STRONGLY FLUORESCENT HETEROCYCLES AND A METHOD FOR THEIR SYNTHESIS

Abstract

This invention provides 1,4-dihydropyrrolo[3,2-b]pyrrole derivatives which can be used as strongly fluorescent compounds and a one-stage method for their synthesis from simple substrates.

Description

This invention provides the novel electron-rich heterocycles possessing unique structure and properties, which can be used as strongly fluorescent compounds and the one-stage method of their synthesis from simple substrates.

There is a requirement for new strongly fluorescent materials, due to the development of fluorometric techniques and intensification of their use in modern biomedical techniques and in diagnostics (e.g. optical imaging). Moreover the development of compounds, which display high fluorescent quantum yields is particularly desirable.

Under such circumstances, invented 1,4-dihydropyrrolo[3,2-b]pyrroles, which possess superb optical properties, have the potential to be molecule of choice for above applications.

The subject mater of invention is a compound of formula (I):

wherein R¹, R² and R³ each independently stands for hydrogen or optionally substituted: alkyl, aryl, arylethynylaryl or heteroaryl, with the exception of the compound of formula (I) wherein R¹═R²═R³═H.

The term “aryl” means, unless otherwise stated, unsubstituted benzene, naphthalene, fluorene, 9,9-dialkylfluorene, or anthracene as well as benzene ring possessing the following substituents in ortho, meta or para positions: CN, CO₂Me, CO₂Et, SO₃H, CHO, CONH₂, F, Cl, Br, I, NO₂, OMe, OCH₂O, NH₂, NMe₂, SF₅.

The term “heteroaryl” refers to five-membered or six-membered aromatic ring that contain at least one heteroatom selected from N, O, S and Se. Examples of heteroaryl groups include pyridine, furan, pyrrole, thiophene, oxazole, imidazole, thiazole, pyrimidine.

The term “arylethynylaryl” refers to two benzene rings linked by carbon-carbon triple bond, possessing such substituents as: NO₂, CN, OMe, SO₂Me, SO₃H, F, Cl, Br, I, CHO, COOH, CONH₂, SF₅.

The term “alkyl” by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain with general formula: C₁H_2n+1 e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.

Preferably, R³ is hydrogen atom. Also preferably, R¹ and R², each independently, are aryl or heteroaryl substituents.

Especially preferably, R¹ and R² are derivatives of benzene, optionally substituted in ortho, meta, para position with a member selected from: NO₂, CN, OMe, SO₂Me, SO₃H, F, Cl, Br, I, CHO, COOH, CONH₂.

Preferably, compounds according to the invention have general formula (II):

wherein Ar¹ and Ar² each independently stands for optionally substituted: aryl or heteroaryl, as defined above.

Preferably, compounds according to the invention have general formula III or IV:

wherein Ar¹, Ar² and Ar³ each independently stands for optionally substituted: aryl or heteroaryl, as defined above.

Preferably, compounds according to the invention have general formula V:

wherein Ar² and Ar⁴ each independently stands for optionally substituted: aryl or heteroaryl, as defined above.

Preferably, the compound according to the invention is selected from the group consisting of: compounds 1-15, compounds 16-26 (i.e. compound possessing general formula II), compounds 27-34 (i.e. compounds possessing general formulas III or IV) and compounds 35-39 (i.e. compound possessing general formula V), which have been enumerated and depicted below:

• 2,5-diphenyl-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (1),
• 1,2,4,5-tetra(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (2),
• 2,5-di(naphthalen-1-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (3),
• 2,5-di(anthracen-9-yl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (4),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (5),
• 2,5-bis(3-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (6),
• 2,5-bis(2-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (7),
• 1,4-bis(4-bromophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (8),
• 2,5-bis(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (9),
• 2,5-bis(benzo[d][1,3]dioxol-5-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (10),
• 1,4-bis(4-chlorophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (11),
• 2,5-bis(4-fluorophenyl)-1,4-bis(4-methoxyphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (12),
• 1,4-bis(4-nitrophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (13),
• 2,5-bis(3-nitrophenyl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (14),
• 2,5-di(pyridin-3-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (15),
• 1,4-bis(4-methylphenyl)-2,5-bis(4-((trimethylsilyl)ethynyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (16),
• 2,5-bis(2-bromophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (17),
• 2,5-bis(2-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (18),
• 2,5-bis(2-(allyloxy)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (19),
• 1,4-bis(4-methylphenyl)-2,5-bis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (20),
• 1,2,4,5-tetrakis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (21),
• 1,4-bis(4-bromophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (22),
• 2,5-bis(4-bromo-2-nitrophenyl)-1,4-bis(4-hexylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (23),
• 2,5-bis(benzo[b]thiophen-2-yl)-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (24),
• 2,5-di(benzofuran-2-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (25),
• 1,4-bis(4-methylphenyl)-2,5-bis(thiazol-2-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (26),
• 2,5-bis(4-cyanophenyl)-3-(9,9-dioctyl-9H-fluoren-3-yl)-1,4-bis(4-methylphenyl)-dihydropyrrolo[3,2-b]pyrrole (27),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole (28),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole (29),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (30),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (31),
• 2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-di(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (32),
• 2,3,5-tris(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (33),
• 2,5-bis(4-cyanophenyl)-3-(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (34),
• 2,5-bis(4-(4-cyanoethynylphenyl)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (35),
• 2,5-bis(4-(4-pentafluorothiophenyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrole (36),
• 2,5-bis(4-(4-trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (37),
• 2,5-bis(4-(3,5-di(trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (38),
• 2,5-bis(4-(methoxy)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (39).

The next subject of the invention is the method of synthesis compound of formula (II):

wherein Ar¹ and Ar² are substituents selected from aryl or heteroaryl. General procedure involves reaction of butane-2,3-dione with arylaldehyde with formula Ar¹CHO and arylamine with formula Ar²NH₂ in acidic conditions. Further isolation leads to compound II.

Preferably, the reaction is performed in acetic acid, particularly in glacial acetic acid. Further, the reaction may be carried out at temperature above 50° C. in particular around 100° C. Compound with a formula II precipitates from reaction mixture and further filtration affords pure product.

Preferably, the reaction is performed in the presence of Brønsted acid as catalyst, especially Brønsted acid with pK_a<2, in particular arylsulfonic acid, especially such as p-toluenosulfonic acid or benzenesulfonic acid. Further, the reaction may be carried out at room temperature or under heating, e.g. at a temperature of 50° C.-110° C. Compound with a formula (II) precipitates from reaction mixture and further filtration affords pure product.

This synthetic methodology has significant advantage over previous one. The yields of products are significantly (1.3-3) higher than without catalyst. This is especially pronounced if Ar¹ possess ortho substituents (entries 4, 5, 6).

			yield[b]	yield[c]
entry	Ar1	Ar2	[%]	[%]
1			30	37
2			28	34
3			21	35
4			35	49
5			29	45
6			26	45
7			8	23
8			14	26
9			15	22
10			34	34
[a]cat.-pTsOH, benzenesulfonic acid
[b]isolated yield without catalyst.
[c]isolated yield after addition of catalyst to the reaction mixture.

The most characteristic feature of compounds synthesized according to the present invention is a strong absorption of UV and visible-light in range violet to greenish-blue. Their color oscillates between colorless, through yellow and orange to red (FIG. 1). Compounds of the invention, which possess electron-donating groups and halogens, are colorless. Moreover, all of synthesized compounds are fluorescent and they emit blue or violet light both in a solution and (what is very rare) in solid state. Few exceptions from this rule are compounds possessing NO₂ group, which quenches fluorescence. However they possess very intense orange-red color in solid state, which makes them dyes. Moreover NO₂ group decrease solubility of a dye in water or in organic solvents. Consequently they can be used as pigments, which is preferable from the point of view of industrial uses. Compounds synthesized according to the present invention possess strong absorption of light in a range 280-520 nm (molar absorption coefficient is 10000-71000 units). It means that in a various practical applications, less substance can be used with the same final effect. However the most important is fact that fluorescence quantum yields are very high (usually above 50%). Detailed optical parameters (i.e. absorption maxima, emission maxima, molar absorption coefficient and fluorescence quantum yield) are shown in Table 1. All, the most characteristic examples are presented there. Compounds synthesized according to the present invention are characterized by their quadrupolic structure what may influence on high value of two photon cross section, thus may be applied in two-photon excited fluorescence (TPEF) microscopy.

