* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
8b. 2-fluoro-5-nitropyridine 2-Chloro-5-nitropyridine (100 g, 0.656 mol, Aldrich), potassium fluoride (84.1 g, 1.45 mol, Aldrich), tetraphenylphosphonium bromide (95.3 g, 0.227 mol, Aldrich), and acetonitrile (1.5 L) were combined and heated at reflux until consumption of the 2-chloro-5-nitropyridine was complete. The volume of the mixture was reduced to 750 mL, diluted with 2 L of ether, filtered and concentrated. The resultant residue was triturated with hot hexane, and the combined hexane extracts were concentrated to give of the title compound (48 g, 54percent): 1 H NMR (CDCl3, 300 MHz) δ 7.15 (dd, J=3, 6 Hz, 1 H), 8.64 (m, 1 H), 9.15 (d, J=1.6 Hz, 1 H).
Reference：
[1] Patent: US6133253, 2000, A,
2
[ 118-45-6 ]
[ 2751-90-8 ]
[ 74-11-3 ]
[ 1823-59-2 ]
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[1] Patent: US5153335, 1992, A,
[2] Patent: US5153335, 1992, A,
[3] Patent: US5153335, 1992, A,
[4] Patent: US5153335, 1992, A,
3
[ 118-45-6 ]
[ 2751-90-8 ]
[ 120-82-1 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
4
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[1] Patent: US5153335, 1992, A,
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[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 2751-90-8 ]
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[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
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[ 120-82-1 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
8
[ 118-45-6 ]
[ 2751-90-8 ]
[ 50-30-6 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
9
[ 118-45-6 ]
[ 2751-90-8 ]
[ 50-79-3 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
10
[ 118-45-6 ]
[ 2751-90-8 ]
[ 99-94-5 ]
[ 120-82-1 ]
[ 1823-59-2 ]
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[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 2751-90-8 ]
[ 118-91-2 ]
[ 120-82-1 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 2751-90-8 ]
[ 74-11-3 ]
[ 120-82-1 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 19398-61-9 ]
[ 2751-90-8 ]
[ 74-11-3 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 95-73-8 ]
[ 2751-90-8 ]
[ 74-11-3 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
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[ 118-45-6 ]
[ 2751-90-8 ]
[ 95-50-1 ]
[ 74-11-3 ]
[ 1823-59-2 ]
Reference：
[1] Patent: US5153335, 1992, A,
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[ 22280-56-4 ]
[ 2751-90-8 ]
[ 19346-46-4 ]
Yield
Reaction Conditions
Operation in experiment
60%
With KF In hexane; acetonitrile
18a. 2-fluoro-3-methyl-5-nitropyridine 2-Chloro-3-methyl-5-nitropyridine (15 g, 86.9 mmol; from Maybridge Chemical Co.), KF (12 g, 258 mmol) and tetraphenylphosphonium bromide (20 g, 47.7 mmol; Aldrich) were combined in 200 mL of acetonitrile and heated at reflux for 4 days. The mixture was diluted with Et2 O (500 mL) and filtered, and the filtrate was concentrated. The residue was triturated with hot hexane (4*200 mL), and the hexane solutions were combined and concentrated to afford the title compound as a solid (8.4 g, 60percent): 1 H NMR (DMSO-d6, 300 MHz) δ2.42 (s, 3H), 8.43 (m, 1H), 8.95 (dd, J=1.6 Hz, 1H); MS (CI/NH3) m/z: 157 (M+H)+.
Reference：
[1] Patent: US5733912, 1998, A,
17
[ 83-38-5 ]
[ 2751-90-8 ]
[ 437-81-0 ]
Reference：
[1] Patent: US6127581, 2000, A,
18
[ 126-33-0 ]
[ 611-06-3 ]
[ 2751-90-8 ]
[ 446-35-5 ]
Reference：
[1] Patent: US6184425, 2001, B2,
19
[ 108-86-1 ]
[ 20472-49-5 ]
[ 1530-32-1 ]
[ 2751-90-8 ]
[ 3878-45-3 ]
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[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
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[ 108-86-1 ]
[ 603-35-0 ]
[ 2751-90-8 ]
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[1] Journal of Organic Chemistry, 2008, vol. 73, # 2, p. 590 - 593
[2] Journal of Fluorine Chemistry, 2000, vol. 101, # 1, p. 45 - 60
[3] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1982, # 10, p. 2289 - 2298
[4] Tetrahedron Letters, 1986, vol. 27, # 5, p. 645 - 648
[5] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1985, p. 1217 - 1226
[6] Bulletin of the Chemical Society of Japan, 1957, vol. 30, p. 667,669
[7] Chemische Berichte, 1958, vol. 91, p. 50
[8] Journal of Solution Chemistry, 1980, vol. 9, p. 841 - 856
[9] Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical & Analytical, 1980, vol. 19, # 6, p. 592 - 594
21
[ 2588-88-7 ]
[ 2751-90-8 ]
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[1] Russian Journal of General Chemistry, 2003, vol. 73, # 2, p. 202 - 203
22
[ 108-86-1 ]
[ 22859-57-0 ]
[ 2751-90-8 ]
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[1] Synthesis, 1980, # 7, p. 551 - 554
23
[ 2588-88-7 ]
[ 1034-39-5 ]
[ 2751-90-8 ]
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[1] Russian Journal of Organic Chemistry, 2001, vol. 37, # 12, p. 1794 - 1794
24
[ 108-86-1 ]
[ 2751-90-8 ]
[ 3376-52-1 ]
Reference：
[1] Russian Journal of General Chemistry, 1998, vol. 68, # 4, p. 566 - 569
25
[ 1079-66-9 ]
[ 1707-03-5 ]
[ 2751-90-8 ]
[ 791-28-6 ]
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[ 108-86-1 ]
[ 14311-22-9 ]
[ 2751-90-8 ]
[ 3878-45-3 ]
[ 791-28-6 ]
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[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
27
[ 108-86-1 ]
[ 829-85-6 ]
[ 2751-90-8 ]
[ 603-35-0 ]
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[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
28
[ 1079-66-9 ]
[ 2751-90-8 ]
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[1] Synthesis, 1980, # 7, p. 551 - 554
29
[ 108-86-1 ]
[ 1079-66-9 ]
[ 1707-03-5 ]
[ 2751-90-8 ]
[ 791-28-6 ]
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[ 108-86-1 ]
[ 20472-49-5 ]
[ 1530-32-1 ]
[ 2751-90-8 ]
[ 3878-45-3 ]
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[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
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[ 506-68-3 ]
[ 2751-90-8 ]
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[1] Angewandte Chemie - International Edition, 2014, vol. 53, # 27, p. 6893 - 6897
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[ 603-35-0 ]
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[1] Bulletin of the Chemical Society of Japan, [2] Bulletin of the Chemical Society of Japan, 1954, vol. 27, p. 509 - 515
[3] , Gmelin Handbook: Ni: MVol.C2, 8.18.1, page 1041 - 1052,
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[ 603-35-0 ]
[ 2751-90-8 ]
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[1] Justus Liebigs Annalen der Chemie, 1970, vol. 732, p. 97 - 106
Preparation of the Precursor To dry a mixture of 609 g of potassium fluoride in 2.3 1 of sulpholane, 500 ml of liquid are distilled off at 145 C. and 20 mbar. 1054 g of 5-chloro-4,6-difluoro-pyrimidine (DE-A 384358) and 25 g of tetraphenylphosphonium bromide are subsequently added, 5 bar of nitrogen are applied and the mixture is stirred at 240 C. for 24 hours, the pressure increasing to 11 bar. The reaction mixture is cooled to 80 C. and vented. The mixture is then slowly heated again at atmospheric pressure, and the product is distilled off. Once the bottom temperature has reached 200 C., the pressure is lowered to 150 mbar to accelerate the distillation and to obtain more product. Altogether, 664 g (70.7% of theory) of 4,5,6-trifluoropyrimidine of boiling point 86 to 87 C. are obtained. The logp values are determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile/0.1% aqueous phosphoric acid).
With potassium fluoride; nitrogen; In thiophene;
Example (VI-1) To dry a mixture of 609 g of potassium fluoride in 2.3 l of sulpholane, 500 ml of liquid are distilled off at 145 C. and 20 mbar. 1054 g of 5-chloro-4,6-difluoropyrimidine (DE-A 383558) and 25 g of tetraphenylphosphonium bromide are then added, a nitrogen pressure of 5 bar is applied and the mixture is stirred at 240 C.for 24 hours, during which the pressure increases to 11 bar. The reaction mixture is cooled to 80 C. and the pressure is released. At atmospheric pressure, the mixture is then once again slowly heated and the product is distilled off. When the temperature of the bottom has reached 200 C., the pressure is reduced to 150 mbar to speed up the distillation and to obtain more product. A total of 664 g (70.7% of theory) of 4,5,6-trifluoropyrimidine of boiling point 86 to 87 C. is obtained.
With potassium fluoride; nitrogen; In thiophene;
Preparation of the precursor: A mixture of 609 g of potassium fluoride in 2.3 l of sulpholan is dried by distilling off 500 ml of liquid at 145 C. and 20 mbar. 1054 g of 5-chloro-4,6-difluoropyrimidine (DE-A 3843558) and 25 g of tetraphenylphosphonium bromide are added, a nitrogen pressure of 5 bar is applied and the mixture is stirred at 240 C. for 24 hours, in the course of which the pressure increases to 11 bar. The reaction mixture is cooled to 80 C. and vented. The mixture is then slowly heated at atmospheric pressure, and the product is distilled off. Once the bottom temperature has reached 200 C., the pressure is lowered to 150 mbar to accelerate the distillation and to obtain further product. This gives a total of 664 g (70.7% of theory) of 4,5,6-trifluoropyrimidine of boiling point 86 to 87 C.
EXAMPLE 1 5-Fluoro-thiophene-2-carbonitrile A mixture of <strong>[16689-02-4]5-nitro-thiophene-2-carbonitrile</strong> (5.0 g, 32 mmol.), potassium fluoride (9.4 g, 162 mmol), tetraphenylphosphonium bromide (1.25 g, 3 mmol) and phthaloyl dichloride (4.3 mL, 32 mmol) in Sulfolane (100 mL) was heated to 180 C. for 2 hours. The mixture was poured into water (500 mL) and extracted two times with 250 mL diethyl ether. The organic extracts were combined, washed with 1N NaOH (80 mL), two times with 80 mL water, brine (80 mL), dried (MgSO4) and concentrated in vacuo to give an oil. Flash chromatography on silica gel eluding with diethyl ether:pentane (1:3) afforded an amber oil. Distillation yielded 2.4 g (63%) of the title product as a clear oil (bp 171-3 C./760 mm Hg). 1 H-NMR (CDCl3): delta 7.32 (m, 1H), 6.55 (m, 1H). GC-MS (m/e, %): 127 (M+, 100).
2.4 g (63%)
With potassium fluoride; In sulfolane;
EXAMPLE 1 5-Fluoro-thiophene-2-carbonitrile A mixture of <strong>[16689-02-4]5-nitro-thiophene-2-carbonitrile</strong> (5.0 g, 32 mmol.), potassium fluoride (9.4 g, 162 mmol), tetraphenylphosphonium bromide (1.25 g, 3 mmol) and phthaloyl dichloride (4.3 mL, 32 mmol) in Sulfolane (100 mL) was heated to 180 C. for 2 hours. The mixture was poured into water (500 mL) and extracted two times with 250 mL diethyl ether. The organic extracts were combined, washed with 1N NaOH (80 mL), two times with 80 mL water, brine (80 mL), dried (MgSO4) and concentrated in vacuo to give an oil. Flash chromatography on silica gel eluding with diethyl ether:pentane (1:3) afforded an amber oil. Distillation yielded 2.4 g (63%) of the title product as a clear oil (bp 171-3 C./760 mm Hg). 1 H-NMR (CDCl3): delta7.32 (m, 1H), 6.55 (m, 1H). GC-MS (m/e, %): 127 (M+, 100).
