NOVEL HETEROCYCLIC FLUORESCENT DYES AND METHOD OF PRODUCTION THEREOF

Abstract

The invention relates to novel compounds of formula (III) that can be used as heterocyclic dyes of unique structure and properties. These compounds can be obtained in a three-step synthesis from simple substrates. The compounds according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the compounds according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

##STR00001##

Claims

1-19. (canceled)

20. A compound of formula ##STR00138## ##STR00139## ##STR00140## ##STR00141## R.sup.3 is hydrogen, halogen; cyano, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms; C.sub.1-C.sub.25alkyl ##STR00142## wherein R.sup.22 to R.sup.25 and R.sup.29 to R.sup.33 represent independently of each other H, F, cyano, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms; or C.sub.1-C.sub.25alkyl, and R.sup.26 is H, F, cyano, phenyl, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, or C.sub.1-C.sub.25alkyl; R.sup.99, R.sup.99, R.sup.99 and R.sup.99* are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, or C.sub.1-C.sub.25alkyl interrupted by one or more oxygen atoms; preferably C.sub.3-C.sub.25alkyl, or C.sub.3-C.sub.25alkyl which is interrupted by one or more oxygen atoms; R.sup.121, R.sup.122, R.sup.123, R.sup.124 and R.sup.125 are independently of each other hydrogen, halogen, C.sub.1-C.sub.18alkoxy or C.sub.1-C.sub.25alkyl; preferably hydrogen; and R.sup.130 is hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, halogen; or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more halogen atoms; or C.sub.7-C.sub.25arylalkyl.

21. The compound of claim 20, wherein the compound is according formula IN-1.

22. The compound of claim 20, wherein the compound is according formula IN-2.

23. The compound of claim 20, wherein the compound is according formula IN-3.

24. The compound of claim 20, wherein the compound is according formula IN-4.

25. The compound of claim 20, wherein the compound is according formula IN-5.

26. The compound of claim 20, wherein the compound is according formula IN-6.

27. The compound of claim 20, wherein the compound is according formula IN-7.

28. The compound of claim 20, wherein the compound is according formula IN-8.

29. The compound of claim 20, wherein the compound is according formula IN-9.

30. The compound of claim 20, wherein the compound is according formula IN-10.

31. The compound of claim 20, wherein the compound is according formula IN-11.

32. The compound of claim 20, wherein the compound is according formula IN-12.

33. The compound of claim 20, wherein the compound is according formula IN-13.

34. The compound of claim 20, wherein the compound is according formula IN-14.

35. The compound of claim 20, wherein the compound is according formula IN-15.

36. The compound of claim 20, wherein the compound is according formula IN-16.

37. The compound of claim 20, wherein the compound is according formula IN-17.

Description

EXAMPLES

Example 1

1. Synthesis of 1,4-Diketo-3,6-di(3,4-dimethoxyphenyl)pyrrolo[3,4-c]pyrrole (1a)

[0182] ##STR00102##

[0183] A three-necked flask equipped with a reflux condenser and magnetic stirrer is charged with 40 ml of tert-amyl alcohol, 1.15 g of sodium (50 mmol) and a catalytic amount of iron(III) chloride. The mixture is heated at the boiling point until the sodium has reacted completely. Then the reaction mixture is cooled to 90 C. and 23 mmol of nitrile is added with a syringe (solid nitriles should be dissolved beforehand in a small amount of tert-amyl alcohol). The mixture is heated to 110 C. and 2.1 ml (10 mmol) of diisopropyl succinate is added dropwise in the space of 30 min. After reaction at 110 C. for 16 h, the flask contents are cooled and 100 ml of a mixture of water, methanol and acetic acid in volumetric proportions 1:1:1 is added. The suspension obtained is heated for some minutes at the boiling point and then cooled to 30 C. The precipitate is filtered off, washed several times with hot water and methanol and dried under reduced pressure.

[0184] Yield: 736 mg (18%). Red powder. M.p.: Decomposition>370 C. .sup.1H-NMR (500 MHz, DMSO-d.sub.6, 80 C.): 10.84 (s, 2H), 8.18 (d, J=2.0 Hz, 2H), 8.10 (dd, J.sub.1=2.0 Hz, J.sub.2=8.4 Hz, 2H), 7.11 (d, J=8.4 Hz, 2H), 3.88 (s, 6H)), 3.86 (s, 6H). .sup.13C-NMR (125 MHz, DMSO-d.sub.6): 163.0, 152.5, 149.7, 143.7, 122.4, 121.5, 112.8, 112.4, 109.9, 56.5, 56.4. HRMS (EI 70 eV) calc. for C.sub.22H.sub.20N.sub.2O.sub.6 (M.sup.+): 408.1321. found: 408.1316. Calc. elem. anal. (%) for the formula C.sub.22H.sub.20N.sub.2O.sub.6: C, 64.70, H, 4.94, N, 6.86. found: C, 64.64, H, 4.99, N, 6.62.

2. General Method of Synthesis of Diketones 2a, 2b and 2c

[0185] ##STR00103##

[0186] A mixture of pigment 1a (1.0 mmol), tetrabutylammonium bisulfate (TBAHS, 17 mg, 0.05 mmol), potassium carbonate (2.07 g, 15 mmol) and 25 ml of DMF is heated to 120 C. under an argon atmosphere. Then a given amount of -bromoketone is added dropwise by a syringe (30 min). The reaction mixture is stirred for 2 h, cooled and diluted with water and methylene chloride. The aqueous layer is extracted with methylene chloride, combined organic layers are washed with water and brine and dried over sodium sulfate. Solvents are evaporated, the product is separated by the column chromatography in the given eluting system.

##STR00104##

2,5-Bis(2-oxo-2-phenylethyl)-1,4-diketo-3,6-bis(3,4-dimethoxyphenyl)pyrrolo[3,4-c]pyrrole (2a)

[0187] Prepared from 1a (408 mg, 1.0 mmol). -Bromoketone used: phenacyl bromide (1.99 g, 10.0 mmol) which is dissolved in 4 ml of DMF prior to use. Purified by the column chromatography (methylene chloride:acetone 49:1.fwdarw.19:1) and recrystallized from CHCl.sub.3/EtOH. Yield: 191 mg (30%). Orange solid. Mp: Decomposition >250 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 8.03-7.96 (m, 4H), 7.66-7.59 (m, 2H), 7.54-7.45 (m, 6H), 7.28 (dd, J=8.5, 2.1 Hz, 2H), 6.87 (d, J=8.5 Hz, 2H), 5.28 (s, 4H), 3.88 (s, 6H), 3.81 (s, 6H). .sup.13C NMR (126 MHz, CDCl.sub.3) ( 193.6, 162.6, 151.6, 149.1, 148.0, 134.7, 134.0, 128.9, 128.1, 121.7, 120.6, 112.1, 111.1, 109.2, 56.0 (2 signals), 48.9. HRMS (ESI) calcd for C.sub.38H.sub.32N.sub.2O.sub.3Na (M+Na.sup.+): 667.2051. found: 667.2062.