Compounds of the invention may be obtained in a multicomponent reaction from simple substrates i.e. aldehydes, amines and diacetyl. Acetic acid, which serves as a solvent as well as precipitation of a product from reaction mixture, make this synthetic process is operationally simple, fast, economic and ecologic.

The following examples exemplify the invention without limiting it.

EXAMPLE 1

General Synthetic Method (Compound of Formula II)

A variant carried out without catalyst:

In a 25 ml round-bottom flask equipped with a reflux condenser and magnetic stirrer were placed 5 mL glacial acetic acid, butane-2,3-dione (1 mmol), arylamine (2 mmol), aldehyde (2 mmol). The resulting mixture was stirred at 100° C. for 3 h. Then reaction mixture was cooled to room temperature. Resulting precipitate was then filtered off and washed with cold glacial acetic acid. Recrystallization from AcOEt followed by drying under vacuum afforded pure product.

A variant carried out in presence of catalyst:

In a 25 ml round-bottom flask equipped with a reflux condenser and magnetic stirrer were placed 5 mL glacial acetic acid, butane-2,3-dione (1 mmol), arylamine (2 mmol), aldehyde (2 mmol) and p-toluenesulfonic acid (0.2 mmol). The resulting mixture was stirred at 100° C. for 3 h. Then reaction mixture was cooled to room temperature. Resulting precipitate was then filtered off and washed with cold glacial acetic acid. Recrystallization from AcOEt followed by drying under vacuum afforded pure product.

In examples 2-16 the syntheses of compounds 1-15 have been described.

EXAMPLE 2

2,5-diphenyl-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (1)

Beige solid. Yield 145 mg (33%).^[b] R_f=0.86 (SiO₂, AcOEt/hexanes, 1:4). Mp 239-244° C. (CH₃CO₂H). ¹H NMR (500 MHz, CDCl₃) δ 7.22 (AA‘XX’, 41-1), 7.21 (AA‘XX’, 41-1), 7.19-7.13 (m, 10H), 6.38 (s, 2H), 2.36 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) 6137.5, 135.7, 135.3, 133.8, 131.6, 129.6, 128.2, 128.1, 126.0, 125.0, 94.5, 21.0. HRMS (EI) calcd for C₃₂H₂₆N₂: 438.2096 [M⁺]. found: 438.2100. Anal. calcd for C₃₂H₂₆N₂: C, 87.64; H, 5.98; N, 6.39. found: C, 87.79; H, 5.97; N, 6.40. λ_abs (CH₃Cl, ε×10⁻³) 348 (33) nm.

EXAMPLE 3

1,2,4,5-tetra(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (2)

White solid. Yield 158 mg (34%)^[b,c] R_f=0.71 (SiO₂, AcOEt/hexanes, 1:4). Mp 261-262° C. (CH₃CO₂H). ¹H NMR (500 MHz, CDCl₃) δ 7.17 (AA‘XX’, 4H), 7.15 (AA‘XX’, 4H), 7.11 (AA‘XX’, 4H), 7.02 (AA‘XX’, 4H), 6.33 (s, 2H), 2.36 (s, 6H), 2.30 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 137.7, 135.7, 135.6, 135.1, 131.3, 131.0, 129.6, 128.8, 128.0, 125.0, 94.1, 21.1, 21.0. HRMS (EI) calcd for C₃₄H₃₀N₂: 466.2409 [M⁺]. found: 466.2406. Anal. calcd for C₃₄H₃₀N₂: C, 87.52; H, 6.48; N, 6.00. found: C, 87.47; H, 6.43; N, 5.94. λ_abs (CH₂Cl₂, ε×10⁻³) 348 (37) nm.

EXAMPLE 4

2,5-di(naphthalen-1-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (3)

Yellow solid. Yield 270 mg (50%).^[b] R_f=0.61 (SiO₂, AcOEt/hexanes, 1:2). Mp 249-252° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 8.26 (d, J=7.9 Hz, 2H), 7.84 (d, J=7.6 Hz, 2H), 7.77 (d, J=7.9 Hz, 2H), 7.46-7.32 (m, 8H), 7.10 (AA‘XX’, 4H), 6.95 (AA‘XX’, 4H), 6.55 (s, 2H), 2.23 (s, 6H). ¹³C NMR (500 MHz, CDCl₃) 6137.4, 134.6, 133.8, 132.9, 132.5, 131.7, 130.4, 129.4, 129.0, 128.0, 127.4, 126.6, 126.0, 125.7, 125.1, 123.9, 97.0, 20.9. HRMS (EI) calcd for C₄₀H₃₀N₂: 538.2409 [M⁺]. found: 538.2419. Anal. calcd for C₄₀H₃₀N₂: C, 89.19; H, 5.61; N, 5.20. found: C, 89.14; H, 5.70; N, 5.17. λ_abs (toluene, ε×10⁻³) 377 (14) nm.

EXAMPLE 5

2,5-di(anthracen-9-yl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (4)

Orange solid. Yield 93 mg (11%).^[b] R_f=0.74 (SiO₂, AcOEt/hexanes, 1:9). Mp 223-224° C. ¹H NMR (500 MHz, CDCl₃) δ 8.46 (s, 2H), 8.22-8.14 (m, 4H), 8.03-7.94 (m, 4H), 7.47-7.34 (m, 8H), 7.01 (AA‘XX’, 4H), 6.72 (AA‘XX’, 4H), 6.61 (s, 2H), 2.37-2.24 (m, 4H), 1.32-1.39 (m, 4H), 1.20-1.27 (m, 4H), 1.14-1.19 (m, 12H), 1.05-1.13 (m, 4H), 0.83 (t, J=7.1 Hz, 6H). ¹³C NMR (500 MHz, CDCl₃) δ 139.3, 137.6, 132.3, 131.3, 130.1, 130.0, 128.9, 128.5, 128.2, 127.4, 127.2, 125.7, 125.1, 122.9, 98.3, 35.1, 31.8, 31.0, 29.3, 29.2, 29.1, 22.6, 14.1. HRMS (EI) calcd for (C₆₂H₆₂N₂), 834.4913 [M⁺]. found, 834.4900. Anal. calcd for C₆₂H₆₂N₂: C, 89.16; H, 7.48; N, 3.35. Found: C, 89.15; H, 7.42; N, 3.29. λ_abs (toluene ε×10⁻³) 387 (35) nm.

EXAMPLE 6

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (5)

Yellow-green solid. Yield 180 mg (37%).^[c] R_f=0.65 (SiO₂, CH₂Cl₂). Mp 319-321° C. (AcOEt). ¹H NMR (600 MHz, CDCl₃) δ 7.47 (AA‘XX’, 4H), 7.27 (AA‘XX’, 4H), 7.21 (AA‘XX’, 4H), 7.14 (AA‘XX’, 4H), 6.45 (s, 2H), 2.40 (s, 6H); ¹³C NMR (150 MHz, CDCl₃) δ 137.7, 136.7, 136.5, 135.0, 133.4, 131.9, 130.1, 127.8, 125.2, 119.1, 109.0, 95.8, 21.1. HRMS (FD-TOF) calcd for C₃₄H₂₄N₄: 488.2001 [M⁺]. found: 488.2014. Anal. calcd for C₃₄H₂₄N₄: C, 83.58; H, 4.95; N, 11.47. found: C, 83.53; H, 4.97; N, 11.33. λ_abs (CH₂Cl₂, ε×10⁻³) 405 (54) nm.