126a. 3-Bromo-2-fluoro-5-nitropyridine <strong>[5470-17-7]3-Bromo-2-chloro-5-nitropyridine</strong> (119 g, 0.500 mol, prepared according to V. Koch and S. Schnatterer, Synthesis, 1990, 497-498), potassium fluoride (79.5 g, 1.37 mol), and tetraphenylphosphonium bromide (109 g, 0.260 mol) were combined in acetonitrile (1.5 L) and heated at reflux for 4 days until GLC indicated complete consumption of the <strong>[5470-17-7]3-bromo-2-chloro-5-nitropyridine</strong>. The volume of the mixture was reduced to 750 mL in vacuo, then the residual liquid was diluted with 2 L of ether. The mixture was filtered and the filtrate concentrated. The residue was triturated with hot hexane, and the combined hexane extracts were concentrated to give 62.8 g (54%) of the title compound: 1 H NMR (DMSO-d6 300 MHz) delta 9.14 (m, 2H).
62.8 g (54%)
With potassium fluoride; In acetonitrile;
131a. 3-Bromo-2-fluoro-5-nitropyridine <strong>[5470-17-7]3-Bromo-2-chloro-5-nitropyridine</strong> (119 g, 0.500 mol, prepared according to V. Koch and S. Schnatterer, Synthesis, 1990, 497-498), potassium fluoride (79.5 g, 1.37 mol), and tetraphenylphosphonium bromide (109 g, 0.260 mol) were combined in acetonitrile (1.5 L) and heated at reflux for 4 days until GLC indicated complete consumption of the <strong>[5470-17-7]3-bromo-2-chloro-5-nitropyridine</strong>. The volume of the mixture was reduced to 750 mL in vacuo then and diluted with 2 L of ether. The mixture was filtered and the filtrate concentrated. The residue was triturated with hot hexane (2*1 L then 2*0.5 L) and the combined hexane extracts were concentrated to give 62.8 g (54%) of the title compound: 1 H NMR (DMSO-d6 300 MHz) delta 9.14 (m, 2H).
EXAMPLE 1 Preparation of Dioxydiphthalic Anhydride A solution of 21.7 grams (0.1 mole) of <strong>[942-06-3]4,5-dichlorophthalic anhydride</strong> in 40 grams of sulfolane was heated and maintained at 210°-215° C. while 0.215 grams of tetraphenylphosphonium bromide was added, followed by the incremental addition of 13.82 grams (0.1 mole) of potassium carbonate over a period of about 4 hours. The temperature was maintained an additional hour and the reaction mixture was then cooled to room temperature. Acetone (100 ml) was added and mixed. The reaction mixture was filtered and the solids washed consecutively with another 100 ml of acetone, two 100 ml portions of water, and again with 100 ml of acetone, to yield about 15 grams of brown solid. After drying, the solid was recrystallized from about 225 grams of 1,2,4-trichlorobenzene to yield 12.5 grams of a tan colored crystalline solid. Mass spectral analysis indicated the product to have a molecular weight of 324 with a fragmentation consistent with dioxydiphthalic anhydride. The identification of dioxydiphthalic anhydride was confirmed by infra-red analysis and C13 NMR (CP/MAS).
With potassium carbonate; In sulfolane; acetone;
EXAMPLE 1 Preparation of Dioxydiphthalic Anhydride A solution of 21.7 grams (0.1 mole) of <strong>[942-06-3]4,5-dichlorophthalic anhydride</strong> in 40 grams of sulfolane was heated and maintained at 210°-215° C. while 0.215 grams of tetraphenylphosphonium bromide was added followed by the incremental addition of 13.82 grams (0.1 mole) of potassium carbonate over a period of about 4 hours. The temperature was maintained an additional hour and the reaction mixture was then cooled to room temperature. Acetone (100 ml) was added and mixed. The reaction mixture was filtered and the solids washed consecutively with another 100 ml of acetone, two 100 ml portions of water, and again with 100 ml of acetone, to yield about 15 grams of brown solid. After drying, the solid was recrystallized from about 225 grams of 1,2,4-trichlorobenzene to yield 12.5 grams of a tan colored crystalline solid. Mass spectral analysis indicated the product to have a molecular weight of 324 with a fragmentation consistent with dioxydiphthalic anhydride. The identification of dioxydiphthalic anhydride was confirmed by infra-red analysis and C13 NMR (CP/MAS).
With potassium carbonate; In sulfolane; acetone;
EXAMPLE 1 Preparation of Dioxydiphthalic Anhydride A solution of 21.7 grams (0.1 mole) of <strong>[942-06-3]4,5-dichlorophthalic anhydride</strong> in 40 grams of sulfolane was heated and maintained at 210°-215° C. while 0.215 grams of tetraphenylphosphonium bromide was added followed by the incremental addition of 13.82 grams (0.1 mole) of potassium carbonate over a period of about 4 hours. The temperature was maintained an additional hour and the reaction mixture was then cooled to room temperature. Acetone (100 ml) was added and mixed. The reaction mixture was filtered and the solids washed consecutively with another 100 ml of acetone, two 100 ml portions of water, and again with a 100 ml of acetone, to yield about 15 grams of brown solid. After drying, the solid was recrystallized from about 225 grams of 1,2,4-trichlorobenzene to yield 12.5 grams of a tan colored crystalline solid. Mass spectral analysis indicated the product to have a molecular weight of 324 with a fragmentation consistent with dioxydiphthalic anhydride. The identification of dioxydiphthalic anhydride was confirmed by infra-red analysis and C13 NMR (CP/MAS).
With potassium carbonate; In sulfolane; acetone;
EXAMPLE 6 Preparation of Dioxydiphthalic Anhydride A solution of 21.7 grams (0.1 mole) of <strong>[942-06-3]4,5-dichlorophthalic anhydride</strong> in 40 grams of sulfolane was heated and maintained at 210-215° C. while 0.215 grams of tetraphenylphosphonium bromide was added followed by the incremental addition of 13.82 grams (0.1 mole) of potassium carbonate over a period of about 4 hours. The temperature was maintained an additional hour and the reaction mixture was then cooled to room temperature. Acetone (100 ml) was added and mixed. The reaction mixture was filtered and the solids washed consecutively with another 100 ml of acetone, two 100 ml portions of water, and again with a 100 ml of acetone, to yield about 15 grams of brown solid. After drying, the solid was recrystallized from about 225 grams of 1,2,4-trichlorobenzene to yield 12.5 grams of a tan colored crystalline solid. Mass spectral analysis indicated the product to have a molecular weight of 324 with a fragmentation consistent with dioxydiphthalic anhydride. The identification of dioxydiphthalic anhydride was confirmed by infra-red analysis and C13 NMR (CP/MAS).
With potassium fluoride; In sulfolane; water; acetone;
EXAMPLE 2 Preparation of Dioxydiphthalic Anhydride 4,5-Difluorophthalic anhydride (18.4 grams, 0.1 mole) was dissolved in 40 grams of anhydrous sulfolane and heated to 165 c. with stirring. <strong>[2751-90-8]Tetraphenylphosphonium bromide</strong> (0.184 grams, 0.0004 mole) and 1.8 grams (0.10 mole) of water were added and the temperature increased to 200 C. Anhydrous potassium fluoride (23.3 grams, 0.4 mole) was added with stirring. The reaction mixture was held at about 200 C. with stirring for about 3 1/2 hours at which time another 0.2 grams of water was added and the reaction mixture was maintained at temperature for an additional hour. The reaction mixture was cooled to less than 150 C. and 35 grams of acetone added and the solids filtered off. The solids were washed with acetone followed by three 100 ml washes with distilled water. The solid material was dried at 150 C. for 16 hours to yield 15.5 grams (95.7% yield) of dioxydiphthalic anhydride.
95.7%
With potassium fluoride; In sulfolane; water; acetone;
EXAMPLE 2 Preparation of Dioxydiphthalic Anhydride 4,5-Difluorophthalic anhydride (18.4 grams, 0.1 mole) was dissolved in 40 grams of anhydrous sulfolane and heated to 165 C. with stirring. <strong>[2751-90-8]Tetraphenylphosphonium bromide</strong> (0.184 grams, 0.0004 mole) and 1.8 grams (0.10 mole) of water were added and the temperature increased to 200 C. Anhydrous potassium fluoride (23.3 grams, 0.4 mole) was added with stirring. The reaction mixture was held at about 200 C. with stirring for about 31/2 hours at which time another 0.2 grams of water was added and the reaction mixture was maintained at temperature for an additional hour. The reaction mixture was cooled to less than 150 C. and 35 grams of acetone added and the solids filtered off. The solids were washed with acetone followed by three 100 ml washes with distilled water. The solid material was dried at 150 C. for 16 hours to yield 15.5 grams (95.7% yield) of dioxydiphthalic anhydride.
95.7%
With potassium fluoride; In sulfolane; water; acetone;
EXAMPLE 7 Preparation of Dioxydiphthalic Anhydride 4,5-Difluorophthalic anhydride (18.4 grams, 0.1 mole) was dissolved in 40 grams of anhydrous sulfolane and heated to 165 C. with stirring. <strong>[2751-90-8]Tetraphenylphosphonium bromide</strong> (0.184 grams, 0.0004 mole) and 1.8 grams (0.10 mole) of water were added and the temperature increased to 200 C. Anhydrous potassium fluoride (23.3 grams, 0.4 mole) was added with stirring. The reaction mixture was held at about 200 C. with stirring for about 31/2 hours at which time another 0.2 grams of water was added and the reaction mixture was maintained at temperature for an additional hour. The reaction mixture was cooled to less than 150 C. and 35 grams of acetone added and the solids filtered off. The solids were washed with acetone followed by three 100 ml washes with distilled water. The solid material was dried at 150 C. for 16 hours to yield 15.5 grams (95.7% yield) of dioxydiphthalic anhydride.
EXAMPLE 2 87 g of potassium fluoride in 225 ml of tetramethylene sulphone were placed in a stirred apparatus and partially distilled at 20 mbar for the purpose of drying. 96.5 g of 2,4-dichloro-5-fluorobenzaldehyde and 5 g of tetraphenylphosphonium bromide were then added and the mixture was heated for 5 hours at 190 C. while stirring. The reaction mixture was subsequently distilled at 20 mbar. This gave 68 g of distillate containing 78% by weight of 2,4,5-trifluorobenzaldehyde and 9.4% by weight of 2-chloro-4,5-difluorobenzaldehyde.
d) 812 g (14 mol) of potassium fluoride and 1400 ml of tetramethylene sulphone are subjected to incipient distillation at 20 mbar (quantity of distillate: 100 ml) in a stirred V4A steel apparatus. Then 40 g of tetraphenylphosphonium bromide and a mixture of 795 g (2.8 mm) of 2H-tetrachlorobenzotrifluoride and 170 g (0.78 mm) of 5-chloro-2,3,4-trifluorobenzotrifluoride are added and the mixture is stirred for 18 hours at 210 C. under the autogenous pressure (max. pressure 3.4 bar). Distillation yields 747 g of a crude distillate which is redistilled in a rotating strip column. 396 g of 2H-tetrafluorobenzotrifluoride and 318 g of 5-chloro-2,3,4-trifluorobenzotrifluoride are obtained. The recovery rate of the isolated yield is 90.5%.
18a. 2-fluoro-3-methyl-5-nitropyridine 2-Chloro-3-methyl-5-nitropyridine (15 g, 86.9 mmol; from Maybridge Chemical Co.), KF (12 g, 258 mmol) and tetraphenylphosphonium bromide (20 g, 47.7 mmol; Aldrich) were combined in 200 mL of acetonitrile and heated at reflux for 4 days. The mixture was diluted with Et2 O (500 mL) and filtered, and the filtrate was concentrated. The residue was triturated with hot hexane (4*200 mL), and the hexane solutions were combined and concentrated to afford the title compound as a solid (8.4 g, 60%): 1 H NMR (DMSO-d6, 300 MHz) delta2.42 (s, 3H), 8.43 (m, 1H), 8.95 (dd, J=1.6 Hz, 1H); MS (CI/NH3) m/z: 157 (M+H)+.
EXAMPLE 26 4-Chlorophthalic anhydride (30 g, 16o mmol), tetraphenyl phosphonium bromide (0.3 g, 0.7 mmol), and 2,6-dichlorobenzoic acid (0.08 g, 0.4 mmol) were heated to approximately 220 C. Potassium carbonate (7.95 g, 58 mmol) was added over 45 minutes. The reaction was sampled after addition of the potassium carbonate and showed a 28.3% conversion to 4,4'-oxydiphthalic anhydride. The reaction mixture was diluted with 1,2,4-trichlorobenzene (90 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize and was collected, washed with 1,2,4-trichlorobenzene followed by hexane, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 11.4 g.