##STR00105##

2,5-Bis(3,3-dimethyl-2-oxobutyl)-1,4-diketo-3,6-bis(3,4-dimethoxyphenyl)pyrrolo[3,4-c]pyrrole (2b)

[0188] Prepared from 1a (408 mg, 1.0 mmol). -Bromoketone used: 1-bromo-3,3-dimethylbutan-2-one (0.67 ml, 5.0 mmol). Purified by the column chromatography (methylene chloride:acetone 49:1.fwdarw.19:1) and recrystallized from CHCl.sub.3/pentane. Yield: 210 mg (35%). Red powder. Mp: 203-204 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.38 (d, J=2.0 Hz, 2H), 7.19 (dd, J=8.4, 2.1 Hz, 2H), 6.91 (d, J=8.5 Hz, 2H), 4.75 (s, 4H), 3.92 (s, 6H), 3.91 (s, 6H), 1.19 (s, 18H). .sup.13C NMR (126 MHz, CDCl.sub.3) 209.3, 162.5, 151.5, 149.2, 148.1, 121.8, 120.7, 112.0, 111.0, 109.2, 56.2, 56.0, 47.1, 43.4, 26.4. HRMS (ESI) calcd for C.sub.34H.sub.40N.sub.2O.sub.3Na (M+Na.sup.+): 627.2682. found: 627.2678.

##STR00106##

2,5-Bis(2-oxo-2-(3-methoxyphenyl)ethyl)-1,4-diketo-3,6-bis(3,4-dimethoxyphenyl)-pyrrolo[3,4-c]pyrrole (2c)

[0189] Prepared from 1a (408 mg, 1.0 mmol). -Bromoketone used: 3-methoxyphenacyl bromide (2.29 g, 10.0 mmol) which is dissolved in 4 ml of DMF prior to use. Purified by the column chromatography (methylene chloride:acetone 19:1) and recrystallized from CHCl.sub.3/MeOH. Yield: 417 mg (59%). Orange solid. Mp: 232-224 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.56 (d, J=8.1 Hz, 2H), 7.51 (d, J=2.0 Hz, 2H), 7.50 (dd, J=2.4, 1.6 Hz, 2H), 7.40 (t, J=8.0 Hz, 2H), 7.30-7.25 (m, 2H), 7.16 (ddd, J=8.3, 2.6, 0.8 Hz, 2H), 6.87 (d, J=8.5 Hz, 2H), 5.27 (s, 4H), 3.89 (s, 6H), 3.85 (s, 6H), 3.83 (s, 6H). .sup.13C NMR (126 MHz, CDCl.sub.3) 193.4, 162.6, 160.0, 151.6, 149.1, 148.0, 135.9, 130.0, 121.6, 120.6 (2 signals), 120.5, 112.3, 112.1, 111.1, 109.2, 56.1, 56.0, 55.5, 49.0. HRMS (EI) calcd for C.sub.40H.sub.36N.sub.2O.sub.10 (M.sup.+): 704.2370. found: 704.2376.

3. Cyclization of Diketones 2a and 2c

[0190] ##STR00107##

[0191] General Specification:

[0192] Diketone 2 (0.25 mmol) is dissolved in 5 ml of dry dichloromethane under argon. Subsequently trifluoromethanesulfonic acid (0.49 ml, 5.5 mmol) is slowly added and the reaction mixture is stirred at room temperature for 1 h. Then triethylamine (0.92 ml, 6.6 mmol) is added dropwise in order to neutralize acid. The reaction mixture is then poured into a beaker containing 100 ml of methanol and cooled. Resulting suspension is then filtered, precipitate is ultrasonificated in boiling methanol for several minutes, filtered off and dried under vacuum.

##STR00108##

[0193] 150 mg (99%) of 3a is obtained from 2a as a dark violet solid. Mp: Decomposition >340 C. .sup.1H NMR (500 MHz, CDCl.sub.3:TFA-d 4:1) 8.49 (s, 2H), 8.41 (s, 2H), 7.67-7.60 (m, 6H), 7.49 (s, 2H), 7.49-7.44 (m, 4H), 4.32 (s, 6), 4.09 (s, 6H). .sup.13C NMR (126 MHz, CDCl.sub.3:TFA-d 4:1) 167.0, 155.2, 148.1, 141.4, 139.3, 132.5, 131.3, 130.3, 130.0, 129.7, 129.1, 122.7, 122.3, 108.0, 107.0, 57.9, 57.5. HRMS (FD) calcd for C.sub.38H.sub.28N.sub.2O.sub.6(M.sup.+): 608.1947. found: 608.1971.

##STR00109##

[0194] Prepared from 2c (176 mg, 0.25 mmol). 155 mg (93%) of 3c is obtained as violet powder. Mp: Decomposition >400 C. .sup.1H NMR (600 MHz, CDCl.sub.3:TFA-d 4:1) 8.50 (s, 2H), 8.41 (s, 2H), 7.58 (t, J=8.0 Hz, 2H), 7.52 (s, 2H), 7.23 (d, J=7.4 Hz, 2H), 7.12 (d, J=7.5 Hz, 2H), 7.07 (s, 2H), 4.32 (s, 6H), 4.11 (s, 6H), 3.95 (s, 6H). HRMS (FD) calcd for C.sub.38H.sub.28N.sub.2O.sub.6 (M.sup.+): 608.1947. found: 608.1971. HRMS (FD) calcd for C.sub.40H.sub.32N.sub.2O.sub.8 (M.sup.+): 668.2159. found: 668.2147.