EXAMPLE 7

2,5-bis(3-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (6)

Yellow solid. Yield 166 mg (34%).^[c] R_f=0.52 (SiO₂, AcOEt/hexanes, 1:2). Mp 314-316° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.51 (t, J=1.5 Hz, 2H), 7.42 (dd, J=7.6, 1.4 Hz, 2H), 7.40-7.36 (m, 2H), 7.20 (AA‘XX’, 4H), 7.13 (AA‘XX’, 4H), 6.41 (s, 2H), 2.40 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 136.6, 136.4, 134.7, 134.0, 132.5, 132.0, 131.0, 130.1, 129.4, 128.9, 125.1, 118.7, 112.4, 95.3, 21.1. HRMS (ESI) calcd for C₃₄H₂₄N₄: 488.2001 [M⁺]. found: 488.1999. Anal. calcd for C₃₄H₂₄N₄: C, 83.58; H, 4.95; N, 11.47. found: C, 83.73; H, 4.86; N, 11.45. λ_abs (CH₂Cl₂, ε×10⁻³) 368 (33) nm.

EXAMPLE 8

2,5-bis(2-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (7)

Yellow solid. Yield 23 mg (5%).^[b] R_f=0.37 (SiO₂, AcOEt/hexanes, 1:4). Mp 344-345° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.66 (dd, J=7.8, 1.1 Hz, 2H), 7.37 (dd, J=7.7, 1.3 Hz, 2H), 7.30-7.27 (m, 2H), 7.16-7.09 (m, 10H), 6.66 (s, 2H), 2.35 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 137.1, 136.6, 135.7, 133.7, 132.0, 131.9, 131.8, 131.1, 129.9, 126.7, 124.9, 118.8, 111.4, 97.2, 21.0. HRMS (EI) calcd for C₃₄H₂₄N₄: 488.1988 [M⁺]. found: 488.1989. Anal. calcd for C₃₄H₂₄N₄: C, 83.58; H, 4.95; N, 11.47. found: C, 83.50; H, 4.91; N, 11.54. λ_abs (toluene, ε×10⁻³) 388 (10) nm.

EXAMPLE 9

1,4-bis(4-bromophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (8)

White solid. Yield 133 mg (22%).^[c] R_f=0.71 (SiO₂, AcOEt/hexanes, 1:4). Mp 297-298° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.46 (AA‘XX’, 4H), 7.14 (AA‘XX’, 4H), 7.09 (AA‘XX’, 4H), 7.05 (AA‘XX’, 4H), 6.34 (s, 2H), 2.32 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 139.1, 136.3, 135.8, 132.2, 131.0, 130.3, 129.1, 128.2, 126.6, 118.9, 94.9, 21.2. HRMS (EI) calcd for C₃₂H₂₄Br₂N₂: 594.0306 [M⁺]. found: 594.0322. Anal. calcd for C₃₂H₂₄Br₂N₂: C, 64.45; H, 4.06; Br, 26.8; N, 4.7. found: C, 64.44; H, 4.15; Br, 26.75; N, 4.60. λ_abs (CHCl₃, ε×10⁻³) 304 (35), 348 (33) nm.

EXAMPLE 10

2,5-bis(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (9)

White solid. Yield 77 mg (15%).^[b] R_f=0.60 (SiO₂, AcOEt/hexanes, 1:2). Mp 241-242° C. (CH₃CO₂H). ¹H NMR (500 MHz, C₆D₆) δ 7.31 (AA‘XX’, 4H), 7.28 (AA‘XX’, 4H), 6.89 (AA‘XX’, 4H), 6.69 (AA‘XX’, 4H), 6.54 (s, 2H), 3.25 (s, 6H), 2.04 (s, 6H). ¹³C NMR (125 MHz, C₆D₆) δ 158.7, 138.6, 135.6, 135.0, 132.1, 130.0, 129.8, 125.6, 114.1, 94.8, 54.7, 20.8. HRMS (FD) calcd for C₃₄H₃₀N₂O₂: 498.2307 [M⁺]. found: 498.2307. Anal. calcd for C₃₄H₃₀N₂O₂: C, 81.90; H, 6.06; N, 5.62. found: C, 81.73; H, 5.87; N, 5.51. λ_abs (toluene, ε×10⁻³) 300 (27), 348 (36) nm.

EXAMPLE 11

2,5-bis(benzo[d][1,3]dioxol-5-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (10)

Colorless solid. Yield 137 mg (13%).^[b] R_f=0.66 (SiO₂, AcOEt/hexanes, 1:2). Mp 236-237° C. (AcOEt). ¹H NMR (500 MHz, C₆D₆) δ 7.23 (AA‘XX’, 4H), 6.92 (d, J=1.7 Hz, 2H), 6.87 (AA‘XX’, 4H), 6.81 (dd, J=8.1, 1.7 Hz, 2H), 6.56 (d, J=8.1 Hz, 2H), 6.43 (s, 2H), 5.23 (s, 4H), 2.02 (s, 6H). ¹³C NMR (125 MHz, C₆D₆) δ 148.0, 146.6, 138.4, 135.7, 135.2, 132.1, 130.0, 128.9, 125.5, 122.3, 109.2, 108.5, 100.9, 95.1, 20.8. HRMS (EI) calcd for C₃₄H₂₆N₂O₄: 526.1879 [M⁺]. found: 526.1882. Anal. calcd for C₃₄H₂₆N₂O₄: C, 77.55; H, 4.98; N, 5.32. found: C, 77.56; H, 4.94; N, 5.35. λ_abs (toluene, ε×10⁻³) 304 (23), 354 (37) nm.

EXAMPLE 12

1,4-bis(4-chlorophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (11)

Yellow solid. Yield 33 mg (6%).^[b] R_f=0.65 (SiO₂, AcOEt/hexanes, 1:2). Mp 324-325° C. (CH₃CO₂H). ¹H NMR (500 MHz, CDCl₃) δ 7.52 (AA‘XX’, 4H), 7.40 (AA‘XX’, 4H), 7.28 (AA‘XX’, 4H), 7.20 (AA‘XX’, 4H), 6.47 (s, 2H). ¹³C NMR (125 MHz, CDCl₃) δ 137.7, 137.1, 135.2, 133.1, 132.4, 132.2, 129.8, 128.0, 126.4, 118.8, 109.7, 96.5. HRMS (EI) calcd for C₃₂H₁₈Cl₂N₄: 528.0905 [M⁺]. found: 528.0905. Anal. calcd for C₃₂H₁₈Cl₂N₄: C, 72.60; H, 3.43; Cl, 13.39; N, 10.58. found: C, 72.50; H, 3.45; Cl, 13.37; N, 10.52. λ_abs (CHCl₃, ε×10⁻³) 399 (49) nm.

EXAMPLE 13

2,5-bis(4-fluorophenyl)-1,4-bis(4-methoxyphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (12)

Colorless solid. Yield 51 mg (7%).^[b] R_f=0.86 (SiO₂, AcOEt/hexanes, 1:2). Mp 261-263° C. (CH₃CO₂H). ¹H NMR (500 MHz, C₆D₆) δ 7.15 (AA‘XX’, 4H), 7.13 (AA‘XX’, 4H), 6.71 (AA‘XX’, 4H), 6.66 (AA‘XX’, 4H), 6.39 (s, 2H), 3.23 (s, 6H). ¹³C NMR (125 MHz, C₆D₆) δ 162.8, 160.9, 158.2, 135.1, 133.6, 132.6, 130.7, 130.6, 130.1, 130.0, 127.0, 115.5, 115.3, 114.7, 94.6, 54.9. HRMS (EI) calcd for C₃₂H₂₄F₂N₂O₂: 506.1806 [M⁺]. found: 506.1815. Anal. calcd for C₃₂H₂₄F₂N₂O₂: C, 75.88; H, 4.78; F, 7.50; N, 5.53. found: C, 76.04; H, 4.79; F, 7.53; N, 5.48. λ_abs (toluene, ε×10⁻³) 345 (34) nm.

