile)palladium(II)chloride [Pd(CH3CN)2Cl2], bis(triphenylphosphine)palladium(II)chloride [Pd(PPh3)2Cl2], bis(triphenylphosphine)palladium(II)acetate [Pd(PPh3)2(OAc)2], tetrakis-(triphenylphosphine)palladium(0) [Pd(PPh3)4], or mixtures thereof; and/or
in said stage (a) said halogenated heteroaryl compound having general formula (III) and said palladium-containing catalyst are used in molar ratios ranging from 100:0.1 to 100:8; and/or
said stage (a) is carried out in the presence of a catalyst containing copper in oxidation state (I) selected from compounds including copper iodide (CuI), copper(I)chloride (CuCl), and copper(I)bromide (CuBr); and/or
in said stage (a) said halogenated heteroaryl compound having general formula (III) and said catalyst containing copper in oxidation state (I) are used in molar ratios ranging from 100:0.5 to 100:20; and/or
said stage (a) is carried out in the presence of at least one dipolar aprotic organic solvent selected from compounds including: triethylamine, N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), or mixtures thereof; and/or
in said stage (a) said halogenated heteroaryl compound having general formula (III) is used in said dipolar aprotic organic solvent at a molar concentration ranging from 0.05 mmol/ml to 2 mmol/ml; and/or
said stage (a) is carried out at a temperature ranging from 40° C. to 130° C.; and/or
said stage (a) is carried out for a time ranging from 30 minutes to 12 hours.

### Claim 3 (depends on 1)

A process according to claim 1, in which:
the palladium-containing catalyst used in said stage (b) is selected from compounds of palladium in oxidation state (II) including palladium(II)chloride [PdCl2], palladium(II)acetate [Pd(OAc)2], palladium(II)bromide [PdBr2], bis-(acetonitrile)palladium(II)chloride [Pd(CH3CN)2Cl2], bis(triphenylphosphine)-palladium(II)chloride [Pd(PPh3)2Cl2], bis(triphenylphosphine)palladium(II)-acetate [Pd (PPh3)2(OAc)2], or mixtures thereof; and/or
in said stage (b) said compound having general formula (IV) and said palladium-containing catalyst are used in molar ratios ranging from 100:0.1 to 100:8; and/or
the copper-containing catalyst used in stage (b) is selected from copper compounds in oxidation state (II) including copper(II)chloride [CuCl2], copper-(II)bromide [CuBr2], and copper(II)acetate [Cu(OAc)2]; and/or
in said stage (b) said compound having general formula (IV) and said copper-containing catalyst are used in molar ratios ranging from 100:0.5 to 100:20; and/or
said stage (b) is carried out in the presence of at least one dipolar aprotic organic solvent selected from compounds including: N,N-dimethylacetamide (DMAc), dimethyl-sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), or mixtures thereof; and/or
in said stage (b) said compound having general formula (IV) is used in said dipolar aprotic organic solvent at a molar concentration ranging from 0.05 mmol/l to 2 mmol/l; and/or
said stage (b) is carried out at a temperature ranging from 60° C. to 140° C.; and/or
said stage (b) is carried out for a time ranging from 30 minutes to 12 hours.

### Claim 4 (depends on 1)

Process according to claim 1, in which:
the iron salt used in said stage (c) is selected from compounds of iron in oxidation state (III) including iron(III)chloride [FeCl3], iron(III)bromide [FeBr3], iron(III)nitrate [Fe(NO3)3], and iron(III)sulfate [Fe2(SO4)3]; and/or
in said stage (c) said compound having general formula (V) and said iron salt are used in molar ratios ranging from 1:1 to 1:10; and/or
said stage (c) is carried out in the presence of at least one apolar organic solvent selected from compounds including: dichloromethane (DCM), chloroform (CHCl3), chlorobenzene (CB), dichlorobenzene (DCB), or mixtures thereof; and/or
in said stage (c) said compound having general formula (V) is used in said apolar organic solvent at a molar concentration ranging from 0.05 mmol/l to 2 mmol/l and/or
said stage (c) is carried out at a temperature ranging from 15° C. to 60° C.; and/or
said stage (c) is carried out for a time ranging from 30 minutes to 12 hours.

### Claim 5 (depends on 1)

Process according to claim 1, in which:
in said stage (d), said compound having general formula (VI) and said alkyl-magnesium bromide having general formula (VII) are used in molar ratios ranging from 1:0.5 to 1:10; and/or
said stage (d) is carried out in the presence of at least one apolar organic solvent selected from compounds including: tetrahydrofuran (THF), diethyl ether, dioxane, or mixtures thereof; and/or
in said stage (d) said compound having general formula (VI) is used in said apolar organic solvent at a molar concentration ranging from 0.01 mmol/l to 2 mmol/l; and/or
said stage (d) is carried out at a temperature ranging from −20° C. to 30° C.; and/or
said stage (d) is carried out for a time ranging from 30 minutes to 12 hours.

### Claim 6 (depends on 3)

Process according to claim 3, in which:
the strong organic acid used in said stage (e) is selected from compounds including:
para-toluenesulfonic acid (p-TsOH), 2-naphthalenesulfonic acid, methanesulfonic acid, or mixtures thereof; and/or
in said stage (e) said compound having general formula (VIII) and said strong organic acid are used in molar ratios ranging from 1:0.1 to 1:1; and/or
said stage (e) is carried out in the presence of at least one apolar organic solvent selected from compounds including: tetrahydrofuran (THF), diethyl ether, dioxane, toluene or mixtures thereof; and/or
in said stage (e) said compound having general formula (VIII) is used in said apolar organic solvent at a molar concentration ranging from 0.01 mmol/l to 2 mmol/l; and/or
said stage (e) is carried out at a temperature ranging from 80° C. to 170° C.; and/or
said stage (e) is carried out for a time ranging from 10 minutes to 3 hours.