Example 2

1. Method of the Synthesis of Diketone 2d

[0195] ##STR00110##

[0196] A mixture of pigment 1d (1.0 mmol), tetrabutylammonium bisulfate (TBAHS, 17 mg, 0.05 mmol), potassium carbonate (2.07 g, 15 mmol) and 25 ml of DMF is heated to 120 C. under an argon atmosphere. Then the solution of phenacyl bromide (1.99, 10 mmol) in 4 ml of DMF is slowly added (30 min). The reaction mixture is stirred for 2 h, cooled and diluted with water and methylene chloride. The aqueous layer is extracted with methylene chloride, combined organic layers are washed with water and brine and dried over sodium sulfate. Solvents are evaporated, the product is purified by the column chromatography (toluene:methylene chloride 1:1) and recrystallized from CHCl.sub.3/MeOH. Yield: 230 mg (28%). Dark brown solid. Mp: Decomposition >320 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 8.75 (s, 2H), 8.11 (s, 2H), 8.09 (d, J=1.3 Hz, 2H), 7.70-7.63 (m, 2H), 7.58-7.52 (m, 4H), 7.51 (d, J=1.5 Hz, 2H), 7.28 (s, 2H), 5.89 (s, 4H), 1.34 (s, 18H), 1.15 (s, 18H). .sup.13C NMR (126 MHz, CDCl.sub.3) 192.3, 160.7, 152.4, 147.0, 144.9, 134.9, 134.7, 133.9, 133.8, 128.8, 128.5, 128.4, 122.7, 117.5, 116.6, 108.6, 49.2, 34.9, 34.0, 31.6, 29.6. HRMS (ESI) calcd for C.sub.54H.sub.57N.sub.2O.sub.6 (M+H.sup.+): 829.4217. found: 829.4194.

2. Synthesis of Compound 3d

[0197] ##STR00111##

[0198] Diketone 2d (207 mg, 0.25 mmol) is dissolved in 5 ml of o-dichlorobenzene. Subsequently trifluoromethanesulfonic acid (0.49 ml, 5.5 mmol) is slowly added and the reaction mixture is stirred at 140 C. for 20 min. Then the reaction mixture is cooled down and triethylamine (0.92 ml, 6.6 mmol) is added dropwise in order to neutralize acid. Obtained mixture is then poured into a beaker containing 100 ml of methanol and cooled. Resulting suspension is then filtered, precipitate is recrystallized from CHCl.sub.3/MeOH to give 116 mg (59%) of 3d as violet powder. Mp: >400 C. (decomposition >360 C.). .sup.1H NMR (500 MHz, CDCl.sub.3) 8.14 (s, 2H), 7.65-7.62 (m, 4H), 7.58-7.52 (m, 8H), 7.31 (d, J=1.9 Hz, 2H), 1.68 (s, 18H), 1.25 (s, 18H). .sup.13C NMR (126 MHz, CDCl.sub.3) 155.1, 154.4, 146.9, 145.5, 135.5, 135.0, 129.1, 128.8, 128.7, 128.3, 127.1, 124.4, 123.6, 122.5, 122.4, 117.1, 110.0, 96.0, 35.0, 34.9, 31.6, 29.9. HRMS (ESI) calcd for C.sub.54H.sub.53N.sub.2O.sub.4 (M+H.sup.+): 793.4005. found: 793.4009.

[0199] Spectroscopic data of compounds 3a, 3b and 3d as well as comparative compounds

##STR00112##

(=compounds (3a) and (3e), respectively disclosed in WO2013/092474) are shown in the table below. Rhodamine B in EtOH or Rhodamine 6G in EtOH are used as standards for quantum yield measurements.

TABLE-US-00001 .sup.max.sub.abs .sup.max.sub.em Stokes shift .sub.max Comp. solvent [nm] [nm] [cm.sup.1] [M.sup.1 cm.sup.1] .sub.fl V-1 CHCl.sub.3 593 600 200 110000 0.19 V-1 DMF 593 601 220 91000 0.22 V-2 CHCl.sub.3 643 652 210 120000 0.05 V-2 DMF 645 655 240 107000 0.02 3a CHCl.sub.3 600 605 140 100000 0.89 3b CHCl.sub.3 601 609 220 85000 0.85 3d CHCl.sub.3 654 661 160 150000 0.81

[0200] The absorption and emission maxima of new compounds 3a, 3b and 3d are similar to those reported for compounds V-1 and V-2. Whereas the fluorescence quantum yield of new compounds 3a, 3b and 3d is typically around 80%, whereas the fluorescence quantum yield of compounds V-1 and V-2 is in the range of 5-40%. High fluorescence quantum yield is critical parameter for application in organic electronics.

[0201] In addition, solubility of new compounds 3a, 3b and 3d (in typical organic solvents) is order of magnitude higher than that of compound V-1. Reference is made to the below table.

TABLE-US-00002 Solubility [mol/l] Solubility [mg/l] Comp. in CHCl.sub.3 in Toluene in CHCl.sub.3 in Toluene V-1 2.72 .Math. 10.sup.4 6.13 .Math. 10.sup.6 126 2.85 3a 3.46 .Math. 10.sup.3 4.70 .Math. 10.sup.5 2110 28.6 3b 9.55 .Math. 10.sup.4 5.34 .Math. 10.sup.5 639 35.7

[0202] Accordingly, the new n-expanded diketopyrroles of the present invention have two clear advantages over the previously -expanded diketopyrroles described in WO2013/092474 and Daniel T. Gryko et al., Organic Letters 14 (2012) 2670: fluorescence quantum yield and solubility.

Example 3

[0203] ##STR00113##

[0204] 7-bromo-9,9-di(2-methoxyethyl)-9H-fluorene-2-carbonitrile 2: A mixture of 2,7-dibromo-9H-fluorene (11.34 g, 35 mmol), potassium iodide (100 mg, 0.60 mmol) and 150 ml of THF is stirred under argon at room temperature. Sodium hydride (7.00 g, 175 mmol, 60% in mineral oil) is carefully added in portions and the mixture is stirred for additional 15 min. Subsequently 1-chloro-2-methoxyethane (9.6 ml, 105 mmol) is added dropwise and the reaction mixture is stirred for 3 days at room temperature. The reaction is quenched by dropwise addition of 200 ml of water. The resulting black mixture is acidified with 6M HCl (color disappeared) and extracted three times with methylene chloride. Combined organic layers are washed twice with water and dried over sodium sulfate. Solvents are removed under reduced pressure and obtained solid residue is recrystallized from ethanol to give 13.40 g (87%) of 2,7-dibromo-9,9-di(2-methoxyethyl)-9H-fluorene as a white powder. Mp: 138-140 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.55 (d, J=1.4 Hz, 2H), 7.53 (d, J=8.1 Hz, 2H), 7.49 (dd, J=8.1, 1.7 Hz, 2H), 3.02 (s, 6H), 2.68 (dd, J=8.4, 6.7 Hz, 4H), 2.49-2.15 (m, 4H). .sup.13C NMR (126 MHz, CDCl.sub.3) 150.8, 138.4, 130.8, 126.5, 121.8, 121.3, 68.1, 58.4, 51.7, 39.4. HRMS (EI) calcd for C.sub.19H.sub.20Br.sub.2O.sub.2 (M.sup.+): 437.9830. found: 437.9831.