EXAMPLE 14

1,4-bis(4-nitrophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (13)

Red solid. Yield 55 mg (11%).^[b] R_f=0.50 (SiO₂, AcOEt/hexanes, 1:2). Mp 317-319° C. (CH₃CO₂H). ¹H NMR (500 MHz, DMSO) δ 8.28 (AA‘XX’, 4H), 7.50 (AA‘XX’, 4H), 7.13-7.17 (m, 8H), 6.69 (s, 2H), 2.30 (s, 6H). HRMS (EI) calcd for C₃₂H₂₄N₄O₄: 528.1790 [M⁺]. found: 528.1798. Anal. calcd for C₃₂H₂₄N₄O₄: C, 72.72; H, 4.58; N, 10.60. found: C, 72.63; H, 4.44; N, 10.57. λ_abs (CHCl₃, ε×10⁻³) 360 (41) nm.

EXAMPLE 15

2,5-bis(3-nitrophenyl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (14)

The resulting orange solid was filtered off and washed with cooled glacial acetic acid. Column chromatography (AcOEt/hexanes, 1:2) and crystallization from AcOEt gave pure product (84 mg, 12%)^[b]. R_f=0.77 (SiO₂, AcOEt/hexanes, 1:9). Mp 193-194° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 8.14 (m, 2H), 7.97 (ddd, J=8.1, 2.3, 1.0 Hz, 2H), 7.42 (ddd, J=7.8, 1.7, 1.1 Hz, 2H), 7.33 (m, 2H), 7.22 (AA‘XX’, 4H), 7.18 (AA‘XX’, 4H), 6.50 (s, 2H), 2.69-2.60 (m, 4H), 1.70-1.59 (m, 4H), 1.40-1.20 (m, 20H), 0.89 (t, J=7.0 Hz, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 148.3, 141.6, 136.7, 135.1, 134.1, 133.4, 132.7, 129.5, 128.9, 125.3, 122.2, 120.6, 95.4, 35.5, 31.9, 31.3, 29.4, 29.3, 29.2, 22.7, 14.1. HRMS (EI) calcd for C₄₆H₅₂N₄O₄: 724.3989 [M⁺]. found: 724.3987. Anal. calcd for C₄₆H₅₂N₄O₄: C, 76.21; H, 7.23; N, 7.73. found: C, 76.21; H, 7.12; N, 7.74. λ_abs (CHCl₃, ε×10⁻³) 361 (39) nm.

EXAMPLE 16

2,5-di(pyridin-3-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (15)

Product didn't precipitate from reaction mixture. Acid was evaporated and residue was dissolved in Na₂CO_3(aq) and extracted three times with dichloromethane (30 ml). Organic layers were combined, dried over Na₂SO₄ and concentrated under reduced pressure. The residual oil was purified by flash column chromatography (SiO₂, CH₂Cl₂/MeOH, 95:5). Beige solid. Yield 10 mg (1%).^[b] R_f=0.41 (SiO₂, CH₂Cl₂/MeOH, 95:5). Mp. 216° C. (AcOEt, decomp.) ¹H NMR (500 MHz, CDCl₃) δ 8.55 (d, J=1.6 Hz, 2H), 8.37-8.40 (m, 2H), 7.45-7.48 (m, 2H), 7.14-7.23 (m, 10H), 6.43 (s, 2H), 2.39 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 147.8, 146.0, 136.6, 136.5, 135.5, 132.7, 132.5, 130.1, 130.0, 125.3, 123.2, 95.1, 21.0. LRMS (API) calcd for C₃₀H₂₄N₄: 441.2 [M+H⁺]. found: 441.5. λ_abs (CHCl₃, ε×10⁻³) 361 (47) nm.

In examples 17-27 the syntheses of compounds 16-26 have been described.

EXAMPLE 17

1,4-bis(4-methylphenyl)-2,5-bis(4-((trimethylsilyl)ethynyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (16)

Yellow solid. Yield 567 mg (15%).^[b] R_f=0.78 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 314-315° C. (toluene, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 7.26 (AA‘XX’, 4H), 7.14 (m, 12H), 6.36 (s, 2H), 2.37 (s, 6H), 0.23 (s, 18H); ¹³C NMR (125 MHz, CDCl₃) δ 137.5, 135.9, 130.0, 125.3, 21.2. HRMS (EI) calcd for C₄₂H₄₂N₂Si₂: 630.2905[M⁺]. found: 630.2905. λ_abs (CH₂Cl₂, ε×10⁻³) 393 (60) nm.

EXAMPLE 18

2,5-bis(2-bromophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (17)

Yellowish solid. Yield 291 mg (49%).^[c] R_f=0.68 (SiO₂, AcOEt/hexanes, 1:4). Mp 239-241° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.57 (dd, J=8.1, 1.1 Hz, 2H), 7.28 (dd, J=7.6, 1.7 Hz, 2H), 7.20 (dt, J=7.5, 1.1 Hz, 2H), 7.10 (m, 10H), 6.45 (s, 2H), 2.31 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 137.4, 135.1, 134.7, 133.4, 133.1, 133.0, 129.8, 129.5, 128.6, 126.9, 124.4, 124.0, 96.3, 20.9. HRMS (EI) calcd for C₃₂H₂₄N₂Br₂: 594.0306 [M⁺]. found: 594.0305. Anal. calcd for C₃₂H₂₄Br₂N₂: C, 64.45; H, 4.06; Br, 26.80; N, 4.70. found: C, 64.51; H, 4.24; Br, 26.78; N, 4.52. λ_abs (CH₂Cl₂, ε×10⁻³) 306 (19) nm, 333 (18) nm.

EXAMPLE 19

2,5-bis(2-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (18)

Beige solid. Yield 224 mg (45%).^[c] R_f=0.61 (SiO₂, AcOEt/hexanes, 1:4). Mp 286-289° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.31 (dd, J=7.4, 1.3 Hz, 2H), 7.23 (dt, J=8.8, 1.4 Hz, 2H), 7.13 (d, J=8.2 Hz, 4H), 7.06 (d, J=8.2 Hz, 4H), 6.92 (t, J=7.4 Hz, 2H), 6.75 (d, J=8.2 Hz, 2H), 6.37 (s, 2H), 3.37 (s, 6H), 2.31 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 156.8, 138.6, 134.1, 131.8, 131.6, 130.0, 129.1, 128.4, 123.7, 123.4, 120.5, 111.0, 95.0, 54.9, 20.9. HRMS (EI) calcd for C₃₄H₃₀N₂O₂: 498.2307 [M⁺]. found: 498.2309. Anal. calcd for C₃₄H₃₀N₂O₂: C, 81.90; H, 6.06; N, 5.62. found: C, 81.62; H, 6.28; N, 5.39. λ_abs (CH₂Cl₂, ε×10⁻³) 309 (23) nm, 338 (27) nm.

EXAMPLE 20

2,5-bis(2-(allyloxy)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (19)

Beige solid. Yield 248 mg (45%).^[c] R_f=0.65 (SiO₂, AcOEt/hexanes, 1:4). Mp 203-204° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.34 (dd, J=7.5, 1.7 Hz, 2H), 7.20 (dt, J=7.5, 1.7 Hz, 2H), 7.14 (d, J=8.2 Hz, 4H), 7.05 (d, J=8.2 Hz, 4H), 6.92 (dt, J=7.4, 0.6 Hz, 2H), 6.76 (d, J=8.2 Hz, 2H), 6.38 (s, 2H), 5.60 (m, 2H), 5.07 (m, 4H), 4.18 (m, 4H), 2.31 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 155.8, 138.7, 134.1, 133.8, 131.8, 130.1, 129.2, 128.3, 124.0, 123.3, 120.6, 116.8, 112.5 95.4, 68.9, 20.9. HRMS (EI) calcd for C₃₈H₃₄N₂O₂: 550.2620 [M⁺]. found: 550.2635. Anal. calcd for C₃₈H₃₄N₂O₂: C, 82.88; H, 6.22; N, 5.09. found: C, 83.05; H, 6.32; N, 5.09. λ_abs (CH₂Cl₂, ε×10⁻³) 308 (24) nm, 336 (28) nm.