EXAMPLE 21 4-Chlorophthalic anhydride (30 g, 160 mmol) and 1,2,4-trichlorobenzene (60 g) were heated to reflux (approximately 224 C.) and tetraphenyl phosphonium bromide (Hokko Chemical, 0.30 g, 0.7 mmol) and 4-methylbenzoic acid (Aldrich, 0.05 g, 0.4 mmol) were added. Dry potassium carbonate (7.95 g, 58 mmol) was then added in portions over one hour. The reaction was monitored by GC and showed 3.7% conversion to 4,4'-oxydiphthalic anhydride (ODPAN) 4 hours after addition of carbonate was completed.
EXAMPLE 39 4-Chlorophthalic anhydride (7.5 g, 41.1 mmol) and 1,2,4-trichlorobenzene (Aldrich, 7.5 g) were heated to reflux and dry potassium carbonate (0.6 g, 4.3 mmol) was added. After refluxing for 30 minutes, 4-benzoyloxyphthalic anhydride (0.024 g, 0.1 mmol), tetraphenyl phosphonium bromide (Hokko Chemical, 0.08 g, 0.2 mmol), and potassium carbonate (2.9 g, 21 mmol) were added. The reaction was heated for 7 hours and was then diluted with 1,2,4-trichlorobenzene (50 g), filtered, and the 4,4'-oxydiphthalic anhydride allowed to crystallize. The solid was collected, washed with solvent, and dried in an air circulating oven to give crude 4,4-oxydiphthalic anhydride, 3.56 g (56% isolated yield).
EXAMPLE 38 4-Chlorophthalic anhydride (7.5 g, 41.1 mmol) and 1,2,4-trichlorobenzene (Aldrich, 7.5 g) were heated to reflux and dry potassium carbonate (0.55 g, 4.1 mmol) was added. After refluxing for 30 minutes, 4-(3-nitrobenzoyl)oxyphthalic anhydride (0.03 g, 0.1 mmol), tetraphenyl phosphonium bromide (Hokko Chemical, 0.08 g, 0.2 mmol), and potassium carbonate (2.9 g, 21 mmol) were added. The reaction was heated for 7 hours and was then diluted with 1,2,4-trichlorobenzene (50 g), filtered, and the 4,4'-oxydiphthalic anhydride allowed to crystallize. The solid was collected, washed with solvent, and dried in an air circulating oven to give crude 4,4-oxydiphthalic anhydride, 3.9 g (61% isolated yield).
4-(4-methylbenzoyl)oxyphthalic anhydride[ No CAS ]
[ 2751-90-8 ]
[ 120-82-1 ]
[ 1823-59-2 ]
Yield
Reaction Conditions
Operation in experiment
24%
With potassium carbonate;
EXAMPLE 41 4-Chlorophthalic anhydride (7.5 g, 41.1 mmol) and 1,2,4-trichlorobenzene (Aldrich, 7.5 g) were heated to reflux and dry potassium carbonate (0.6 g, 4.3 mmol) was added. After refluxing for 30 minutes, 4-(4-methylbenzoyl)oxyphthalic anhydride (0.029 g, 0.10 mmol), tetraphenyl phosphonium bromide (Hokko Chemical, 0.08 g, 0.2 mmol), and potassium carbonate (2.9 g, 21 mmol) were added. The reaction was heated for 10 hours and was then diluted with 1,2,4-trichlorobenzene (30 g), filtered, and the 4,4'-oxydiphthalic anhydride allowed to crystallize. The solid was collected, washed with solvent, and dried in an air circulating oven to give crude 4,4-oxydiphthalic anhydride, 1.53 g (24% isolated yield).
EXAMPLE 16 4-Chlorophthalic anhydride (30 g, 160 mmol) and 1,2,4-trichlorobenzene (60 g) were heated to reflux (approximately 224 C.) and tetraphenyl phosphonium bromide (Hokko Chemical, 0.30 g, 0.7 mmol) and 2-chlorobenzoic acid (Aldrich, 0.06 g, 0.4 mmol) were added. Dry potassium carbonate (7.95 g, 58 mmol) was then added in portions over one hour. The reaction was monitored by GC and showed 14.9% conversion to 4,4'-oxydiphthalic anhydride (ODPAN) 4 hours after addition of carbonate was completed.
EXAMPLE 12 4-Chlorophthalic anhydride (30 g, 160 mmol) and 1,2,4-trichlorobenzene (30 g) were heated to reflux (approximately 224 C.) and tetraphenyl phosphonium bromide (Hokko Chemical, 0.30 g, 0.7 mmol) and 4-chlorobenzoic acid (Aldrich, 0.06 g, 0.4 mmol) were added. Dry potassium carbonate (7.95 g, 58 mmol) was then added in portions over one hour. The reaction was monitored by GC and showed 62.9% conversion to 4,4'-oxydiphthalic anhydride (ODPAN) 3 hours after addition of carbonate was completed.
COMPARATIVE EXAMPLE 2 4-Chlorophthalic anhydride (7.5 g, 41.1 mmol) and 1,2,4-trichlorobenzene (Aldrich, 7.5 g) were heated to reflux and dry potassium carbonate (0.7 g, 5.1 mmol) was added. After refluxing for 30 minutes, tetraphenyl phosphonium bromide (Hokko Chemical 0.075 g, 0.2 mmol), and potassium carbonate (2.9 g, 21 mmol) were added. The reaction was heated for 22.5 hours and was then diluted with 1,2,4-trichlorobenzene (22 g), filtered, and the 4,4'-oxydiphthalic anhydride allowed to crystallize. The solid was collected, washed with solvent, and dried in an air circulating oven to give crude 4,4-oxydiphthalic anhydride, 0.6 g (10% isolated yield).
EXAMPLE 40 4-Chlorophthalic anhydride (7.5 g, 41.1 mmol) and 1,2,4-trichlorobenzene (Aldrich, 7.5 g) were heated to reflux and dry potassium carbonate (0.6 g, 4.3 mmol) was added. After refluxing for 30 minutes, 4-(4-methoxybenzyol)oxyphthalic anhydride (0.04 g, 0.1 mmol), tetraphenyl phosphonium bromide (Hokko Chemical, 0.08 g, 0.2 mmol), and potassium carbonate (2.84 g, 20.5 mmol) were added. The reaction was heated for 6.5 hours and was then diluted with 1,2,4-trichlorobenzene (30 g), filtered, and the 4,4'-oxydiphthalic anhydride allowed to crystallize. The solid was collected, washed with solvent, and dried in an air circulating oven to give crude 4,4-oxydiphthalic anhydride, 0.62 g (10% isolated yield).
EXAMPLE 5 4-Chlorophthalic anhydride (30 g, 160 mmol) and 2,5-dichlorotoluene (Aldrich, 15 g) were heated to reflux at approximately 230 C. Dry potassium carbonate (1.26 g, 9.1 mmol) was added and the mixture heated for about 1 hour. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol). The reaction was heated for about 5 hours and then was diluted with 2,5-dichlorotoluene (60 g) and filtered. The 4,4-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 20.9 g.
EXAMPLE 3 4-Chlorophthalic anhydride (30 g, 160 mmol) and 2,4-dichlorotoluene (Aldrich, 30 g) were heated to reflux at approximately 218 C. Dry potassium carbonate (1.32 g, 12 mmol) was added and the mixture heated for about 30 minutes. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol) over 45 minutes. The reaction was heated for about 6 hours and then was diluted with 2,4-dichlorotoluene (60 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 20.3 g.
EXAMPLE 1 4-Chlorophthalic anhydride (30 g, 160 mmol) and benzonitrile (Aldrich, 30 g, containing 110 ppm water) were heated to reflux. Dry potassium carbonate (1.2 g, 8.7 mmol) was added and the mixture heated for 30 minutes. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol). The reaction was heated for about 9 hours and then was diluted with benzonitrile (30 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 24.7 g.
With potassium carbonate;
EXAMPLE 24 4-Chlorophthalic anhydride (30 g, 160 mmol), tetraphenyl phosphonium bromide (0.3 g, 0.7 mmol), and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were heated to approximately 220 C. Potassium carbonate (7.95 g, 58 mmol) was added over 45 minutes. The reaction was sampled after an additional 30 minutes and showed a 68.3% conversion to 4,4'-oxydiphthalic anhydride. The reaction mixture was diluted with 1,2,4-trichlorobenzene (90 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize and was collected, washed with 1,2,4-trichlorobenzene followed by hexane, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 15.6 g (88% yield based on conversion).
With potassium carbonate;
EXAMPLE 6 4-Chlorophthalic anhydride (30 g, 160 mmol) and mixed dichlorotoluenes (15 g) were heated to reflux. Dry potassium carbonate (1.29 g, 9.3 mmol) was added and the mixture heated for about 1 hour. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol). The reaction was heated for about 10 hours and then was diluted with mixed dichlorotoluenes (60 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 18.4 g.
With potassium carbonate; In water; nitrobenzene;
EXAMPLE 11 4-Chlorophthalic anhydride (30 g, 160 mmol), and nitrobenzene (Aldrich, 30 g, containing 500 ppm water) were heated to reflux. Dry potassium carbonate (1.32 g, 9.6 mmol) was added and the mixture heated for 30 minutes. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol). The reaction was heated for about 9 hours and then was diluted with nitrobenzene (30 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 10.0 g.
EXAMPLE 2 4-Chlorophthalic anhydride (30 g, 1 60 mmol) and 1,2-dichlorobenzene (Aldrich, 30 g) were heated to reflux. Dry potassium carbonate (1.04 g, 7.5 mmol) was added and the mixture heated for 30 minutes. Tetraphenyl phosphonium bromide (0.36 g, 0.9 mmol) and 4-chlorobenzoic acid (0.06 g, 0.4 mmol) were added followed by addition of potassium carbonate (11.4 g, 82.2 mmol). The reaction was heated for about 10 hours and then was diluted with 1,2-dichlorobenzene (60 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize, was washed with solvent, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 22.3 g.
EXAMPLE 25 4-Chlorophthalic anhydride (30 g, 160 mmol), tetraphenyl phosphonium bromide (0.3 g, 0.7 mmol), and 2,5-dichlorobenzoic acid (0.08 g, 0.4 mmol) were heated to approximately 220 C. Potassium carbonate (7.95 g, 58 mmol) was added over 45 minutes. The reaction was sampled after addition of the potassium carbonate and showed a 24.9% conversion to 4,4'-oxydiphthalic anhydride. The reaction was heated for an additional 45 minutes. The reaction mixture was diluted with 1,2,4-trichlorobenzene (90 g) and filtered. The 4,4'-oxydiphthalic anhydride was allowed to crystallize and was collected, washed with 1,2,4-trichlorobenzene followed by hexane, and dried in an air circulating oven at 120 C. to give crude 4,4'-oxydiphthalic anhydride, 12.9 g.
EXAMPLE 4 This example illustrates the manner in which 5-chloro-4,4'-oxydiphthalic anhydride may be prepared. A solution of equal molar amounts of <strong>[118-45-6]4-chlorophthalic anhydride</strong> (18.2 g, 0.1 mole) and 4,5-dichlorophthalic anhydride (21.7 g, 0.1 mole) and tetraphenylphosphonium bromide (0.215 g) in 60 g of sulfolane is heated to 180-210 C. Temperature is maintained, with stirring, while 0.05 mole (6.91 g) of potassium carbonate is added over a period of about one hour. The temperature is maintained for an additional two hours, then lowered to room temperature.