2,7-Dibromo-9,9-di(2-methoxyethyl)-9H-fluorene (13.21 g, 30 mmol), copper(I) cyanide (2.78 g, 31 mmol) and 100 ml of DMF are stirred under argon at 160 C. in a tightly closed pressure vessel. After 40 h the reaction mixture is cooled down and a solution of 26 g of FeCl.sub.3.6H.sub.2O in 40 ml of concentrated hydrochloric acid and 10 ml of water is added. Resulting mixture is stirred for 20 min at 90 C., cooled down, diluted with water and extracted with 5 portions of methylene chloride. Organic layers are combined, washed twice with water and dried over MgSO.sub.4. The product is purified by silica-gel chromatography (chloroform.fwdarw.chloroform:ethyl acetate 9:1) and recrystallized from ethanol. 5.20 g (45%) of 0f is obtained as off-white powder. Mp: 193-196 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.75 (dd, J=7.9, 0.6 Hz, 1H), 7.70 (dd, J=1.4, 0.6 Hz, 1H), 7.66 (dd, J=7.9, 1.4 Hz, 1H), 7.64-7.59 (m, 2H), 7.55 (dd, J=8.1, 1.8 Hz, 1H), 2.99 (s, 6H), 2.78-2.70 (m, 2H), 2.70-2.62 (m, 2H), 2.41-2.27 (m, 4H). .sup.13C NMR (126 MHz, CDCl.sub.3) 151.9, 149.6, 143.8, 137.5, 131.9, 131.1, 127.0, 126.8, 123.4, 122.2, 120.5, 119.30, 110.7, 68.0, 58.4, 52.0, 39.2. HRMS (ESI) calcd for C.sub.20H.sub.20BrNO.sub.2Na (M+Na.sup.+): 408.0570. found: 408.0575.

1. Synthesis of Diketopyrrolopyrroles 1f and 1g

[0205] ##STR00114##

3,6-Bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole (0f)

[0206] Prepared from 7-bromo-9,9-di(2-methoxyethyl)-9H-fluorene-2-carbonitrile (N-3, 4.87 g, 12.6 mmol). After the reaction mixture is acidified and cooled down, obtained precipitate is filtered off, washed several times with hot water and methanol and dried under vacuum. Of (1.66 g, 32%) was obtained as dark brown powder. Mp >400 C. .sup.1H NMR (500 MHz, CDCl.sub.3:TFA-d 4:1) 8.48 (br s, 2H, 1-H at fluorenyl), 8.22 (br s, 2H, 3-H at fluorenyl), 7.96 (br s, 2H, 4-H at fluorenyl), 7.72 (d, J=8.0 Hz, 2H, 5-H at fluorenyl), 7.69-7.62 (m, 4H, 6-H and 8-H at fluorenyl), 3.17 (s, 12H, OCH.sub.3), 3.11-2.95 (m, 8H, CH.sub.2CH.sub.2OCH.sub.3), 2.59 (br s, 4H, CH.sub.2CH.sub.2OCH.sub.3), 2.50 (br s, 4H, CH.sub.2CH.sub.2OCH.sub.3). HRMS (ESI) calcd for C.sub.44H.sub.42Br.sub.2N.sub.2O.sub.6Na (M+Na.sup.+): 875.1301. found: 875.1307.

3,6-Bis(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole (0g)

[0207] Under an argon atmosphere, in a three-necked flask equipped with a reflux condenser and magnetic stirrer are placed 20 ml of tert-amyl alcohol, catalytic amount of iron(III) chloride and sodium (0.690 g, 30 mmol). The mixture is heated under reflux until sodium is completely reacted (about 1 h). Then the reaction mixture is cooled to 90 C. and 7-bromo-9,9-dioctyl-9H-fluorene-2-carbonitrile (6.23 g, 12.6 mmol) is added. The mixture is then heated to 110 C. and 1.23 ml (6.0 mmol) of diisopropyl succinate is added dropwise (30 min). After 16 h of reaction at 110 C., the mixture is cooled and 30 nil of water/acetic acid 1:1 is added. Resulting mixture is refluxed for a few minutes and cooled to 30 C. Water and dichloromethane are added and layers are separated. Aqueous layer is extracted three times with dichloromethane, combined organic layers are washed twice with water and dried over Na.sub.2SO.sub.4. Solvents are evaporated and obtained residue is dissolved in hot toluene. Product is precipitated by an excess addition of EtOH and the resulting mixture is cooled down. Precipitate is filtered off and dried under vacuum. 0g (1.53 g, 24%) is obtained as brown powder. Mp 383-389 C. .sup.1H NMR (500 MHz, CDCl.sub.3:TFA-d 4:1) 8.34 (br s, 2H, 1-H at fluorenyl), 8.18 (br s, 2H, 3-H at fluorenyl), 7.91 (d, J=7.2 Hz, 2H, 4-H at fluorenyl), 7.68 (d, J=7.8 Hz, 2H, 5-H at fluorenyl), 7.62-7.52 (m, 4H, 6-H and 8-H at fluorenyl), 2.13 (td, J=12.1, 3.8 Hz, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 2.03 (td, J=12.1, 3.8 Hz, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.29-1.02 (m, 40H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.82 (t, J=7.1 Hz, 12H, CH.sub.3), 0.77-0.60 (m, 8H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3:TFA-d 4:1) 165.2, 155.2, 152.6, 147.8, 146.8, 139.0, 131.2, 128.4, 127.2, 125.6, 125.4, 124.2, 123.8, 122.9, 121.4, 56.4, 40.5, 32.3, 30.3, 29.7, 29.6, 24.3, 23.1, 14.2. HRMS (ESI) calcd for C.sub.64H.sub.82Br.sub.2N.sub.2O.sub.2 (M.sup.+): 1068.4743. found: 1068.4716.