EXAMPLE 21

1,4-bis(4-methylphenyl)-2,5-bis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (20)

Yellowish solid. Yield 241 mg (35%).^[c] R_f=0.70 (SiO₂, AcOEt/hexanes, 1:4). Mp 322-324° C. (AcOEt, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 7.57 (d, J=8.8 Hz, 4H), 7.23 (m, 8H), 7.16 (d, J=8.2 Hz, 4H), 6.43 (s, 2H), 2.41 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 136.9, 136.7, 136.4, 134.6, 133.0, 130.1, 127.3, 125.8, 125.2, 95.6, 21.0. HRMS (EI) calcd for C₃₂H₂₄F₁₀N₂S₂: 690.1221 [M⁺]. found: 690.1230. Anal. calcd for C₃₂H₂₄F₁₀N₂S₂: C, 55.65; H, 3.50; F, 27.51; N, 4.06; S, 9.29. found: C, 55.64; H, 3.50; N, 4.12; F, 27.41; S, 9.18. λ_abs (CH₂Cl₂, ε×10⁻³) 381 (41) nm.

EXAMPLE 22

1,2,4,5-tetrakis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (21)

Yellowish solid. Yield 238 mg (26%).^[c] R_f=0.67 (SiO₂, AcOEt/hexanes, 1:4). Mp 329-331° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.83 (d, J=8.2 Hz, 4H), 7.68 (d, J=8.2 Hz, 4H), 7.34 (d, J=8.1 Hz, 4H), 7.28 (d, J=8.1 Hz, 4H) 6.54 (s, 2H); ¹³C NMR (125 MHz, CDCl₃) δ 151.2, 141.7, 135.7, 134.8, 132.5, 127.7, 127.6, 126.4, 124.6, 97.9. HRMS (EI) calcd for C₃₀H₁₈F₂₀N₂S₄: 914.0034 [M⁺]. found: 914.0029. Anal. calcd for C₃₀H₁₈F₂₀N₂S₄: C, 39.39; H, 1.98; F, 41.54; N, 3.06; S, 14.02. found: C, 39.57; H, 2.06; F, 41.32; N, 3.09; S, 14.18. λ_abs (CH₂Cl₂, ε×10⁻³) 319 (23) nm, 376 (42) nm.

EXAMPLE 23

1,4-bis(4-bromophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (22)

Yellow solid. Yield 142 mg (23%).^[c] R_f=0.56 (SiO₂, AcOEt/hexanes, 1:4). Mp 351-353° C. (AcOEt, decomp.). ¹H NMR (500 MHz, CDCl₃,) δ 7.55 (dd, J=6.8, 1.9 Hz, 4H), 7.52 (dd, J=6.8, 1.9 Hz, 4H), 7.27 (dd, J=6.9, 2.0 Hz, 4H), 7.13 (dd, J=6.9, 2.0 Hz, 4H) 6.54 (s, 2H) ¹³C NMR (125 MHz, CDCl₃) δ 138.2, 137.1, 135.2, 133.1, 132.8, 132.2, 128.0, 126.8, 120.3, 118.9, 109.8, 96.6. HRMS (EI) calcd for C₃₂H₁₈N₄Br₂: 615.9898 [M⁺]. found: 615.9924. Anal. calcd for C₃₂H₁₈Br₂N₄: C, 62.16; H, 2.93; Br, 25.85; N, 9.06. found: C, 62.11; H, 3.03; Br, 25.94; N, 9.15. λ_abs (CH₂Cl₂, ε×10⁻³) 399 (50) nm.

EXAMPLE 24

2,5-bis(4-bromo-2-nitrophenyl)-1,4-bis(4-hexylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (23)

Purple solid. Yield 208 mg (25%).^[b] R_f=0.75 (SiO₂, CH₂Cl₂/hexanes, 1:1). ¹H NMR (500 MHz, CDCl₃) δ 7.86 (d, J=2.0 Hz, 2H), 7.59 (dd, J=8.3, 2.0 Hz, 2H), 7.28 (s, 2H), 7.11 (AA‘XX’, 4H), 7.07 (AA‘XX’, 4H), 6.32 (s, 2H), 2.66-2.52 (m, 4H), 1.60 (quin, J=14.5 Hz, 4H), 1.31 (s, 12H), 0.89 (t, J=6.8 Hz, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 149.2, 141.3, 136.1, 135.3, 134.2, 132.0, 129.9, 129.5, 127.3, 127.3, 124.7, 121.0, 95.7, 35.6, 31.8, 31.4, 29.0, 22.8, 14.2. HRMS (EI) calcd for C₄₂H₄₂Br₂N₄O₄: 824.1588 [M⁺]. found: 824.1589. Anal. calcd for C₄₂H₄₂Br₂N₄O₄: C, 61.03; H, 5.12; N, 6.78; Br, 19.33. found: C, 60.94; H, 5.20; N, 6.69; Br, 19.29.

EXAMPLE 25

2,5-bis(benzo[b]thiophen-2-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (24)

Purple solid. Yield 20 mg (4%).^[b] R_f=0.72 (SiO₂, AcOEt/hexanes, 4:6). ¹H NMR (500 MHz, CDCl₃) δ 7.69 (d, J=7.8, 2H), 7.54 (d, J=7.2 Hz, 2H), 7.34 (AA‘XX’, 4H), 7.26 (AA‘XX’, 4H), 7.23 (dd, J=4.4, 1.5 Hz; 2H), 7.21 (dd, J=7.1, 1.0 Hz, 2H), 6.77 (s, 2H), 6.45 (s, 2H), 2.44 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) 3140.3, 139.0, 136.9, 136.8, 135.8, 132.8, 130.2, 130.2, 130.0, 126.1, 124.2, 123.7, 123.1, 121.8, 120.2, 95.0, 21.2. HRMS (EI) calcd for C₃₆H₂₆N₂S₂: 550.1537 [M⁺]. found: 550.1551.

EXAMPLE 26

2,5-di(benzofuran-2-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (25)

Orange solid. Yield 78 mg (15%).^[b]1H NMR (500 MHz, CDCl₃) δ 7.41 (AA‘XX’, 4H), 7.36 (m, 4H), 7.32 (AA‘XX’, 4H), 7.18 (m, 2H), 7.13 (dd, J=7.6, 1.0 Hz, 2H), 6.68 (s, 2H), 5.96 (s, 2H), 2.49 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 153.9, 149.8, 137.4, 136.9, 133.5, 130.0, 129.2, 128.0, 126.4, 123.6, 122.7, 120.3, 110.6, 101.0, 93.7, 21.2. HRMS (ESI) calcd for C₃₆H₂₆N₂O₂: 518.1992 [M⁺]. found: 518.1992.

EXAMPLE 27

1,4-bis(4-methylphenyl)-2,5-bis(thiazol-2-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (26)

Yellow solid. Yield 45 mg (10%).^[b]1H NMR (500 MHz, CDCl₃) δ 7.67 (d, J=3.3 Hz, 2H), 7.31 (AA‘XX’, 4H), 7.27 (AA‘XX’, 4H), 7.08 (d, J=3.3 Hz, 2H), 6.77 (s, 2H), 2.44 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 160.0, 142.6, 137.8, 136.2, 133.8, 130.1, 127.0, 117.6, 95.8, 21.4. HRMS (ESI) calcd for C₂₆H₂₀N₄S₂: 452.1139 [M⁺]. found: 452.1129.