EXAMPLE 5 Into a three-necked 50 ml flask equipped with a condenser and a stirrer, 1.9 g (33 mmol) of spray-dried potassium fluoride (purchased from Laporte Industry), 1.1 g (2.5 mmol) of <strong>[2751-90-8]tetraphenyl phosphonium bromide</strong>, 0.7 g (2.5 mmol) of 18-crown-6 and 6.4 g (25 mmol) of ethyl 3,4,5-trichlorobenzoate were introduced, and the mixture was heated in an oil bath and reacted under a nitrogen atmosphere at 210 C. for 2 hours. The reactor was cooled, and the mixture was diluted with 40 ml of toluene. Inorganic salts were filtered off, and toluene was concentrated to give the residue, which was distilled under reduced pressure to obtain 3.4 g of ethyl 3,5-dichloro-4-fluorobenzoate. The yield was 57%. The physical properties are shown below. Boiling point: 109-115 C./5 mmHg Mass m/e: 236(M+), 208(M+ --CH2 =CH2)
With potassium fluoride; In sulfolane; water; toluene;
EXAMPLE 1 Into a 50 ml three-necked flask equipped with a condenser and a stirrer, 6.0 g (104 mmol) of spray-dried potassium fluoride (purchased from Morita Kagaku Kogyo K.K.), 1.7 g (4 mmol) of <strong>[2751-90-8]tetraphenyl phosphonium bromide</strong>, 12 g of anhydrous sulfolane and 20 ml of toluene, and the mixture was heated and stirred in an oil bath to distill off toluene and to conduct azeotropic removal of water. The mixture was heated at 140 C., and then the pressure was reduced to a level of 45 mmHg to distill off substantially all the remaining toluene. The content of the flask was cooled to 100 C. and substituted by nitrogen gas. Then, 13.1 g (40 mmol) of neopentyl 2,3,4,5-tetrachlorobenzoate was added thereto, and the mixture was reacted under a nitrogen gas atmosphere at 190 C. under stirring for 15 hours. After completion of the reaction, the reaction mixture was cooled and after an addition of 100 ml of toluene, subjected to filtration to remove inorganic substances. The filtrate was washed three times with 200 ml of water. The toluene layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure by a rotary evaporator to obtain 11.0 g of a brown oily substance. The oily substance thus obtained was distilled under reduced pressure to obtain 7.2 g of neopentyl 3,5-dichloro-2,4-difluorobenzoate as a colorless oil. The yield was 61%.
EXAMPLE 4 Synthesis of N-ethyl-tetrafluorophthalimide (Process using sulfolane as solvent) In a 1 l three neck distillation flask was placed 500 ml of sulfolane and about 100 ml thereof was distilled off under a reduced pressure. Thereafter 93.9 g (0.3 mol) of N-ethyl-tetrachlorophthalimide, 104.4 g (1.8 mols) of spray-dried potassium fluoride, and 10.4 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> were added thereto and they were reacted for 2 hours at 150 to 160 C. with stirring. After cooling, the reaction mixture was poured into 500 ml of toluene, washed three times with 2 l of an aqueous sodium chloride solution, dried with anhydrous magnesium sulfate, and concentrated by distillation under a reduced pressure to provide 56 g (yield 75.6%) of N-ethyl-tetrafluorophthalimide as yellow ocher-color crystals. The analysis of the product was as follows: 19 F NMR (ppm/acetone, external standard CF3 CO2 H): 60, 67(d-d, each 2F, JFF =8.09, 19.76 Hz). 1 H NMR (ppm/CDCl3): 1.26(3H, t, J=8 Hz),. 3.68(2H, q, J=8 Hz) IR (cm-1 /KBr): nuC=O 1700.
EXAMPLE 7 Synthesis of N-isopropyl-tetrafluorophthalimide (Process using sulfolane as solvent) In a 1 l three neck distillation flask was placed 500 ml of sulfolane and then about 100 ml thereof was distilled off under a reduced pressure. Thereafter, 81.8 g (0.25 mol) of N-isopropyl-tetrachlorophthalimide, 87 g (1.5 mols) of spray-dried potassium fluoride, and 8.7 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> were added thereto and they were reacted for 3 hours at 140 to 150 C. with stirring. After cooling, the reaction mixture was poured into 500 ml of toluene, washed three times with 2 l of an aqueous sodium chloride solution, dried with anhydrous magnesium sulfate, and concentrated by distillation under a reduced pressure to provide 56 g (yield 75.6%) of N-isopropyl-tetrafluorophthalimide as yellow ocher-color crystals, analyzed as follows: 19 F NMR (ppm/acetone, external standard CF3 CO2 H): 61, 67(d-d, each 2F, JFF =7.71, 18.91 Hz). 1 H NMR (ppm/CDCl3): 1.46(6H, d, J=7 Hz), 4.44(1H, hep, J=7 Hz).
4,5,6,7-tetrafluoro-2-benzylisoindoline-1,3-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
With potassium fluoride; In sulfolane; toluene;
EXAMPLE 12 Synthesis of N-benzyl-tetrafluorophthalimide In a 300 ml three neck distillation flask were placed 200 ml of sulfolane and then about 50 ml thereof was distilled off under a reduced pressure. Thereafter, 75 g (0.2 mol) of N-benzyltetrachlorophthalimide, 69.6 g (1.2 mols) of spray-dried potassium fluoride, and 4.2 g (0.01 mol) of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> were added thereto and the mixture was reacted for one hour at 150 to 160 C. with stirring. After cooling, the reaction mixture was poured into 400 ml of toluene, and the toluene layer formed was washed four times with 400 ml of an aqueous sodium chloride solution, dried with anhydrous magnesium sulfate, and concentrated by distillation under a reduced pressure to provide 55 g (yield 89%) of N-benzyltetrafluorophthalimide as grey crystals, analyzed as follows: 19 F NMR (ppm/ethyl acetate, external standard CF3 CO2 H): 59.3, 66.7(d-d, each 2F, JFF =8.47, 19.76 Hz). 1 H NMR (ppm/CDCl3): 4.72 (s, 2H), 7.05 to 7.45(m, 5H). IR (cm-1 /KBr) nuC=O 1705.
Comparison Example 6 Preparing 2,4-difluoronitrobenzene by Reacting 2,4-dichloronitrobenzene Using tetraphenylphosphonium bromide as Catalyst 192 g (1 mol) of 2,4-dichloronitrobenzene, 550 ml of tetramethylene sulfone, 136.8 g (2.4 mol) of potassium fluoride and 6.29 g (0.015 mol) of tetraphenylphosphonium bromide are employed and the procedure described in Example 7 and 8 is followed.
Comparison Example 1 Preparing 4-nitrofluorobenzene by Reacting 4-nitrobenzene Using tetraphenylphosphonium bromide as Catalyst 157 g (1mol) of 4-nitrochlorobenzene, 400 ml of tetramethylene sulfone, and 62.7 g (1.1 mol) of potassium fluoride, but 4.19 g (0.01 mol) of tetraphenylphosphonium bromide, are employed and the procedure described in Example 1 is followed.
Comparison Example 8 Preparing 2,3-difluoro-5-chloropyridine by Reacting <strong>[823-56-3]2-fluoro-3,5-dichloropyridine</strong> Using tetraphenylphosphonium bromide as Catalyst 166 g (1 mol) of <strong>[823-56-3]2-fluoro-3,5-dichloropyridine</strong>, 68.4 g (1.2 mol) of potassium fluoride and 4.19 g (0.01 mol) of tetraphenylphosphonium bromide are employed and the procedure described in Example 11 is followed. The reaction conditions (reaction temperature, time) and conversion and yield for Example 11 and Comparison Example 8 are given in Table 4 below.
Preparation of Amido-Borate 12; To a slurry of sodium salt of imidazole (4.5 g, 50 mmol) and <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (21 g, 50 mmol) in 200 mL of THF was added triethylborane (9.8 g, 100 mmol) slowly via syringe over 60 minutes and the resulting mixture was stirred overnight at room temperature. The salts formed were filtered and washed with 25 mL of THF twice. The solvent of the filtrate was removed in vacuo to afford the desired product as brown solids. The crude product was used without further purification (27.47 g, 91.2 percent yield).
potassium (trifluoromethyl)trifluoroborate[ No CAS ]
tetraphenylphosphonium dicyanomethoxytrifluoromethylborate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
Example 5. Tetraphenylphosphonium dicyanomethoxytrifluoro- methylborate; K[CF3BF3] (0.2 g, 1.1 mmol) is weighed out into a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and a magnetic stirrer bar. A mixture of trimethylsilyl cyanide and methoxytnmethylsilane (10 ml, -10:1 v/v) is condensed onto the salt. The reaction mixture is stirred at room temperature for 12 hours. All volatile constituents are removed in vacuo, and the residue is dissolved in deionized water (15 ml). Slow dropwise addition of a solution of [Ph4P]Br (0.6 g, 1.4 mmol) in deionized water (30 ml) causes the formation of a colourless precipitate, which is filtered off and subsequently dried in vacuo. The yield of tetraphenylphosphonium dicyanomethoxytrifluoromethylborate is 0.5 g (1.1 mmol), 92% based on the potassium trifluorotrifluoromethylborate, K[CF3BF3], employed. Melting point: 160C; decomposition from 240C. Raman spectroscopy: v (CN) = 2203 cm"1. The product is characterized by N M R-spectroscopy :1H-NMR: delta, ppm = 7.8-7.92 m (4C6H5, 16 H); 7.97-8.05 m (4C6H5, 4 H).13C{ H}-NMR (Cation): delta, ppm = 136.3 s (4 C), 135.6 d (8 C), JC p = 10 Hz, 131.3 d (8 C), JC,P = 13 Hz, 118.9 d (4 C), JC,P = 91 Hz.11B{1H}-NMR: delta, ppm = -13.5 q (1 B), 2JF, B = 33.3 Hz .19F{1H}-NMR: delta, ppm = -71.2 q (CF3, 3F), 2JF, B = 33.4 Hz.Elemental analysis: found, %: C 66.97, H 4.55, N 5.37; calculated for C28H23BF3N2OP: C 66.96, H 4.62, N 5.58.
potassium trimethoxy(trifluoromethyl)boranuide[ No CAS ]
tetraphenylphosphonium dicyanomethoxytrifluoromethylborate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96%
K[CF3B(OCH3)3] (1.1 g, 5.2 mmol) is initially introduced into a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and a magnetic stirrer bar. Trimethylsilyl cyanide (10.0 ml, 74.9 mmol) is condensed in. The reaction mixture is stirred at 70C for 2.5 hours. The volatile constituents are then removed in vacuo, and the residue is dissolved in deionized water (20 ml). An aqueous solution of [Ph4P]Br (2.6 g, 6.2 mmol, 200 ml) is added to the solution. The precipitate is filtered off and dried in vacuo. The yield of tetraphenylphosphonium dicyano-methoxy- trifluoromethylborate is 2.4 g (4.8 mmol), 96% based on the potassium trimethoxytrifluoromethylborate, K[CF3B(OCH3)3], employed. The NMR spectra of the obtained product are conside with spectra described in the Example 5A.
(Ph4P)2[Co(4-cyanobenzene-1,2-dithiolate)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54.6%
Under anaerobic conditions, 1 (0.1 g, 0.48 mmol) was added to a sodium methoxide solution (0.113 g, 1.9 mmol), in methanol (8 mL). After 4 h of stirring, a solution of CoCl2·6H2O (0.06 g, 0.24 mmol) in methanol (4 mL) was added. One hour later, the red solution was filtered and a solution of Ph4PBr (0.2 g, 0.48 mmol) in 4 mL of methanol was added. No precipitate formation was observed. The mixture was allowed to stand overnight at room temperature, and a red polycrystalline precipitate appeared, which was collected and recrystallised from CH2Cl2/hexane to be recovered as dark red platelet crystals (0.14 g, 0.131 mmol, eta = 54.6%). IR (KBr pellet) upsilon? = 3050 (w, Ar-H), 2220 (s, C?N), 1565 (m, C=C), 418 (w, S-Co) cm-1; C62H46CoN2P2S4 (1068.18): Anal. Calc. C 69.71, H 4.34, N 2.26, S 12.01. Found: C 69.43, H 4.19, N 2.18, S 12.31%.