2. Synthesis of Diketones 2f and 2g

[0208] ##STR00115##

[0209] 3,6-Bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl).sub.2,5-bis(2,2-diethoxyethyl)-1,4-diketopyrrolo[3,4-c]pyrrole (2f): A mixture of 3,6-bis(7-bromo-9,9-di(2-methoxyethyl)-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole (1f, 684 mg, 0.80 mmol), tetrabutylammonium bisulfate (TBAHS, 14 mg, 0.04 mmol), potassium carbonate (1.66 g, 12 mmol) and 20 ml of DMF is heated to 130 C. under an argon atmosphere. Then bromoacetaldehyde diethyl acetal (1.20 ml, 8.0 mmol) is added dropwise by a syringe (30 min). The reaction mixture is stirred for 16 h at 130 C., cooled and diluted with water and dichloromethane. The aqueous layer is extracted with five portions of dichloromethane, combined organic layers are washed with water and brine and dried over sodium sulfate. Solvents are evaporated, the product is separated by the column chromatography (dichloromethane:acetone 19:1.fwdarw.9:1) and recrystallized by slow addition of MeOH to the solution of product in small amount of CHCl.sub.3. 2f (440 mg, 51%) is obtained as orange-yellow fluorescent powder. Mp 197-199 C. (CHCl.sub.3/MeOH). .sup.1H NMR (500 MHz, CDCl.sub.3) 8.23 (d, J=1.1 Hz, 2H, 1-H at fluorenyl), 8.16 (dd, J=8.0, 1.5 Hz, 2H, 3-H at fluorenyl), 7.82 (d, J=8.0 Hz, 2H, 4-H at fluorenyl), 7.65-7.60 (m, 4H, 5-H and 8-H at fluorenyl), 7.53 (dd, J=8.2, 1.7 Hz, 2H, 6-H at fluorenyl), 4.97 (t, J=5.6 Hz, 2H, NCH.sub.2CH(OEt).sub.2), 3.90 (d, J=5.6 Hz, 4H, NCH.sub.2CH(OEt).sub.2), 3.73 (dq, J=9.3, 7.0 Hz, 4H, OCH.sub.2CH.sub.3), 3.55 (dq, J=9.4, 7.0 Hz, 4H, OCH.sub.2CH.sub.3), 3.05 (s, 12H, OCH.sub.3), 2.85-2.73 (m, 8H, CH.sub.2CH.sub.2OCH.sub.3), 2.45 (ddd, J=14.0, 9.5, 5.6 Hz, 4H, CH.sub.2CH.sub.2OCH.sub.3), 2.34 (ddd, J=14.0, 9.5, 5.6 Hz, 4H, CH.sub.2CH.sub.2OCH.sub.3), 1.19 (t, J=7.0 Hz, 12H, OCH.sub.2CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 163.4, 152.1, 149.1 (2 signals), 142.3, 138.5, 130.9, 129.7, 127.1, 126.8, 124.3, 122.5, 121.8, 120.3, 109.6, 100.4, 68.3, 63.8, 58.4, 51.8, 45.8, 39.3, 15.5. HRMS (ESI) calcd for C.sub.56H.sub.66Br.sub.2N.sub.2O.sub.10Na (M+Na.sup.+): 1107.2982. found: 1107.3010.

3,6-Bis(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-2,5-bis(2,2-diethoxyethyl)-1,4-diketopyrrolo[3,4-c]pyrrole (2g)

[0210] A mixture of 3,6-bis(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-1,4-diketopyrrolo[3,4-c]pyrrole (1g, 1.24 g, 1.16 mmol), potassium carbonate (2.40 g, 17.4 mmol) and 25 ml of NMP is heated to 120 C. under an argon atmosphere. Then bromoacetaldehyde diethyl acetal (1.75 ml, 11.6 mmol) is added dropwise by a syringe (30 min). The reaction mixture is stirred for 1 h at 120 C., then the second portion of bromoacetaldehyde diethyl acetal (1.75 ml, 11.6 mmol) is added and the reaction is stirred overnight at 130 C., cooled and diluted with water. The product is extracted with three portions of hexane, combined organic layers are washed twice with water and brine and dried over sodium sulfate. Solvents are evaporated, the product is separated by the column chromatography (hexanes:ethyl acetate 29:1.fwdarw.19:1). After evaporation and drying under vacuum, 2g (0.696 g, 46%) is obtained as red-orange fluorescent oil, which solidifies after standing overnight at ambient temperature. The product can be used in next steps without further purification. If higher purity is necessary, it can be recrystallized by slow addition of MeOH to the solution of product in small amount of CHCl.sub.3. Mp 100-102 C. (CHCl.sub.3/MeOH). .sup.1H NMR (500 MHz, CDCl.sub.3) 8.18 (s, 2H, 1-H at fluorenyl), 8.15 (dd, J=8.0, 1.4 Hz, 2H, 3-H at fluorenyl), 7.80 (d, J=7.9 Hz, 2H, 4-H at fluorenyl), 7.61 (d, J=8.2 Hz, 2H, 5-H at fluorenyl), 7.54-7.46 (m, 4H, ArH, 6-H and 8-H at fluorenyl), 4.99 (t, J=5.6 Hz, 2H, NCH.sub.2CH(OEt).sub.2), 3.90 (d, J=5.6 Hz, 4H, NCH.sub.2CH(OEt).sub.2), 3.73 (dq, J=9.3, 7.0 Hz, 4H, OCH.sub.2CH.sub.3), 3.55 (dq, J=9.3, 7.0 Hz, 4H, OCH.sub.2CH.sub.3), 2.06 (ddd, J=13.3, 10.5, 6.3 Hz, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.96 (ddd, J=13.3, 10.5, 6.3 Hz, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.31-1.00 (m, 52H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3 and OCH.sub.2CH.sub.3), 0.82 (t, J=7.2 Hz, 12H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.73-0.61 (m, 8H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 163.5, 153.9, 150.7, 149.3, 143.0, 139.3, 130.2, 129.4, 126.8, 126.4, 124.1, 122.2, 121.7, 120.1, 109.5, 100.5, 63.7, 55.8, 45.9, 40.1, 31.8, 30.0, 29.3, 29.2, 23.9, 22.6, 15.5, 14.1. HRMS (ESI) calcd for C.sub.76H.sub.106Br.sub.2N.sub.2O.sub.6Na (M+Na.sup.+): 1323.6315. found: 1323.6322.

3. Synthesis of Compounds 5f and 5g

[0211] ##STR00116##

General Specification

[0212] Dye 2f (109 mg, 0.100 mmol) or 2g (130 mg, 0.100 mmol) is dissolved in 2 ml of chloroform under an argon atmosphere. Subsequently trifluoromethanesulfonic acid (0.44 ml, 5.0 mmol) is slowly added and the reaction mixture is stirred at 60 C. for 1 h. Then the reaction mixture is cooled down and triethyl amine (0.84 ml, 6.0 mmol) is slowly added in order to neutralize acid. To obtained dark blue mixture 100 ml of MeOH is slowly added and the resulting suspension is cooled down and the precipitate is filtered off, washed with hot methanol and dried under vacuum.