EXAMPLE 28

General procedure for the synthesis of arylated 1,4-dihydropyrrolo[3,2-b]pyrroles (27-34)

Parent 1,4-dihydropyrrolo[3,2-b]pyrrole (0.25 mmol), aryl bromide (1 mmol), KOAc (1 mmol) and PdCl(C₃H₅)(dppb) (0.01 mmol) were placed in a 25 ml Schlenk flask, which was flushed with Argon prior to use. Then 8 ml of dry DMA was added and resulting mixture was stirred at 150° C. for 3 days. Product was purified by means of flash column chromatography, and then recrystallized from toluene or ethyl acetate. Obtained crystals were dried under reduced pressure.

The examples 29-36 present synthetic results of applied procedure—compounds 27-34.

EXAMPLE 29

2,5-bis(4-cyanophenyl)-3-(9,9-dioctyl-9H-fluoren-3-yl)-1,4-bis(4-methylphenyl)-dihydropyrrolo[3,2-b]pyrrole (27)

Yellow solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/hexanes 1:1). Yield 66 mg (30%). R_f=0.66 (SiO₂, AcOEt/hexanes, 1:4). Mp 228-231° C. (toluene). ¹H NMR (500 MHz, CDCl₃) δ 7.62 (d, J=7.2 Hz 1H), 7.42 (AA‘XX’, 2H), 7.33 (m, 1H), 7.29 (m, 3H), 7.27 (m, 1H), 7.21 (m, 5H), 7.12 (AA‘XX’, 2H), 7.07 (d, J=8.4 Hz, 2H), 6.86 (s, 1H), 6.79 (s, 4H), 6.64 (dd, J=7.7, 1.3 Hz, 1H), 6.54 (s, 1H), 2.40 (s, 3H), 2.25 (s, 3H), 1.80 (m, 2H), 1.63 (m, 2H), 1.21 (m, 4H), 1.15 (m, 8H), 1.04 (m, 4H), 0.99 (m, 4H), 0.82 (t, J=7.0 Hz, 6H), 0.49 (quin, J=7.8 Hz, 4H). ¹³C NMR (125 MHz, CDCl₃) δ 150.7, 150.2, 140.9, 139.4, 137.8, 136.9, 136.2, 135.6, 131.9, 131.3, 130.8, 130.0, 129.2, 127.9, 127.1, 125.3, 122.8, 119.4, 118.6, 112.3, 109.0, 94.1, 54.8, 40.3, 31.8, 30.0, 29.5, 29.3, 23.7, 22.6, 21.0, 14.1. HRMS (ESI) calcd for C₆₃H₆₄N₄:876.5131 [M⁺]. found: 876.5124. Anal. calcd for C₆₃H₆₄N₄: C, 86.26; H, 7.35; N, 6.39. found: C, 86.02; H, 7.38; N, 6.30. λ_abs (CH₂Cl₂, ε×10⁻³) 404 (40) nm.

EXAMPLE 30

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole (28)

Orange solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/hexanes 1:1). Yield 36 mg (24%). R_f=0.51 (SiO₂, AcOEt/hexanes, 1:4). Mp 344-346° C. (toluene). ¹H NMR (500 MHz, CDCl₃) δ 7.80 (AA‘XX’, 2H), 7.44 (AA‘XX’, 2H), 7.39 (AA‘XX’, 2H), 7.20 (t, J=8.5 Hz, 4H), 7.08 (AA‘XX’, 2H), 7.03 (AA‘XX’, 2H), 6.95 (d, J=8.0 Hz, 2H), 6.84-6.81 (m, 2H), 6.51 (s, 1H), 2.40 (s, 3H), 2.34 (s, 3H). ¹³C NMR (125 MHz, CDCl₃) δ 145.8, 140.4, 138.0, 137.4, 136.9, 136.2, 136.1, 136.0, 135.9, 132.0, 131.9, 131.8, 131.1, 130.7, 130.1, 129.6, 128.0, 127.5, 125.5, 124.8, 122.7, 119.0, 118.6, 110.3, 109.4, 109.0, 94.5, 21.1, 21.0. HRMS (EI) calcd for C₄H₂₇N₅O₂: 609.2165 [M⁺]. found: 609.2184. λ_abs (CH₂Cl₂, ε×10⁻³) 393 (40) nm.

EXAMPLE 31

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole (29)

Orange solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/hexanes 2:1) Yield 97 mg (53%). R_f=0.42 (SiO₂, AcOEt/hexanes, 1:4). ¹H NMR (500 MHz, CDCl₃) δ 7.79 (d, 4H), 7.35 (d, 4H), 6.98 (d, 4H), 6.91 (d, 4H), 6.82 (d, 4H), 6.77 (d, 4H), 2.32 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 145.8, 140.0, 138.2, 135.8, 135.2, 133.3, 131.8, 131.4, 131.0, 129.5, 129.2, 127.6, 124.8, 122.8, 118.5, 110.6, 108.0, 21.1. HRMS (EI) calcd for C₄₆H₃₀N₆O₄ [M⁺]=730.2329. found [M⁺]=730.2345. Anal. calcd for C₄₆H₃₀N₆O₄: C, 75.60; H, 4.14; N, 11.50 found: C, 75.56; H, 4.20; N, 11.41. λ_abs (CH₂Cl₂, ε×10⁻³) 381 (45) nm.

EXAMPLE 32

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis(4-(pentafluoro-λ⁶-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (30)

Yellow-greenish solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/hexanes 1:1-3:1). Yield 78 mg (35%). R_f=0.56 (SiO₂, AcOEt/hexanes, 1:4). ¹H NMR (500 MHz, CDCl₃) δ 7.36 (AA‘XX’, 4H), 7.30 (AA‘XX’, 4H), 7.01 (AA‘XX’, 4H), 6.86 (d, J=8.0 Hz, 4H), 6.78 (d, J=8.5 Hz, 4H), 6.70 (AA‘XX’, 4H), 2.29 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 137.8, 136.7, 135.9, 135.2, 132.3, 131.8, 131.1, 130.4, 129.5, 129.4, 127.4, 125.2, 125.1, 118.7, 110.2, 108.0, 20.8. HRMS (EI) calcd for C₄₆H₃₀N₄F₁₀S₂: 892.1752 [M+]. found: 892.1734. λ_abs (CH₂Cl₂, ε×10⁻³) 395 (33) nm.

EXAMPLE 33

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (31)

Yellow solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/MeOH 95:5). Yield 30 mg (21%). R_f=0.71 (SiO₂, CH₂Cl₂/MeOH, 95:5). Mp 319-320° C. (toluene, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 8.34 (d, J=2.0 Hz, 1H), 8.02 (s, 1H), 7.43 (d, J=7.8 Hz, 2H), 7.36 (d, J=7.8 Hz, 2H) 7.20 (m, 4H), 7.09 (d, J=7.6 Hz, 2H), 7.01 (m, 3H), 6.91 (m, 3H), 6.80 (d, J=7.5 Hz, 2H), 6.52 (s, 1H), 2.39 (s, 3H), 2.31 (s, 3H). ¹³C NMR (125 MHz, CDCl₃) δ 150.0, 147.0, 137.9, 137.6, 137.5, 136.6, 136.3, 136.2, 136.0, 135.6, 132.1, 131.9, 131.8, 131.7, 131.3, 131.0, 130.1, 129.6, 129.3, 127.9, 127.3, 125.4, 122.4, 119.0, 118.8, 109.9, 109.2, 107.2, 94.5, 21.1, 21.0. HRMS (EI) calcd for C₃₉H₂₇N₅: 565.2266 [M⁺]. found: 565.2280. λ_abs (CH₂Cl₂, ε×10⁻³) 395 (33) nm.