(Ph4P)2[Cu(4-cyanobenzene-1,2-dithiolate)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54.4%
Under anaerobic conditions, 1 (0.1 g, 0.48 mmol) was added to a sodium methoxide solution (0.113 g, 1.9 mmol), in methanol (8 mL). After 4 h of stirring, a solution of CuCl2·2H2O (0.041 g, 0.24 mmol) in methanol (4 mL) was added. One hour later, the red solution was filtered and a solution of Ph4PBr (0.2 g, 0.48 mmol) in 4 mL methanol was added. No precipitate formation was observed. The mixture was layered with isopropanol and allowed to stand overnight at room temperature. A red polycrystalline precipitate appeared, which was collected and recrystallised from CH2Cl2/hexane to be recovered as red crystalline needles (0.14 g, 0.13 mmol, eta = 54.4%). M.p. 209-210 C. IR (KBr pellet) upsilon? = 3042 (w, Ar-H), 2213 (m, C?N), 1583-1482 (s-m, C=C), 421 (w, S-Cu) cm-1; C62H46CuN2P2S4 (1072.79): Anal. Calc. C 69.41, H 4.32, N 2.61, S 11.96. Found: C 69.24, H 4.59, N 2.33, S 12.06%.
4-Cyanobenzene-1,2-dithiol (0.1 g, 0.6 mmol) was dissolved in aqueous NaOH (15 mL, 5%). A solution of Ph4PBr (0.25 g, 0.6 mmol) in EtOH/H2O (1:1) (15 ml) was added, followed by a solution of CoCl2·6H2O (0.07 g, 0.3 mmol) in the same solvent (10 mL). The mixture was cooled and filtered and the precipitate was recrystallised from CH3CN/i-buOH to give 5a as a dark blue powder (0.1 g, 0.14 mmol, eta = 46.6%). M.p. 139-141 C. IR (KBr pellet) upsilon? = 3057 (w, Ar-H), 2210 (s, C?N), 1560 (m, C=C), 415 (w, S-Co) cm-1. C38H26N2CoS4P (728.79): Anal. Calc. C 62.63, H 3.59, N 3.84, S 17.59. Found: C 62.38, H 4.24, N 3.62, S 16.18%.
potassium (pentafluoroethyl)trimethoxyborate[ No CAS ]
[ 1825-61-2 ]
tetraphenylphosphonium dicyano(methoxy)pentafluoroethylborate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
KCN (3.0 g, 46.1 mmol) and KI (0.6 g, 3.9 mmol) are dried for 4 hours at 115 C. in vacuo in a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and a magnetic stirrer bar. Trimethylsilyl chloride (3.0 ml, 2.6 g, 23.6 mmol) is subsequently added, and the reaction mixture is stirred at 100 C. for 3 days. K[C2F5B(OCH3)3] (200 mg, 0.76 mmol) is added in a counterstream of argon, and the mixture is stirred at room temperature for 3 days. The reaction mixture is taken up in 30% H2O2 (20 ml) and stirred for 2 hours. [Ph4P]Br (500 mg, 1.2 mmol) is subsequently dissolved in deionized water (50 ml) and slowly added dropwise to the reaction mixture. The precipitate is filtered off, dried and extracted with acetone (20 ml). The combined acetone phases are evaporated to dryness. The yield of tetraphenylphosphonium dicyanomethoxypentafluoroethylborate is 250 mg (0.45 mmol), 60% based on the potassium trimethoxypentafluoroethylborate, K[C2F5B(OCH3)3], employed. Melting point: 155 C.; decomposition from 280 C. Raman spectroscopy: v (CN)=2206 cm-1. 1H-NMR: delta, ppm=7.8-7.92 m (4C6H5, 16H); 7.97-8.05 m (4C6H5, 4H). 13C{1H}-NMR (Cation): delta, ppm=136.3 s (4C), 135.6 d (8C), JC,P=10 Hz, 131.3 d (8C), JC,P=13 Hz, 118.9 d (4C), JC,P=91 Hz. 11B{1H}-NMR: delta, ppm=-12.7 t (1B), 2JF,B=23.1 Hz. 19F{1H}-NMR: delta, ppm=-82.0 s (CF3, 3F); -128.9 q (CF2, 2F), 2JF,B=23.3 Hz.
potassium (trifluoromethyl)trifluoroborate[ No CAS ]
[ 420-56-4 ]
tetraphenylphosphonium dicyanomethoxytrifluoromethylborate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
K[CF3BF3] (0.2 g, 1.1 mmol) is weighed out into a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and a magnetic stirrer bar. A mixture of trimethylsilyl cyanide and methoxytrimethylsilane (10 ml, 10:1 v/v) is condensed onto the salt. The reaction mixture is stirred at room temperature for 12 hours. All volatile constituents are removed in vacuo, and the residue is dissolved in deionized water (15 ml). Slow dropwise addition of a solution of [Ph4P]Br (0.6 g, 1.4 mmol) in deionized water (30 ml) causes the formation of a colourless precipitate, which is filtered off and subsequently dried in vacuo. The yield of tetraphenylphosphonium dicyanomethoxytrifluoromethylborate is 0.5 g (1.1 mmol), 92% based on the potassium trifluorotrifluoromethylborate, K[CF3BF3], employed. Melting point: 160 C.; decomposition from 240 C. Raman spectroscopy: v (CN)=2203 cm-1. The product is characterized by NMR-spectroscopy: 1H-NMR: delta, ppm=7.8-7.92 m (4C6H5, 16H); 7.97-8.05 m (4C6H5, 4H).13C{1H}-NMR (Cation): delta, ppm=136.3 s (4C), 135.6 d (8C), JC,P=10 Hz, 131.3 d (8C), JC,P=13 Hz, 118.9 d (4C), JC,P=91 Hz.11B{1H}-NMR: delta, ppm=-13.5 q (1B), 2JF,B=33.3 Hz.19F{1H}-NMR: delta, ppm=-71.2 q (CF3, 3F), 2JF,B=33.4 Hz.Elemental analysis: found, %: C, 66.97; H, 4.55; N, 5.37; calculated for C28H23BF3N2OP: C, 66.96; H, 4.62; N, 5.58.
potassium trimethoxy(trifluoromethyl)boranuide[ No CAS ]
[ 1825-61-2 ]
tetraphenylphosphonium dicyanomethoxytrifluoromethylborate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96%
K[CF3B(OCH3)3] (1.1 g, 5.2 mmol) is initially introduced into a cylindrical reaction vessel with a glass valve and PTFE spindle (Young, London) and a magnetic stirrer bar. Trimethylsilyl cyanide (10.0 ml, 74.9 mmol) is condensed in. The reaction mixture is stirred at 70 C. for 2.5 hours. The volatile constituents are then removed in vacuo, and the residue is dissolved in deionized water (20 ml). An aqueous solution of [Ph4P]Br (2.6 g, 6.2 mmol, 200 ml) is added to the solution. The precipitate is filtered off and dried in vacuo. The yield of tetraphenylphosphonium dicyano-methoxytrifluoromethylborate is 2.4 g (4.8 mmol), 96% based on the potassium trimethoxytrifluoromethylborate, K[CF3B(OCH3)3], employed. The NMR spectra of the obtained product are conside with spectra described in the Example 5A.
potassium trifluoro(1,1,2,2,2-pentafluoroethyl)borate[ No CAS ]
[ 1314568-71-2 ]
Yield
Reaction Conditions
Operation in experiment
93%
Example 24Tetraphenylphosphonium cyanodifluoropentafluoroethylborate-[(C5H6)4P][C2F5BF2(CN)] Potassium trifluoropentafluoroethylborate, K[C2F5BF3] (495 mg, 2.2 mmol), is weighed out into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer bar. Trimethylsilyl cyanide (7.0 ml; 52.5 mmol) is condensed in under an argon atmosphere. The reaction mixture is stirred at 100 C. for 5 hour. All volatile constituents are subsequently removed in vacuo. Most of the unreacted trimethylsilyl cyanide (6.1 ml, 45.7 mmol) is recovered by fractional distillation. The residue is dissolved in deionised water (15 ml), and [Ph4P]Br (1.3 g; 3.1 mmol) dissolved in deionised water (150 ml) is added. The precipitate is filtered off and dried in vacuo. The yield of solid colourless tetraphenylphosphonium cyanodifluoropentafluoroethylborate is 1.1 g (2.0 mmol), 93%, based on the potassium trifluoropentafluoroethylborate, K[C2F5BF3], employed. Melting point: 130 C.; decomposition from 310 C. Raman spectroscopy: v (CN)=2211 cm-1.1H-NMR: delta, ppm=7.8-7.92 m (4C6H5, 16H); 7.97-8.05 m (4C6H5, 4H).13C{1H}-NMR (cation): delta, ppm=136.3 s (4C), 135.6 d (8C), JC,P=10 Hz, d (8C), JC,P=13 Hz, 118.9 d (4C), JC,P=91 Hz.11B-NMR: delta, ppm=-2.7 tt (1B), 1JF,B=51.0 Hz, 2JF,B=25.3 Hz.19F-NMR: delta, ppm=-83.3 t (CF3, 3F), 4JF,F=5.2 Hz; -136.3 q (CF2, 2F), 2JF,B=23.3 Hz; -167.2 qq (BF2, 2F), 1JF,B=51.1 Hz, 4JF,F=5.1 Hz.
potassium trifluoro(1,1,2,2,2-pentafluoroethyl)borate[ No CAS ]
[ 1314568-76-7 ]
Yield
Reaction Conditions
Operation in experiment
73%
Example 28 Tetraphenylphosphonium dicyanofluoropentafluoroethylborate-[(C5H6)4P][C2F5BF(CN)2] A solution of potassium trifluoropentafluoroethylborate, K[C2F5BF3] (50 mg, 0.22 mmol), in trimethylsilyl cyanide (0.7 ml, 5.2 mmol) is heated successively at 70 C. for 7 hours, at 100 C. for 5 hours, at 125 C. for 7.5 hours, at 140 C. for 5 hours and then at 150 C. for 72 hours in an NMR tube with a glass valve and a PTFE spindle (Young, London). The solution is evaporated in vacuo, and the residue is taken up in alkaline aqueous solution (0.1 g of KOH, 10 ml), and [Ph4P]Br (0.5 g, 1.2 mmol), dissolved in deionised water (50 ml), is added dropwise. The colourless precipitate formed is filtered off and dried in vacuo. The yield of tetraphenylphosphonium dicyanofluoropentafluoroethylborate is 85 mg (0.16 mmol), 73%, based on the potassium trifluoropentafluoroethylborate, K[C2F5BF3], employed. Melting point: 103 C. 1H-NMR: delta, ppm=7.8-7.92 m (4C6H5, 16H); 7.97-8.05 m (4C6H5, 4H). 13C{1H}-NMR (cation): delta, ppm=136.3 s (4C), 135.6 d (8C), JC,P=10 Hz, d (8C), JC,P=13 Hz, 118.9 d (4C), JC,P=91 Hz. 11B-NMR: delta, ppm=-12.0 d,t (1B), 1JF,B=51.6 Hz, 2JF,B=25.2 Hz. 19F-NMR: delta, ppm=-82.6 d,t (CF3, 3F), 3JF,F=1.0 Hz, 4JF,F=6.3 Hz; -132.0 q,d (CF2, 2F), 3JF,F=5.0 Hz, 2JF,B=25.3 Hz; -219.1 q,q,t (BF, 1F), 1JF, B=52 Hz, 3JF,F=5-6 Hz, 4JF,F=5-6 Hz.
potassium (trifluoromethyl)trifluoroborate[ No CAS ]
[ 1314568-59-6 ]
Yield
Reaction Conditions
Operation in experiment
97%
Example 13Tetraphenylphosphonium cyanodifluorotrifluoromethylborate-[(C6H5)4P][CF3BF2(CN)] Potassium trifluorotrifluoromethylborate, K[CF3BF3] (0.3 g, 1.7 mmol), is introduced into a cylindrical reaction vessel with a glass valve and a PTFE spindle (Young, London) and a magnetic stirrer bar. Trimethylsilyl cyanide (5.0 ml, 37.5 mmol) is added under an argon atmosphere. The reaction mixture is stirred at room temperature for 24 hours. All volatile constituents are removed in vacuo, and most of the unreacted trimethylsilyl cyanide (4.3 ml, 32.3 mmol) is recovered by fractional distillation. The residue is dissolved in deionised water (10 ml) and precipitated using [Ph4P]Br (1.2 g, 2.8 mmol) dissolved in deionised water (20 ml), filtered off and dried in vacuo. Yield of tetraphenylphosphonium cyanodifluorotrifluoromethylborate: 0.8 g (1.7 mmol), 97%, based on the potassium trifluorotrifluoromethylborate, K[CF3BF3], employed.Melting point: 219 C.1H-NMR: delta, ppm=7.80-7.92 m (4C6H5, 16H); 7.97-8.05 m (4C6H5, 4H).13C{1H}-NMR (cation): delta, ppm=136.3 s (4C), 135.6 d (8C), JC,P=10 Hz. 131.3 d (8C), JC,P=13 Hz, 118.9 d (4C), JC,P=91 Hz.11B-NMR: delta, ppm=-3.8 tq (1B), 1JF,B=49.0 Hz, 2JF,B=34.5 Hz.19F-NMR: delta, ppm=-77.4 q (CF3, 3F), 2JF,B=34.5 Hz; -169.1 q (BF2, 2F), 1JF,B=49.3 HzElemental analysis: found, %, C, 64.22; H, 4.65; N, 2.91; calculated for C26H20BF5NP, %, C, 64.62; H, 4.17; N, 2.90.