6,17-Dibromo-8,8,19,19-tetra(2-methoxyethyl)-8H,19H-fluoreno[3,2: 7,8]indolizino-[21: 3,4]pyrrolo[2,1-a]indeno[1,2-g]isoquinoline-10,21-dione (5f)

[0213] Prepared from 2f (109 mg, 0.10 mmol). Yield: 82 mg (91%). Dark violet crystals. Mp 354-356 C. (CHCl.sub.3/MeOH). .sup.1H NMR (500 MHz, CDCl.sub.3) 9.26 (s, 2H, 9-H and 20-H), 7.91 (d, J=7.3 Hz, 2H, 1-H and 12-H), 7.84 (s, 2H, 3-H and 14-H), 7.70 (d, J=8.1 Hz, 2H, 4-H and 15-H), 7.67 (d, J=1.4 Hz, 2H, 7-H and 18-H), 7.57 (dd, J=8.1, 1.8 Hz, 2H, 5-H and 16-H), 6.88 (d, J=7.3 Hz, 2H, 2-H and 13-H), 3.01 (s, 12H, OCH.sub.3), 2.92-2.78 (m, 8H, CH.sub.2CH.sub.2OCH.sub.3), 2.61 (ddd, J=14.5, 8.9, 5.7 Hz, 4H, CH.sub.2CH.sub.2OCH.sub.3), 2.40 (ddd, J=14.1, 9.0, 5.5 Hz, 4H, CH.sub.2CH.sub.2OCH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 155.8, 152.7, 150.0, 144.4, 141.4, 137.8, 134.6, 131.1, 127.2, 124.1, 123.6, 123.2, 122.7, 122.3, 117.4, 112.3, 101.5, 68.4, 58.3, 51.9, 39.5. HRMS (ESI) calcd for C.sub.48H.sub.42Br.sub.2N.sub.2O.sub.6 (M.sup.+): 900.1410. found: 900.1396.

6,17-Dibromo-8,8,19,19-tetraoctyl-8H,19H-fluoreno[3,2: 7,8]indolizino-[21: 3,4]pyrrolo[2,1-a]indeno[1,2-g]isoquinoline-10,21-dione (5g)

[0214] Prepared from 2g (130 mg, 0.10 mmol). Yield: 104 mg (93%). Dark blue powder. Mp 194-197 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 9.19 (s, 2H, 9-H and 20-H), 7.91 (d, J=7.3 Hz, 2H, 1-H and 12-H), 7.83 (s, 2H, 3-H and 14-H), 7.70 (d, J=7.9 Hz, 2H, 4-H and 15-H), 7.59-7.50 (m, 4H, 7-H and 18-H+, 5-H and 16-H), 6.88 (d, J=7.4 Hz, 2H, 2-H and 13-H), 2.29-2.15 (m, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 2.12-1.98 (m, 4H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.32-0.94 (m, 40H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.78 (t, J=7.1 Hz, 12H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.72-0.62 (m, 8H, CH.sub.2CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 156.0, 154.4, 151.6, 145.2, 141.5, 138.4, 134.3, 130.5, 126.7, 124.1, 123.5, 123.0, 122.3, 122.2, 117.1, 112.4, 101.4, 55.8, 40.4, 31.8, 29.8, 29.2 (2 signals), 23.4, 22.6, 14.0. HRMS (ESI) calcd for C.sub.63H.sub.83Br.sub.2N.sub.2O.sub.2 (M.sup.+): 1117.4821. found: 1117.4784.

4. Synthesis of Compounds 4f and 4g

[0215] ##STR00117##

[0216] In a 20 ml Schlenk flask containing a magnetic stirring bar are placed: dye 5f (45 mg, 0.050 mmol) or 5g (56 mg, 0.050 mmol), 4,4-bismethoxydiphenylamine (34 mg, 0.148 mmol), (2-dicyclohexylphosphino-2,6-diisopropoxy-1,1-biphenyl)[2-(2-amino-1,1-biphenyl)]-palladium(II) methanesulfonate ((RuPhos)precatalyst (Buchwald et al., Chem. Sci. 4 (2013) 916, 2.5 mg, 0.003 mmol), 2-dicyclohexylphosphino-2,6-diisopropoxybiphenyl (RuPhos, 1.4 mg, 0.003 mmol) and caesium carbonate (98 mg, 0.300 mmol). The vessel is evacuated and backfilled with argon (3 times). Then 3 ml of anhydrous toluene is added under a positive pressure of argon. The flask was again carefully evacuated and backfilled with argon three-times, the vessel is tightly closed and the reaction mixture is stirred for given time at 120 C. (above boiling point). After the mixture is cooled, water and dichloromethane are added, layers are separated. The aqueous layer is extracted with dichloromethane 3 times. Combined organic layers are washed with water twice and dried over Na.sub.2SO.sub.4. Solvents are evaporated and the product is purified by column chromatography in the given eluting system.

6,17-Bis(di(4-methoxyphenyl)amino)-8,8,19,19-tetra(2-methoxyethyl)-8H,19H-fluoreno-[3,2: 7,8]indolizino[21:3,4]pyrrolo[2,1-a]indeno[1,2-g]isoquinoline-10,21-dione (4f)

[0217] Prepared from 5f (45 mg, 0.050 mmol). Reaction time: 40 h. Purified by column chromatography (dichloromethane:acetone 9:1.fwdarw.17:3) and recrystallized by slow addition of MeOH to the solution of product in hot toluene. Yield: 23 mg (38%). Black powder. Mp 376-380 C. (CHCl.sub.3/MeOH). .sup.1H NMR (500 MHz, CDCl.sub.3, 50 C.) 9.20 (s, 2H, 9-H and 20-H), 7.87 (br s, 2H, ArH), 7.65 (s, 2H, 3-H and 14-H), 7.57 (d, J=8.4 Hz, 2H, ArH), 7.13-7.05 (m, 8H, 2-H and 6-H at 4-methoxyphenyl), 7.02 (s, 2H, ArH), 6.92 (br s, 2H, ArH), 6.89-683 (m, 8H, 3-H and 5-H at 4-methoxyphenyl), 6.80 (d, J=7.4 Hz, 2H, 2-H and 13-H), 3.82 (s, 12H, C.sub.6H.sub.4OCH.sub.3), 3.05 (s, 12H, CH.sub.2CH.sub.2OCH.sub.3), 2.98-2.87 (m, 8H, CH.sub.2CH.sub.2OCH.sub.3), 2.54-2.44 (m, 4H, CH.sub.2CH.sub.2OCH.sub.3), 2.29-2.18 (m, 4H, CH.sub.2CH.sub.2OCH.sub.3). HRMS (ESI) calcd for C.sub.76H.sub.70N.sub.4O.sub.10 (M.sup.+): 1198.5092. found: 1198.5092.