EXAMPLE 34

2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-di(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole (32)

Yellow solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/MeOH 95:5). Yield 76 mg (47%). R_f=0.55 (SiO₂, CH₂Cl₂/MeOH, 95:5). Mp 345-347° C. (toluene, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 8.33 (d, J=3.0 Hz, 2H), 8.01 (s, 2H), 7.32 (d, J=8.2 Hz, 4H), 7.01 (d, J=7.6 Hz, 2H), 6.97 (d, J=8.2 Hz, 4H), 6.89 (m, 6H), 6.75 (d, J=8.0 Hz, 4H), 2.31 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 151.0, 147.0, 137.8, 137.6, 136.1, 135.1, 133.1, 131.7, 131.2, 129.5, 129.4, 129.2, 127.4, 122.5, 118.7, 110.1, 106.1, 21.1. HRMS (EI) calcd for C₄₄H₃₀N₆: 642.2532 [M+]. found: 642.2521. λ_abs (CH₂Cl₂, ε×10⁻³) 396 (36) nm.

EXAMPLE 35

2,3,5-tris(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (33)

Yellow solid. Product was purified by means of flash column chromatography (SiO₂, CH₂Cl₂/hexanes 1:1-3:1). Yield 71 mg (48%). R_f=0.41 (SiO₂, AcOEt/hexanes, 1:4). Mp 325-326° C. (toluene). ¹H NMR (500 MHz, CDCl₃) δ 7.43 (d, J=8.2 Hz, 2H), 7.38 (d, J=8.2 Hz, 2H), 7.20 (m, 6H), 7.07 (d, J=8.1 Hz, 2H), 7.00 (d, J=8.2 Hz, 2H), 6.94 (d, J=7.9 Hz, 2H), 6.79 (m, 4H), 2.39 (s, 3H), 2.36 (s, 3H). ¹³C NMR (125 MHz, CDCl₃) δ 138.3, 137.8, 136.8, 136.3, 136.1, 136.0, 135.9, 131.9, 131.8, 131.7, 131.2, 131.1, 130.7, 130.1, 129.5, 128.0, 127.4, 125.4, 119.0, 118.7, 110.1, 109.5, 109.4, 109.3, 94.5, 21.1, 21.0. HRMS (EI) calcd for C₄₁H₂₇N₅: 589.2266 [M⁺]. found: 589.2259. Anal. calcd for C₄₁H₂₇N₅: C, 83.51; H, 4.62; N, 11.88. found: C, 83.47; H, 4.63; N, 11.72. λ_abs (CH₂Cl₂, ε×10⁻³) 400 (43) nm.

EXAMPLE 36

2,5-bis(4-cyanophenyl)-3-(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (34)

Yellow solid. Product was purified by means of flash column chromatography (SiO₂, AcOEt/hexanes 1:4). Yield 50 mg (34%). R_f=0.45 (SiO₂, AcOEt/hexanes, 1:4). Mp 298-300° C. (toluene). ¹H NMR (500 MHz, CDCl₃) δ 7.42 (d, J=8.3 Hz, 2H), 7.33 (d, J=8.3 Hz, 2H), 7.20 (d, J=8.3 Hz, 2H), 7.17 (d, J=8.3 Hz, 2H), 7.08 (d, J=8.1 Hz, 2H), 7.03 (d, J=8.2 Hz, 2H), 6.89 (d, J=8.0 Hz, 2H), 6.78 (d, J=8.1 Hz, 2H), 6.62 (d, J=8.5 Hz, 2H), 6.52 (d, J=6.8 Hz, 2H), 6.51 (s, 1H), 3.75 (s, 3H), 2.39 (s, 3H), 2.32 (s, 3H). ¹³C NMR (125 MHz, CDCl₃) δ 158.1, 137.8, 137.1, 136.8, 136.7, 136.1, 135.8, 135.6, 131.9, 131.7, 131.7, 131.6, 131.4, 130.9, 130.0, 129.2, 127.9, 127.3, 125.3, 125.0, 113.1, 111.3, 109.1, 108.9, 94.6, 55.2, 21.1, 21.0. HRMS (EI) calcd for C₄₁H₃₀N₄O: 594.2420 [M⁺]. found: 594.2430. λ_abs (CH₂Cl₂, ε×10⁻³) 400 (43) nm.

EXAMPLE 37

General procedure for the synthesis of 2,5-bis(arylethynyl)-1,4-bis(aryl)-1,4-dihydropyrrolo[3,2-b]pyrroles (35-39)

An oven-dried 25 ml Schlenk flask was charged with 1,4-bis(4-methylphenyl)-2,5-bis(4-((trimethylsilyl)ethynyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (16, 20 mg, 3.17×10⁻⁵ mol), PdCl₂(PPh₃)₂ (2.2 mg, 3.17×10⁻⁶ mol), CuI (0.6 mg, 3.17×10⁻⁶ mol) and bromo- or iodoarene (6.317×10⁻⁵ mol). Then anhydrous THF (0.5 ml) was added, followed by Et₃N (0.5 ml, 3.6 mmol). Reaction mixture were deoxygenated by freeze-pump-thaw cycles and purged with argon. TBAF (21 mg, 7.92×10⁻⁶ mol) was added, and the reaction mixture was stirred for 16 h at room temperature under argon atmosphere. The crude mixture was filtered through celite and the solvent was distilled off. Purification using DCVC method afforded pure product.

The examples 38-42 present synthetic results of applied procedure—compounds 35-39.

EXAMPLE 38

2,5-bis(4-(4-cyanophenylethynyl)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (35)

Product was purified by means of DCVC method (SiO₂, hexanes/CH₂Cl₂, 4:1) afforded pure product as a yellow solid, 12 mg (56%). R_f=0.27 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 313-314° C. (AcOEt, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 7.61 (AA‘XX’, 4H), 7.57 (AA‘XX’, 4H), 7.38 (AA‘XX’, 4H), 7.21 (AA‘XX’, 4H), 7.19 (m, 8H), 6.42 (s, 2H), 2.39 (s, 6H); ¹³C NMR (125 MHz, CDCl₃) δ 137.5, 136.1, 135.7, 134.5, 132.9, 132.2, 132.1, 131.8, 130.1, 128.5, 127.9, 125.4, 119.6, 118.6, 111.5, 95.2, 88.5, 21.2. HRMS (EI) calcd for C₅₀H₃₂N₄: 688.2627 [M⁺]. found: 688.2596. λ_abs (CH₂Cl₂, ε×10⁻³) 428 (70) nm.

EXAMPLE 39

2,5-bis(4-(4-pentafluorothiophenyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (36)

Purification using DCVC method (SiO₂, hexanes/CH₂Cl₂, 4:1) afforded pure product as a yellow solid, 6 mg (21%). R_f=0.72 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 207-208° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.65 (AA‘XX’, 4H), 7.48 (AA‘XX’, 4H), 7.33 (AA‘XX’, 4H), 7.14 (AA‘XX’, 4H), 7.13-7.08 (m, 8H), 6.36 (s, 2H), 2.32 (s, 6H); ¹³C NMR (125 MHz, CDCl₃) δ 137.3, 135.9, 135.5, 134.2, 132.6, 131.6, 131.5, 129.9, 127.7, 127.1, 126.0, 125.2, 119.5, 95.0, 92.7, 87.9, 29.7, 21.0. HRMS (EI) calcd for C₄₈H₃₂F₁₀N₂S₂: 890.1847[M⁺]. found: 890.1843. λ_abs (CH₂Cl₂, ε×10⁻³) 418 (45) nm.

EXAMPLE 40

2,5-bis(4-(4-trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (37)

Purification using DCVC method (SiO₂, hexanes/CH₂Cl₂, 6:1) afforded pure product as a orange solid, 4 mg (15%). R_f=0.76 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 347-348° C. (AcOEt, decomp.). ¹H NMR (500 MHz, CDCl₃) δ 7.59 (s, 8H), 7.39 (AA‘XX’, 4H), 7.19 (m, 12H), 6.42 (s, 2H), 2.38 (s, 6H). ¹³C NMR (125 MHz, CDCl₃) δ 137.5, 136.0, 131.9, 130.1, 125.4, 125.4, 21.2. HRMS (EI) calcd for C₅₀H₃₂F₆N₂: 774.2470 [M⁺]. found: 774.2461. λ_abs (CH₂Cl₂, ε×10⁻³) 414 (62) nm.