General procedure: Sodium metal (30 mg) was added to the 10 mL methanol solution of f-g (2 mmol); after getting clear solution, NiCl2?6H2O (1 mmol) was added and it was stirred for 10 min, followed by the addition of [PPh4]Br (2 mmol). The stirring was continued for an additional 15 min by the addition of 10 mL water, whereby the product was obtained as precipitate, which was filtered and air dried (Scheme 4). The crystals of compounds 2 and 3, suitable for single crystal X-ray structure determination, were obtained by crystallizing the above mentioned precipitates of 2 and 3 by the diffusion of diethyl ether to their acetonitrile-methanol solution and acetonitrile solution respectively. Compounds 1, 4 and 5 were crystallized also by diffusion of diethyl ether to the respective acetonitrile solutions, but we could not obtain crystals, suitable for single crystal X-ray crystallography because of their tiny sizes. The characterization data for compounds 1-5 are described below. Compounds 2 and 3 are additionally characterized by single crystal X-ray crystallography.
General procedure: Sodium metal (30 mg) was added to the 10 mL methanol solution of f-g (2 mmol); after getting clear solution, NiCl2?6H2O (1 mmol) was added and it was stirred for 10 min, followed by the addition of [PPh4]Br (2 mmol). The stirring was continued for an additional 15 min by the addition of 10 mL water, whereby the product was obtained as precipitate, which was filtered and air dried (Scheme 4). The crystals of compounds 2 and 3, suitable for single crystal X-ray structure determination, were obtained by crystallizing the above mentioned precipitates of 2 and 3 by the diffusion of diethyl ether to their acetonitrile-methanol solution and acetonitrile solution respectively. Compounds 1, 4 and 5 were crystallized also by diffusion of diethyl ether to the respective acetonitrile solutions, but we could not obtain crystals, suitable for single crystal X-ray crystallography because of their tiny sizes. The characterization data for compounds 1-5 are described below. Compounds 2 and 3 are additionally characterized by single crystal X-ray crystallography.
(PPh4)2[NiII(C8H2N2S2(thiophen-2-yl)2)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
General procedure: Sodium metal (30 mg) was added to the 10 mL methanol solution of f-g (2 mmol); after getting clear solution, NiCl2?6H2O (1 mmol) was added and it was stirred for 10 min, followed by the addition of [PPh4]Br (2 mmol). The stirring was continued for an additional 15 min by the addition of 10 mL water, whereby the product was obtained as precipitate, which was filtered and air dried (Scheme 4). The crystals of compounds 2 and 3, suitable for single crystal X-ray structure determination, were obtained by crystallizing the above mentioned precipitates of 2 and 3 by the diffusion of diethyl ether to their acetonitrile-methanol solution and acetonitrile solution respectively. Compounds 1, 4 and 5 were crystallized also by diffusion of diethyl ether to the respective acetonitrile solutions, but we could not obtain crystals, suitable for single crystal X-ray crystallography because of their tiny sizes. The characterization data for compounds 1-5 are described below. Compounds 2 and 3 are additionally characterized by single crystal X-ray crystallography.
General procedure: Sodium metal (30 mg) was added to the 10 mL methanol solution of f-g (2 mmol); after getting clear solution, NiCl2?6H2O (1 mmol) was added and it was stirred for 10 min, followed by the addition of [PPh4]Br (2 mmol). The stirring was continued for an additional 15 min by the addition of 10 mL water, whereby the product was obtained as precipitate, which was filtered and air dried (Scheme 4). The crystals of compounds 2 and 3, suitable for single crystal X-ray structure determination, were obtained by crystallizing the above mentioned precipitates of 2 and 3 by the diffusion of diethyl ether to their acetonitrile-methanol solution and acetonitrile solution respectively. Compounds 1, 4 and 5 were crystallized also by diffusion of diethyl ether to the respective acetonitrile solutions, but we could not obtain crystals, suitable for single crystal X-ray crystallography because of their tiny sizes. The characterization data for compounds 1-5 are described below. Compounds 2 and 3 are additionally characterized by single crystal X-ray crystallography.
General procedure: Sodium metal (30 mg) was added to the 10 mL methanol solution of f-g (2 mmol); after getting clear solution, NiCl2?6H2O (1 mmol) was added and it was stirred for 10 min, followed by the addition of [PPh4]Br (2 mmol). The stirring was continued for an additional 15 min by the addition of 10 mL water, whereby the product was obtained as precipitate, which was filtered and air dried (Scheme 4). The crystals of compounds 2 and 3, suitable for single crystal X-ray structure determination, were obtained by crystallizing the above mentioned precipitates of 2 and 3 by the diffusion of diethyl ether to their acetonitrile-methanol solution and acetonitrile solution respectively. Compounds 1, 4 and 5 were crystallized also by diffusion of diethyl ether to the respective acetonitrile solutions, but we could not obtain crystals, suitable for single crystal X-ray crystallography because of their tiny sizes. The characterization data for compounds 1-5 are described below. Compounds 2 and 3 are additionally characterized by single crystal X-ray crystallography.
In toluene; at 150℃; under 18751.9 Torr; for 15h;Autoclave;
The same procedure described above for the preparation of [nBu4P][PtBr3(C2H4)] was adopted, except for the use of PtBr2 (49.6 mg, 0.140 mmol) and Ph4PBr (59.0 mg, 0.141 mmol), with the addition of 10 mL of dry toluene. At the end of the reaction, the recovered mixture contained a large amount of yellow-brown precipitate. The autoclave was washed with 5 mL of toluene and the resulting suspension added to the reaction mixture. Then, the autoclave was further washed with 5 mL of CH2Cl2, which completely dissolved the residual precipitate. The combined liquids were evaporated to dryness. The residue was redissolved in 3 mL of CH2Cl2 and filtered, leaving behind a small amount of black solid. The product was obtained as a yellow-ochre precipitate after partial solvent evaporation to ca. 0.5 mL and addition of diethyl ether (2 mL). After separation from the mother liquor, the solid was washed twice with Et2O (2 * 5 mL) and dried. Yield 93 mg (82%). 1H NMR (CD2Cl2): delta 8.0 (m, 4H, Ph), 7.8 (m, 8H, Ph), 7.7 (m, 8H, Ph), 4.52 (s + d, 4H, 2JPt-H = 65 Hz, C2H4). 195Pt NMR (CD2Cl2): delta -3428 (quint, 2JPt-H = 65 Hz). Anal. % Calcd. for C26H24Br3PPt (M = 802.242): C, 38.93; H, 3.02. Found: C, 38.8; H, 2.6.
PPh4[Co(2-amino-1-(2-hydroxybenzamide)-2-methylpropane-2H)2]·1.5CH3CN·2H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
In methanol; at 20℃; for 2h;
A methanol solution (10 mL) of KOtBu (0.22 g, 2.0 mmol) was added with stirring to a methanol solution (20 mL) containing H2L1 (0.20 g, 1.0 mmol) and CoCl2·6H2O (0.14 g, 0.59 mmol). After stirring for 2 h at room temperature in air, PPh4Br (0.42 g, 1.0 mmol) was added to the reaction mixture, and the solvent was evaporated off under reduced pressure. The brown oily residue was dissolved in dichloromethane (15 mL), and the undissolved white precipitate was filtered off. The filtrate was evaporated to dryness, again, and the residue was dissolved in acetonitrile. Diethyl ether vapor was diffused into the solution, depositing dark brown platelet crystals. Yield: 0.61 g (68%). Anal. Calc. for PPh4[1]·0.5CH3CN·H2O = C47H51.5CoN4.5O5P: C, 66.46; H, 6.11; N, 7.42. Found: C, 66.42; H, 5.98; N, 7.74%. 1H NMR (CDCl3, 22 C): delta 1.08 (s, 6H, -CH3), 1.16 (s, 6H, -CH3), 1.70 (d, J = 10.6 Hz, 2H, -NH2), 2.59 (d, J = 11.1 Hz, 2H, -NH2), 3.71 (d, J = 12.9 Hz, 2H, -CH2-), 4.10 (d, J = 12.8 Hz, 2H, -CH2-), 6.61 (ddd, J = 7.8, 6.6 and 1.3 Hz, 2H, aryl-H), 6.48 (dd, J = 8.2 and 1.3 Hz, 2H, aryl-H), 6.56 (ddd, J = 8.3, 6.6 and 1.9 Hz, 2H, aryl-H), 8.02 (dd, J = 7.8 and 1.8 Hz, 2H, aryl-H).
tetraphenylphosphonium tetrakis(diethyldithiocarbamate) europium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
30%
In methanol; for 12.0h;
. Tetraphenylphosphonium tetrakis (diethyl-dithiocarbamate) europium (III) ((PPh4)[Eu(S2CEt2)4]) was synthesized by adding a solution of (Na(S2CNEt2)3H2O) (14 g) in 30 ml of methanol to EuCl36H2O (5.6 g) dissolved in 30 ml of methanol while stirring and reacted for 3 h. After the reaction mixture was filtered, a solution of BrPPh4 (6.4 g) in 30 ml of methanol was added to the filtrate and stirred for 9 h. The resulting precipitate was separated by filtration and washed 2 times with ethanol. Yield: 30%.
Potassium tris(trifluoromethanesulfonyl)methide (0.52 g, 1.14 mmol) was introduced into a pear-shaped flask, and the compound was dissolved in ethyl acetate (10 mL). An ethyl acetate solution (10 mL) of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (0.48 g, 1.14 mmol) was slowly added dropwise to the solution, and the mixture was stirred for one hour at room temperature. The organic layer was thoroughly washed with water, and then the solvent was distilled off. Thus, 0.84 g of a target ionic compound G was obtained as a white powder. Yield: 98.2%. The reaction scheme of this Synthesis Example is shown below.
A solution of (Ph4P)Br (0.37g, 0.87mmol) in 2mL of MeCN was added with stirring to a slurry of KSPh (0.13g, 0.88mmol) in 2mL of MeCN, affording a yellow-orange solution and a white precipitate. The solution was filtered through diatomaceous earth, and a solution of CoCl2 (16mg, 0.12mmol) in 2mL of MeCN was added to the filtrate to afford a dark green solution. This solution was stirred briefly, then allowed to sit undisturbed for 24h to yield 0.11g (76%) of product as large green, block-shaped crystals of product with a unit cell matching that previously reported [16].
To a solution of [PPh4]Br (0.42 g, 1.0 mmol) in a mixture of water (18 mL) and ethanol (2 mL) was added upon stirring at room temperature a solution of AgNO3 (0.17 g, 1.0 mmol) in water (2 mL). Immediately, a yellowish powder of AgBr began to precipitate. The reaction mixture was stirred in darkness for 1 h, then it was centrifuged for 10 min at 5000 rpm and filtered off. The resulting colorless filtrate was concentrated to ~2 mL in vacuum and then kept overnight in refrigerator. The next day, the precipitated colorless crystals of [PPh4]NO3 were filtered off, washed with cold water (4×0.5 mL) and dried at 20 C in vacuum for 5 h. Yield: 0.33 g (82%). Anal. Calcd. for C24H20NO3P (%): C, 71.81; H, 5.02; N, 3.49; P, 7.72. Found: C, 71.96; H, 4.88; N, 3.46; P, 7.72.