6, 17-Bis(di(4-methoxyphenyl)amino)-8, 8, 19, 19-tetraoctyl-8H,19H-fluoreno[3,2: 7,8]-indolizino[21: 3,4]pyrrolo[2,1-a]indeno[1,2-g]isoquinoline-10,21-dione (4g)

[0218] Prepared from 5g (56 mg, 0.050 mmol). Reaction time: 20 h. Yield: 46 mg (65%). Purified by the column chromatography (toluene:acetone 1000:1.fwdarw.100:1) and recrystallized by slow addition of MeOH to the solution of product in CHCl.sub.3. Dark green solid. Mp 223-226 C. .sup.1H NMR (500 MHz, C.sub.6D.sub.6) 9.70 (s, 2H, 9-H and 20-H), 7.81 (d, J=7.3 Hz, 2H, 1-H and 12-H), 7.56 (d, J=8.3 Hz, 2H, 4-H and 15-H), 7.39 (d, J=1.8 Hz, 2H, 7-H and 18-H), 7.36 (s, 2H, 3-H and 14-H), 7.24-7.19 (m, 8H, 2-H and 6-H at 4-methoxyphenyl), 7.19 (d, J=1.8 Hz, 2H, 5-H and 16-H partially covered by benzene residual peak), 6.86-6.76 (m, 8H, 3-H and 5-H at 4-methoxyphenyl), 6.23 (d, J=7.4 Hz, 2H, 2-H and 13-H), 3.32 (s, 12H, C.sub.6H.sub.4OCH.sub.3), 2.46-2.33 (m, 4H, CH.sub.2(CH.sub.2).sub.6CH.sub.3), 2.06-1.92 (m, 4H, CH.sub.2(CH.sub.2).sub.6CH.sub.3), 1.46-1.00 (m, 48H, CH.sub.2(CH.sub.2).sub.6CH.sub.3), 0.82 (t, J=7.0 Hz, 12H, CH.sub.2(CH.sub.2).sub.6CH.sub.3). .sup.13C NMR (126 MHz, C.sub.6D.sub.6) 156.9, 156.2, 154.6, 152.2, 150.7, 146.5, 141.4, 141.3, 134.7, 133.0, 127.2, 123.8, 123.2, 122.4, 122.1, 120.3, 116.0, 115.5, 115.3, 111.9, 101.6, 55.7, 55.1, 40.9, 32.3, 30.5, 29.8, 29.7, 24.7, 23.1, 14.4. HRMS (ESI) calcd for C.sub.96H.sub.111N.sub.4O.sub.6 (M+H.sup.+): 1415.8504. found: 1415.8467.

Example 4

Synthesis of Compound 6a

[0219] ##STR00118##

[0220] 50g of [286438-45-7] are dissolved in 300 ml of dry dimethylformamide, followed by the addition of 7.16g CuCN. The reaction mixture is then stirred for 24 hours at reflux. The reaction mixture is cooled to RT, poured on water and the product is then extracted with ethylacetate. After drying the organic phase with MgSO.sub.4, the ethylacetate solution is filtered over HYFLO and then the solvent is evaporated. The product is purified by chromatography over silicagel to obtain a compound of formula 6a. .sup.1H-NMR data (ppm, CDCl.sub.3): 7.77 1H d, 7.74-7.61 3H m, 7.55-7.51 2H m, 1.97 4H t, 1.33-1.07 36H m, 0.89 6H t, 0.65-0.49 4H m.

Synthesis of Compound 6b

[0221] ##STR00119##

[0222] 200 ml of tert-amylacohol are placed in a reactor under nitrogen, and then 50 mg of Fe(III)C.sub.13 are added. The mixture is heated to 90 C. and then 1.88g of sodium metal is added and the mixture is heated to reflux. As soon as the sodium is dissolved and reacted completely, a solution of 200 ml of tert-amylalcohol containing 19.35g of compound 6a and 4.15g of di-tert-amylsuccinate is added dropwise to the first solution. The reaction mixture is then stirred over night at reflux. The violet reaction mixture is then cooled to 40 C. and poured on methanol/ice mixture. The mixture is filtered and the violet precipitate is washed with water, methanol and acetone and then dried to give a compound of formula 6b. The product is directly used in the next step.

Synthesis of Compound 6c

[0223] ##STR00120##

[0224] 2g of compound 6b, 2.43g of 1-bromo-2,2-diethoxyethane, 0.13g of KI and 1.71g of K.sub.2CO.sub.3 are added to 40 ml of dry dimethylformamide. The mixture is then stirred over night at 90 C. The reaction mixture is cooled and poured on water/ice. The product is extracted with ethylacetate. The organic phase is dried over MgSO.sub.4 and evaporated. The crude product is used directly in the next step.

Synthesis of Compound 6d

[0225] ##STR00121##

[0226] 2.6g of compound 6c is dissolved in 10 ml of methylenechloride. Then 10 ml of concentrated sulfuric acid are added and the mixture is stirred at reflux overnight. The reaction mixture is then poured on ice/water, and the product is extracted with chloroform. The organic phase is dried over MgSO.sub.4 and evaporated. The product is purified by chromatography over silica gel to give a compound of formula 6d. .sup.1H-NMR data (ppm, CDCl.sub.3): 9.21 2H s, 7.93 2H d, 7.85 2H s, 7.72 2H d, 7.58 2H s, 7.55 2H d, 6.90 2H d, 2.30-2.20 4H m, 2.12-2.01 4H m, 1.30-1.02 72H m, 0.66 12H t, 0.73-0.65 8H m.

Example 5

Synthesis of Compound 7a [403699-44-5]

[0227] ##STR00122##

[0228] Compound 7a is obtained from compound [189367-54-2] according to compound 6a. .sup.1H-NMR data (ppm, CDCl.sub.3): 7.77 1H d, 7.74-7.61 3H m, 7.55-7.51 2H m, 1.97 4H t, 1.25-1.02 12H m, 0.80 6H t, 0.65-0.50 4H m.