EXAMPLE 41

2,5-bis(4-(3,5-di(trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (38)

Purification using DCVC method (SiO₂, hexanes/CH₂Cl₂, 8:1) afforded pure product as a yellow solid, 10 mg (33%). R_f=0.78 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 316-317° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.92 (s, 4H), 7.80 (s, 2H), 7.40 (AA‘XX’, 4H), 7.23 (AA‘XX’, 4H), 7.20 (m, 8H), 6.45 (s, 2H), 2.39 (s, 6H); ¹³C NMR (125 MHz, CDCl₃) δ 137.4, 136.1, 134.6, 132.9, 132.2, 132.0, 131.8, 131.4, 130.1, 127.9, 125.9, 125.3, 124.2, 122.0, 119.1, 95.2, 93.3, 87.0, 21.2. HRMS (EI) calcd for C₅₂H₃₀F₁₂N₂: 910.2215 [M⁺]. found: 910.2188. λ_abs (CH₂Cl₂, ε×10⁻³) 421 (67) nm.

EXAMPLE 42

2,5-bis(4-(methoxy)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole (39)

Purification using DCVC method (SiO₂, hexanes/CH₂Cl₂, 3:1) afforded pure product as a yellow solid, 7 mg (30%). R_f=0.44 (SiO₂, hexanes/CH₂Cl₂, 1:1). Mp 315-316° C. (AcOEt). ¹H NMR (500 MHz, CDCl₃) δ 7.44 (AA‘XX’, 4H), 7.35 (AA‘XX’, 4H), 7.18 (s, 12H), 6.87 (AA‘XX’, 4H), 6.40 (s, 2H), 3.82 (s, 6H), 2.38 (s, 6H); ¹³C NMR (125 MHz, CDCl₃) δ 159.7, 137.5, 135.8, 133.1, 131.3, 123.0, 129.2, 128.4, 127.8, 125.5, 125.3, 114.1, 55.5, 21.2. HRMS (EI) calcd for C₅₀H₃₈N₂O₂: 698.2933 [M⁺]. found: 698.2955. λ_abs (CH₂Cl₂, ε×10⁻³) 401 (71) nm.

EXAMPLE 43

Optical Properties of Compounds Synthesized According to the Present Invention

Optical measurements were performed for compounds synthesized according to the present invention. For this purpose each compound was dissolved in CH₂Cl₂, unless otherwise noted, and absorption spectra were measured. The same solutions were exposed to monochromatic light with wavelength 325-345 nm and emission spectra were measured. Comparison with reference spectrum (quinine bisulfate (VI) in H₂SO₄, 0.5 M) gave the fluorescence quantum yield coefficient. All the measurements were performed at room temperature. Results are shown in Table 1.

TABLE 1
Spectroscopic properties of selected compounds.
			Stokes	Molar absorption	Fluorescence
	λabs	λem	Shift	coefficient	quantum yield
Cpd	[nm]	[nm]	[cm−1]	εmax [M−1 cm−1]	Φfl
2	348	410	4300	37 000	0.37
3	377	443	4000	14 000	0.51
5	405	459	3000	54 000	0.24
6	368	462	5500	33 000	0.17
9[a]	348	412	4500	36 000	0.52
11	400	455	3000	49 000	0.78
12	345	400	4000	34 000	0.57
13	360	—	—	41 000	—
19	336	414	5600	28 000	0.62
22	399	454	3000	50 000	0.86
27	404	472	3600	40 000	0.57
29	381	—	—	45 000	—
30	395	463	3700	33 000	0.63
32	396	465	3800	36 000	0.64
33	400	474	3900	43 000	0.48
35	428	549	5200	70 000	0.22
36	418	523	4800	45 000	0.16
37	414	511	4600	62 000	0.42
38	421	522	4600	67 000	0.37
39	401	479	4100	71 000	0.53
[a]spectra measured in toluene

FIG. 1 shows fluorescence of selected compounds in solutions.

EXAMPLE 44

Electrochemical Properties of Compound According to the Invention

Electrochemistry of two compounds (19 and 32) has been studied via cyclic voltammetry (Table 2, FIG. 2-3). It was shown that some of these compounds have interesting behavior such as low oxidation potential and large HOMO-LUMO gap. This can be advantageous in such applications as bulk-heterojunction solar cells, organic field-effect transistors etc.

TABLE 2
Electrochemical data for compounds 19 and 32 vs. Fc/Fc+).
	E1/2ox1 [V]	E1/2ox2 [V]	E1/2red [V]	HOMO-LUMO gap [eV]
19	−0.01	0.62	−1.46	1.45
32	0.32 V	−1.46	1.78

FIG. 2 shows a cyclic voltammetry for compound 19 and FIG. 3 the cyclic voltammetry for compound 32.

Claims

1. A compound of formula (I):

2. A compound according to claim 1, wherein R3 stands for H.

3. A compound according to claim 2, wherein R1 and R2 each independently stands for aryl or heteroaryl group.

4. A compound according to claim 2, wherein R1 and R2 each independently stands for derivatives of benzene, optionally substituted in ortho, meta or para position with a substituent selected from the group NO2, CN, OMe, SO2Me, SO3H, F, Cl, Br, I, CHO, COOH, CONH2 or SF5.

5. A compound according to claim 1, possessing general formula (II):

6. A compound according to claim 1, possessing general formula III or IV:

7. A compound according to claim 1, possessing general formula V:

8. A compound according to claim 1, selected from the group consisting of: 2,5-diphenyl-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,2,4,5-tetra(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-di(naphthalen-1-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-di(anthracen-9-yl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(3-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(2-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-bromophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(benzo[d][1,3]dioxol-5-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-chlorophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-fluorophenyl)-1,4-bis(4-methoxyphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-nitrophenyl)-2,5-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(3-nitrophenyl)-1,4-bis(4-octylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-di(pyridin-3-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-methylphenyl)-2,5-bis(4-((trimethylsilyl)ethynyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(2-bromophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(2-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(2-(allyloxy)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-methylphenyl)-2,5-bis(4-(pentafluoro-λ6-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,2,4,5-tetrakis(4-(pentafluoro-λ6-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-bromophenyl)-2,5-bis(4-cyanophenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-bromo-2-nitrophenyl)-1,4-bis(4-hexylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(benzo[b]thiophen-2-yl)-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-di(benzofuran-2-yl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,1,4-bis(4-methylphenyl)-2,5-bis(thiazol-2-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-3-(9,9-dioctyl-9H-fluoren-3-yl)-1,4-bis(4-methylphenyl)-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis-(4-nitrophenyl)-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-bis(4-(pentafluoro-λ6-sulfanyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3-(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-1,4-bis(4-methylphenyl)-3,6-di(pyridin-3-yl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,3,5-tris(4-cyanophenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-cyanophenyl)-3-(4-methoxyphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-(4-cyanoethynylphenyl)phenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-(4-pentafluorothiophenyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrole,2,5-bis(4-(4-trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-(3,5-di(trifluoromethyl)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole,2,5-bis(4-(methoxy)ethynylphenyl)-1,4-bis(4-methylphenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole.

9. A process for the preparation of compound of formula (II):

10. A process according to claim 9, wherein the reaction is carried out in an acetic acid, possibly glacial acetic acid.

11. A process according to claim 9, wherein the reaction is carried out in temperature above 50° C., possibly around 100° C.

12. A process according to claim 9, wherein the compound of formula (II) is precipitated from cooled reaction mixture.

13. A process according to claim 9, wherein the reaction is performed in the presence of Brønsted acid as catalyst.

14. A process according to claim 9, wherein the reaction is performed in the presence of acid with pKa<2, especially arylsulfonic acid, in particular such as p-toluenosulfonic acid or benzenesulfonic acid, as catalyst.