5(C2H5)4N(1+)*V12O32(4-)*Cl(1-)*CH3CN=[(C2H5)4N]5[V12O32(Cl)]*CH3CN[ No CAS ]
[ 2751-90-8 ]
2C8H20N(1+)*3C24H20P(1+)*Cl(1-)*H2V14O38(4-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
9%
A mixture of (Et4N)5[Cl?V12O32] (80 mg, 0.05 mmol), n-Bu4NCl (400 mg, 1.4 mmol), and Co(NO3)2·6H2O (15 mg, 0.05 mmol) in 2 mL acetonitrile was allowed to stand for 2 days at 25 C. The addition of Et4NCl (350 mg, 2.1 mmol) to the mixture produced a brown precipitate after 1 h. The crude product was collected and washed with acetonitrile three times. After suspending the precipitate in acetonitrile, Ph4PBr (210 mg, 0.5 mmol) was added and stirred to give a red-brown solution. After filtering any undissolved material, brown crystals of (Et4N)2(Ph4P)3[H2V14O38Cl] were obtained (10 mg, 9% based on V). Anal. Calc. for C88H102N2ClO38P3V14: C, 40.08; H, 3.90; N, 1.06; Cl, 1.34. Found: C, 39.76; H, 3.93; N, 1.10; Cl, 1.28%. IR (Nujol, 1000-500 cm-1): 978(s), 914(w), 842(s), 787(w), 750(m), 721(s), 688(w), 647(m), 522(w). 51V NMR (CH3CN): delta = -547 (2V), -567 (2V), -579 (6V), -592 (4V).
[tetraphenylphosphonium]4[(silver)44(3,4-difluorobenzenethiolate)30][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
General procedure: In a typical synthesis, 20 mg AgNO3 were dissolved in methanol. Dichloromethane was then added to the solution to form a mixture. The mixture was cooled to 0 C in an ice bath, 10 muL 3,4-difluorobenzenethiol and 12 mg bis(triphenylphosphoranylidene)ammonium chloride were then added. After 20 min, 1ml NaBH4 aqueous solution (45 mg/mL) and 50 mul triethylamine were added quickly to above mixture under vigorous stirring. The reaction was aging for 12 h at 0 C. The aqueous phase was then removed. The mixture in organic phase was then washed several times with water. Black block crystals were crystallized in CH2Cl2/hexane at 4 C.
General procedure: 2.2.1.1. [NMe4] [InIII(dmit)2]. To a stirred suspension of 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (0.298 g, 2.20 mmol) in methanol (10 ml) under argon was added a sodium methoxide solution, prepared from sodium (0.101 g, 4.40 mmol) and methanol (10 ml).Indium trichloride (0.243 g, 1.10 mmol) was added to the resulting purple solution of [Na]2[dmit]. After stirring for 30 min at room temperature, a solution of [NMe4]Br (0.169 g, 1.10 mmol) in MeOH (10 ml) was added, with immediate precipitation of a bright orange solid. This was collected and recrystallised from methanol. 2.2.1.3. [PPh4][InIII(dmit)2]. This orange coloured compoundwas synthesizedsimilarly to [NMe4][InIII(dmit)2], using 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (0.813 g, 2.0mmol), sodium (0.120 g, 4.00mmol), InCl3 (0.223 g, 1.00 mmol), [PPh4]Br (0.409 g, 1.00mmol)andMeOH(total volume 30ml). Yield 49%, 0.418 g;m.p .225 C (dec).Anal. Calc. for C30H20InPS10: C, 42.6; H, 2.5. Found: C, 42.3; H,2.1%.IR (cm1): 1437, 1070, 1036, 883.UV (nm, max): 446,340,294, 272.
tripotassium sodium tetracyanodioxomolybdate(IV) hexahydrate[ No CAS ]
[ 109-84-2 ]
[ 2751-90-8 ]
(PPh4)2[Mo(CN)4O(2-hydroxyethylhydrazine)]*3H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
General procedure: Synthesis of (PPh4)2[Mo(CN)4O(L)]·3H2O, L = amet, ampro and ethyd (1-3) The complexes (PPh4)2[Mo(CN)4O(amet)]?3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]?3H2O (2) and (PPh4)2[Mo(CN)4O(ethyd)]?3H2O (3) were synthesized in water-ethanol solutions. All three ligands: 2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine (10 mmol) were dissolved in 10 ml of ethanol and heated to 40 C for several minutes. The solution of K3Na[Mo(CN)4O2]?6H2O (1 mmol) in 20 ml of water was added to these three ligands separately. Then solid PPh4Br (1 mmol) was added and the obtained blue crystals were filtered off, washed with the water and dried in air at room temperature. The yields are: 58%, 42% and 67% for 1, 2 and 3 respectively. The Anal. Calcd. for C54H53MoN5O5P2 (1): C, 64.29; H, 5.20; N, 6.94%. Found: C, 64.55; H, 5.25; N, 6.91%, Anal. Calcd. for C55H55MoN5O5P2 (2): C, 64.58; H, 5.32; N, 6.85%. Found: C, 64.86; H, 5.22; N, 6.78% and Anal. Calcd. for C54H54MoN6O5P2 (3): C, 63.28; H, 5.31; N, 8.20%. Found: C, 63.25; H, 5.39; N, 8.36%.
tripotassium sodium tetracyanodioxomolybdate(IV) hexahydrate[ No CAS ]
[ 2751-90-8 ]
[ 141-43-5 ]
(PPh4)2[Mo(CN)4O(2-aminoethanol)]*3H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
General procedure: Synthesis of (PPh4)2[Mo(CN)4O(L)]·3H2O, L = amet, ampro and ethyd (1-3) The complexes (PPh4)2[Mo(CN)4O(amet)]?3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]?3H2O (2) and (PPh4)2[Mo(CN)4O(ethyd)]?3H2O (3) were synthesized in water-ethanol solutions. All three ligands: 2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine (10 mmol) were dissolved in 10 ml of ethanol and heated to 40 C for several minutes. The solution of K3Na[Mo(CN)4O2]?6H2O (1 mmol) in 20 ml of water was added to these three ligands separately. Then solid PPh4Br (1 mmol) was added and the obtained blue crystals were filtered off, washed with the water and dried in air at room temperature. The yields are: 58%, 42% and 67% for 1, 2 and 3 respectively. The Anal. Calcd. for C54H53MoN5O5P2 (1): C, 64.29; H, 5.20; N, 6.94%. Found: C, 64.55; H, 5.25; N, 6.91%, Anal. Calcd. for C55H55MoN5O5P2 (2): C, 64.58; H, 5.32; N, 6.85%. Found: C, 64.86; H, 5.22; N, 6.78% and Anal. Calcd. for C54H54MoN6O5P2 (3): C, 63.28; H, 5.31; N, 8.20%. Found: C, 63.25; H, 5.39; N, 8.36%.
[PPh4][InIII(1,3-dithiole-2-thione-4,5-dithiolate)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49%
General procedure: 2.2.1.1. [NMe4] [InIII(dmit)2]. To a stirred suspension of 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (0.298 g, 2.20 mmol) in methanol(10 ml) under argon was added a sodium methoxide solution, preparedfrom sodium (0.101 g, 4.40 mmol) and methanol (10 ml).Indium trichloride (0.243 g, 1.10 mmol) was added to the resultingpurple solution of [Na]2[dmit]. After stirring for 30 min at roomtemperature, a solution of [NMe4]Br (0.169 g, 1.10 mmol) in MeOH(10 ml) was added, with immediate precipitation of a brightorange solid. This was collected and recrystallised from methanol.Yield 86%, 0.500 g; m.p. 250 C (dec).Anal. Calc. for C10H12NInS10: C, 20.6; H, 2.1; N, 2.4. Found: C,20.3; H, 2.0; N, 2.0%.IR (cm1): 1435, 1066, 1051, 889.UV (nm, max): 472,363,297, 273.
(4'-bromobiphenyl-4-yl)diphenylphosphine[ No CAS ]
[ 2751-90-8 ]
C24H20P(1+)*C42H33BP(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
31%
General procedure: The following procedure was adapted from the literature method.6 Ph2P(4-BrC6H4) (0.500 g, 1.47 mmol) was dissolved in THF (10 mL) and cooled to -90C. Next, t-BuLi (0.86 mL of a 1.7 M solution in pentane, 1.47 mmol) was added dropwise via syringe to the cooled solution, turning it orange. The solution was allowed to stir for an additional 60 minutes at -90C. Next, BPh3 (0.356 g, 1.47 mmol) in THF (5 mL) was added via syringe to the solution. The flask was removed from the cooling bath and the yellow solution was left to stir while warming to room temperature slowly over 2 hours. The volatiles were removed under reduced pressure, and then CH2Cl2 (10 mL) and Ph4PBr (0.615 g, 1.47 mmol) were added to the flask. The cloudy, colourless mixture was allowed to stir for 90 minutes, and then it was filtered through Celite. The nearly colourless filtrate was concentrated to dryness under reduced pressure yielding an off-white, oily solid. The solid was redissolved in MeCN (15 mL) and stirred for several minutes, after which time a white solid began to precipitate. The mixture was allowed to stand overnight, and then the next day the supernatant was decanted. The white solid was washed with diethyl ether (30 mL) and dried under reduced pressure.
Ph2PCH2(4-BrC6H4) (0.500 g, 1.41 mmol) was dissolved in THF (15 mL) and cooled to -80C. Next, n-BuLi (0.88 mL of a 1.6 M solution in hexanes, 1.41 mmol) was added dropwise via syringe to the cooled solution yielding an orange solution. The solution was allowed to warm gradually to -40C where it was left to stir for an additional 90 minutes. Next, BPh3 (0.341 g, 1.41 mmol) in THF (7 mL) was added via syringe to the solution, and the mixture was allowed to stir for an additional 10 minutes. After this time, the flask was removed from the cooling bath and the yellow solution was left to stir while warming to room temperature slowly over 2 hours. The volatiles were removed under reduced pressure, and then CH2Cl2 (15 mL) and Ph4PBr (0.590 g, 1.41 mmol) were added to the flask. The cloudy, colourless mixture was allowed to stir for 30 minutes, and then it was filtered through Celite. The nearly colourless filtrate was concentrated to dryness under reduced pressure yielding an off-white, oily solid. The solid was redissolved in MeCN (15 mL) and stirred for several minutes, after which time a white solid began to precipitate. The mixture was allowed to stand overnight, and then the next day the supernatant was decanted. The white solid was washed with diethyl ether (30 mL) and dried under reduced pressure. Yield: 0.998 g (83%). Anal. Calcd. for C61H51BP2?2CH3CN: C, 83.2; H, 6.12. Found: C, 83.6; H, 5.95. 1H NMR (500 MHz, 22C, CDCl3): 7.77-6.69 (overlapping m, 49H, Ph and Ar), 3.26 (s, 2H, -CH2-). 31P{1H} NMR (202 MHz, 22C, CDCl3): 23.0 (s, Ph4P+), -11.9 (s, Ph2P-). 11B{1H} NMR (160 MHz, 22C, CDCl3): -6.91 ppm.
General procedure: Ph2PCH2(4-BrC6H4) (0.500 g, 1.41 mmol) was dissolved in THF (15 mL) and cooled to -80C. Next, n-BuLi (0.88 mL of a 1.6 M solution in hexanes, 1.41 mmol) was added dropwise via syringe to the cooled solution yielding an orange solution. The solution was allowed to warm gradually to -40C where it was left to stir for an additional 90 minutes. Next, BPh3 (0.341 g, 1.41 mmol) in THF (7 mL) was added via syringe to the solution, and the mixture was allowed to stir for an additional 10 minutes. After this time, the flask was removed from the cooling bath and the yellow solution was left to stir while warming to room temperature slowly over 2 hours. The volatiles were removed under reduced pressure, and then CH2Cl2 (15 mL) and Ph4PBr (0.590 g, 1.41 mmol) were added to the flask. The cloudy, colourless mixture was allowed to stir for 30 minutes, and then it was filtered through Celite. The nearly colourless filtrate was concentrated to dryness under reduced pressure yielding an off-white, oily solid. The solid was redissolved in MeCN (15 mL) and stirred for several minutes, after which time a white solid began to precipitate. The mixture was allowed to stand overnight, and then the next day the supernatant was decanted. The white solid was washed with diethyl ether (30 mL) and dried under reduced pressure.