Synthesis of Compound 7b

[0229] ##STR00123##

[0230] Compound 7b is obtained from compound 7a according to compound 6b. .sup.1H-NMR data (ppm, DMSO-d.sub.6): 8.67 2H d, 8.51 2H s, 8.00 2H d, 7.87 2H d, 7.74 2H s, 7.57 2H d, 2.12-1.95 8H bs, 1.12-0.95 24H bm, 0.80-0.65 12H bt, 0.62-0.48 8H bs.

Synthesis of Compound 7c

[0231] ##STR00124##

[0232] Compound 7c is obtained from compound 7b according to compound 6c. .sup.1H-NMR data (ppm, CDCl.sub.3): 8.18 2H s, 8.16 2H d, 7.82 2H d, 7.63 2H d, 7.52 2H s, 7.50 2H d, 5.00 2H t, 3.91 4H d, 3.80-3.70 4H m, 3.62-3.51 4H m, 2.11-1.93 8H m, 1.23 12H t, 1.21-1.05 24H m, 0.79 12H t, 0.75-0.65 8H bm.

Synthesis of Compound 7d

[0233] ##STR00125##

[0234] Compound 7d is obtained from compound 7c according to compound 6d. .sup.1H-NMR data (ppm, CDCl.sub.3): 9.21 2H s, 7.93 2H d, 7.85 2H s, 7.72 2H d, 7.58 2H s, 7.55 2H d, 6.91 2H d, 2.29-2.19 4H m, 2.11-2.01 4H m, 1.20-1.00 24H m, 0.76 12H t, 0.73-0.65 8H m.

Example 6

Synthesis of Compound 8a

[0235] ##STR00126##

[0236] 18g of [365547-20-2] are dissolved in 150 ml of dry tetrahydrofuran under nitrogen. This solution is then cooled to 60 C. Then 18.2 ml of 2.7M butyllithium in heptane are added slowly. The reaction mixture is stirred for 30 minutes at 60 C. Then it is allowed to warm to 0 C. for 5 minutes, and cooled again to 60 C. Then 4.2 ml of anhydrous dimethylformamide are added and the reaction mixture is allowed to warm up to room temperature. The reaction is quenched with water and the aqueous layer is extracted with ethylacetate. The organic phase is dried with MgSO.sub.4 and evaporated to give a compound of formula 8a. .sup.1H-NMR data (ppm, CDCl.sub.3): 9.85 1H s, 7.58 1H s, 7.39 1H d, 7.01 1H d, 2.05-1.85 4H m, 1.12-0.81 16H m, 0.81-0.70 6H m, 0.70-0.55 8H m.

Synthesis of Compound 8b

[0237] ##STR00127##

[0238] 18.57g of compound 8a are dissolved in 190 ml of absolute ethanol. Then 4.2 ml of pyridine are added, followed by 3.63g of hydroxylamine-hydrochloride. The reaction mixture is refluxed for 6 hours under nitrogen. Then the mixture is still stirred over night at room temperature. The ethanol is evaporated under reduced pressure and the residue is dissolved in ethylacetate, then washed with 4M HCl. The organic phase is separated and dried over MgSO.sub.4. The product of formula 8b is obtained and is used directly in the next step.

Synthesis of Compound 8c

[0239] ##STR00128##

[0240] To 20.12g of compound 8b are added 190 ml of acetic anhydride and the solution is stirred at reflux overnight. The solution is cooled to room temperature and is poured slowly on ice/water. The product is extracted with ethylacetate. The organic phase is separated, dried over MgSO.sub.4 and the solvent is evaporated. The product is purified by chromatography over silica gel to get a compound of formula 8c. .sup.1H-NMR data (ppm, CDCl.sub.3): 7.44 1H s, 7.34 1H d, 6.99 1H d, 1.98-1.85 4H m, 1.12-0.81 16H m, 0.81-0.70 6H m, 0.70-0.50 8H m.

Synthesis of Compound 8d

[0241] ##STR00129##

[0242] Compound 8d is obtained from compound 8c according to compound 6b. .sup.1H-NMR data (ppm, CDCl.sub.3): 9.55 2H very broad s, 8.11-8.05 2H m, 7.35 2H d, 7.03 2H d, 2.20-1.93 8H m, 1.10-0.82 32H m, 0.82-0.68 12H m, 0.68-0.55 16H m.

Synthesis of Compound 8e

[0243] ##STR00130##

[0244] Compound 8e is obtained from compound 8d according to compound 6c.

Synthesis of Compound 8f

[0245] ##STR00131##

[0246] Compound 8f is obtained from compound 8e according to compound 6d.

Example 7

Synthesis of Compound 9a

[0247] ##STR00132##

[0248] Compound 9a is obtained from compound [1201921-87-0] according to compound 8a. .sup.1H-NMR data (ppm, CDCl.sub.3): 9.86 1H s, 7.59 1H s, 7.41 1H d, 7.00 1H d, 2.00-1.83 4H m, 1.42-1.08 36H m, 1.06-0.95 4H m, 0.90 6H t.

Synthesis of Compound 9b

[0249] ##STR00133##

[0250] Compound 9b is obtained from compound 9a according to compound 8b. The product has been used directly in the next step.

Synthesis of Compound 9c

[0251] ##STR00134##

[0252] Compound 9c is obtained from compound 9b according to compound 8c. .sup.1H-NMR data (ppm, CDCl.sub.3): 7.43 1H s, 7.35 1H d, 6.98 1H d, 1.90-1.82 4H m, 1.38-1.10 36H m, 0.98-0.85 10H m.

Synthesis of Compound 9d

[0253] ##STR00135##

[0254] Compound 9d is obtained from compound 9c according to compound 8d. .sup.1H-NMR data (ppm, CDCl.sub.3): 8.36 2H broad s, 8.06 2H broad s, 7.36 2H d, 7.00 2H d, 2.00-1.88 8H m, 1.32-1.10 72H m, 1.06-0.90 8H m, 0.87 12H t.

Synthesis of Compound 9e

[0255] ##STR00136##

[0256] Compound 9e is obtained from compound 9d according to compound 8e. .sup.1H-NMR data (ppm, CDCl.sub.3): 8.66 2H s, 7.34 2H d, 7.01 2H d, 4.94 2H t, 4.26 4H d, 3.87-3.80 4H m, 3.63-3.57 4H m, 2.01-1.85 8H m, 1.38-1.10 72H m, 1.10-0.92 8H m, 0.89 12H t.

Synthesis of Compound 9f

[0257] ##STR00137##

[0258] Compound 9f is obtained from compound 9e according to compound 8f.