The following procedure was adapted from the literature method.6 Ph2P(4-BrC6H4) (0.500 g, 1.47 mmol) was dissolved in THF (10 mL) and cooled to -90C. Next, t-BuLi (0.86 mL of a 1.7 M solution in pentane, 1.47 mmol) was added dropwise via syringe to the cooled solution, turning it orange. The solution was allowed to stir for an additional 60 minutes at -90C. Next, BPh3 (0.356 g, 1.47 mmol) in THF (5 mL) was added via syringe to the solution. The flask was removed from the cooling bath and the yellow solution was left to stir while warming to room temperature slowly over 2 hours. The volatiles were removed under reduced pressure, and then CH2Cl2 (10 mL) and Ph4PBr (0.615 g, 1.47 mmol) were added to the flask. The cloudy, colourless mixture was allowed to stir for 90 minutes, and then it was filtered through Celite. The nearly colourless filtrate was concentrated to dryness under reduced pressure yielding an off-white, oily solid. The solid was redissolved in MeCN (15 mL) and stirred for several minutes, after which time a white solid began to precipitate. The mixture was allowed to stand overnight, and then the next day the supernatant was decanted. The white solid was washed with diethyl ether (30 mL) and dried under reduced pressure. Yield: 0.681 g (55%). Anal. Calcd. for C60H49BP2?2CH3CN: C, 83.1; H, 5.99. Found: C, 83.0; H, 5.77. 1H NMR (500 MHz, 22C, CDCl3): 7.73-6.74 (m, 49H, Ph and Ar). 31P{1H} NMR (202 MHz, 22C, CDCl3): 23.1 (s, Ph4P+), -5.86 (s, Ph2P-). 11B{1H} NMR (160 MHz, 22C, CDCl3): -6.79 ppm.
An acetonitrile solution (4 mL) of 6-methylpicolinic acid (6Me-picH, 0.274 g, 2.0 mmol) was added to an acetonitrile solution(4 mL) containing Mn(OAc)3·2H2O (0.232 g, 1.0 mmol) to give a brown suspension. To the suspension was added (n-Bu4N)(OAc) (120 mg, 0.40 mmol) in acetonitrile (2 mL) at 60 C to give a clear solution. The resulting solution was cooled to ambient temperature, to which was added NEt3 (28 muL, 0.20 mmol) in acetonitrile (0.4 mL). A stream of CO2 gas was passed over the resulting solution at ambient temperature for 1 minute to afford a yellowish brown solution, to which was added Ph4PBr (251 mg, 0.60 mmol) in acetonitrile (2 mL) and diethyl ether (~12 mL). The resulting solution was allowed to stand for several days at -40 C to afford brown crystals suitable for X-ray crystallography together with brown powder. It was found that this complex gradually decomposed at ambient temperature under air. This complex was stored at -40 C. Yield: 0.509 g (65 %). Anal. Calcd for C40H38.5MnN2.5O9.5P: C,60.65; H, 4.90; N, 4.42 %. Found: C, 60.43; H, 5.19; N, 4.64 %. IR (KBr, cm-1): 1637 (COO),1571 (CO3), 1591 (C=C), 1571 (CO3), 1460 (CO3), 1259 (CO3) 1107 (PPh4). ESI-TOF/MS(acetonitrile): m/z = 387.0 [M]-. UV-vis [lambdamax/nm (epsilon/M-1 cm-1)] in acetonitrile at -40 C: 225nm (epsilon = 10000 M-1 cm-1), 269 nm (epsilon = 3400 M-1 cm-1), and 310 nm (epsilon = 620 M-1 cm-1).
(Ph4P)[Fe(6-methylpicolinate)2(CO3)]·0.5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
To a suspension of[Fe(6Me-pic)2(mu-OH)2]·3H2O (149 mg, 0.20 mmol) in acetonitrile (4 mL) was added(n-Bu4N)(OAc) (120 mg, 0.40 mmol) at 60 C to give a clear solution. The resulting solution was cooled to ambient temperature, to which was added NEt3 (28 muL, 0.20 mmol) in acetonitrile (0.4 mL). A stream of CO2 gas was passed over the resulting solution at ambient temperature for 1 minute to afford a yellowish brown solution, to which was added Ph4PBr(251 mg, 0.60 mmol) in acetonitrile (2 mL) and diethyl ether (~12 mL). The resulting solution was allowed to stand for several days at -40 C to afford yellow crystals suitable for X-ray crystallography together with yellow powder. It was found that this complex gradually decomposed at ambient temperature under air. Therefore, it was stored at -40 C. Yield: 76.6 mg (52 %). Anal. Calcd for C39H33FeN2O7.5P: C, 63.60; H, 4.52; N, 3.80 %. Found: C, 63.86; H, 4.51; N, 3.94 %. IR (KBr, cm-1): 1654 (COO), 1604 (C=C), 1571 (CO3), 1253 (CO3), 1107(PPh4). ESI-TOF/MS (acetonitrile): m/z = 388.1 [M]-. UV-vis [lambdamax/nm (epsilon/M-1 cm-1)] in acetonitrile at -40 C: featureless spectrum with an absorption around 300-450 nm with a shoulder at 350 nm (epsilon = 1800 M-1 cm-1).
A 30mL of MeOH solution of K2SeO3 (0.100g, 0.486mmol), Ru3(CO)12 (0.547g, 0.852mmol), and KOH (0.308g, 5.48mmol) was stirred and refluxed for 2d. The resultant solution was filtered and concentrated, and a 10mL of MeOH solution of PPh4Br (0.409g, 0.975mmol) was added dropwise in an ice-water bath to precipitate the solid. The solid was washed with deionized water, MeOH, and Et2O, and solvent was pumped off to give a residue. The residue was then extracted with CH2Cl2 which was recrystallized with Hexanes/Et2O/CH2Cl2 to give [PPh4]2[ 1] (0.545g, 0.328mmol, 67% based on Ru). IR (vCO, CH2Cl2): 2029 (w), 1973 (s), 1921 (m), 1757 (w) cm-1. [Et4N]2[1] was synthesized with a similar procedure. Anal. Calcd for C62H40O14P2SeRu5: C, 44.99; H, 2.44. Found: C, 45.39; H, 2.03.
21.3 g of salicylanilide was added to 100 g of MeOH, followed by adding 21.6 g of 25 wt % sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. To the solution, 21.4 g of 2,4-dihydroxy benzophenone was added and dissolved, followed by slowly adding 41.9 g of tetraphenylphosphonium bromide previously dissolved in 50 g of methanol. The mixture was allowed to further react for 1 hout The resulting white solid was filtered to obtain 54.4 g of a compound. The compound was identified by NMR data as a compound represented by Formula 2b ?HNMR(300MHz,DMSO)oe 13.87(s, 1H), 12.51(s, 1H), 8.03-7.90 (m, 4H), 7.88-7.64 (m, 18H), 7.64-7.47 (m,5H), 7.29 (dd, J=10.9, 5.3 Hz, 3H), 7.09 (ddd, J=8.6, 6.9, 2.0Hz, 1H), 6.99 (dd, J=10.5, 4.2 Hz, 1H), 6.59 (dd, J=8.3, 1.0Hz, 1H), 6.44-6.34 (m, 1H), 6.31-6.19 (m, 2H). In the compound represented by Formula 2b, phosphonium, salicylanilide and a dihydroxy compound corresponding to an anionic part were found to be present in a ratio of 1:1:1 through integration of the ?H NMR spectrum. When salicylanilide was used in an amount exceeding 2 equivalent weights, phosphonium, salicylanilide and pyrocatechol were found to maintain the ratio of 1:1:1 through integration of the ?H NMR spectrum. Therefore, it was determined that the structure represented by Formula 2b was a stable form.
54.4 g
Was added to 21.3g of 100gMeOH salicylanilide, followed by adding a solution of sodium methoxide 21.6g25wt%, while it was completely dissolved and then reacted at room temperature for 30 minutes.Adding to the solution 21.4g2,4- dihydroxy benzophenone and dissolved, followed by slowly adding 41.9g previously dissolved in 50g methanol tetraphenylphosphonium bromide.So that the reaction mixture was further 1 hour.The resulting white solid was filtered to give 54.4g compound.The identification of compounds by NMR data represented by a compound of formula 2b:[Formula 2b]
26.3 g of 3-hydroxy 2-naphthanalide was added to100 g of MeOH/DMF (weight ratio 1:1), followed by adding21.6 g of 25 wt % sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. To the solution, 21.4 g of <strong>[10425-11-3]3,4-dihydroxy benzophenone</strong> was added and dissolved, followed by slowly adding 41.9 g of tetraphenylphosphonium bromide previously dissolved in 50 g of methanol. The mixture was allowed to further react for 1 hour. The resulting yellow solid was filtered to obtain 70.7 g of a compound. The compound was identified by NMR data as a compound represented by Formula 2f: ?H NMR (300 MHz, DMSO) oe 8.36 (s, 1H), 7.97(ddd, J=7.4, 5.5, 1.9 Hz, 4H), 7.77 (tdd, J=8.5, 7.3, 2.6 Hz,17H), 7.67-7.46 (m, 6H), 7.42-7.27 (m, 3H), 7.25-7.15 (m,2H), 7.08 (dd, J=8.3, 2.2 Hz, 1H), 7.01 (t, J=7.4 Hz, 1H), 6.93(t, J=6.9 Hz, 1H), 6.82-6.72 (m, 2H). In the compound represented by Formula 2f, phosphonium, 3-hydroxy 2-naphthanalide and 3,4-dihydroxyben- zophenone corresponding to an anionic part were found to be present in a ratio of 1:1:1 through integration of the ?H NMR spectrum. When 3-hydroxy 2-naphthanalide was used in an amount exceeding 2 equivalent weights, phosphonium, 3-hy- droxy 2-naphthanalide and <strong>[10425-11-3]3,4-dihydroxybenzophenone</strong> were found to maintain the ratio of 1:1:1 through integration of the ?H NMR spectrum. Therefore, it was determined that the structure represented by Formula 2f was a stable form.
70.7 g
Adding 100gMeOH / DMF (1:1) in 2-naphthoylamino 26.3g3- hydroxy aniline, followed by adding a solution of sodium methoxide 21.6g25 wt%, while it was completely dissolved and then reacted at room temperature for 30 minutes.The solution was added to 21.4g 3,4- dihydroxy benzophenone and dissolved, followed by slowly adding 41.9g previously dissolved in 50g methanol tetraphenylphosphonium bromide.The mixture was further reacted for 1 hour.The resulting yellow solid was filtered to give 70.7g compound.Said compound by NMR data discrimination by the compounds of formula 2f represented by:[Formula 2f]
13.7 g of salicylamide was added to 50 g of MeOH, followed by adding 21.6 g of 25 wt % sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. To the solution, a solution of 41.9 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> previously dissolved in 50 g of methanol was slowly added. The mixture was allowed to further react for 1 hout The resulting white solid was filtered to obtain 41 g of a compound. The compound was identified by NMR data as a compound rep-resented by Formula ih: ?H NMR oe 8.00-7.94 (4H, dt), 7.85-7.70 (17H, m),7.29 (1H, dt), 6.82 (1H, d), 6.72 (1H, t)
41g
50gMeOH added to 13.7g of salicylamide, followed by adding a solution of sodium methoxide 21.6g25wt%, while it was completely dissolved without following the reaction at room temperature for 30 minutes.Was slowly added previously dissolved in 50g methanol solution 41.9g <strong>[2751-90-8]tetraphenyl phosphonium bromide</strong> to the solution.The mixture was further reacted for 1 hour.The resulting white solid was filtered, to obtain compound 41g.The identification of compounds by NMR data represented by a compound of formula 1h:[Formula 1h]
27.4 g of salicylamide was added to 50 g of MeOH, followed by adding 21.6 g of 25 wt % sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. To the solution, a solution of 41.9 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> previously dissolved in 50 g of methanol was slowly added. The mixture was allowed to further react for 1 hout The resulting white solid was filtered to obtain 50.8 g of a compound. The compound was identified by NMR data as a compound represented by Formula ii: ?H NMR oe 8.00-7.94 (4H, dt), 7.85-7.70 (18H, m),7.33 (2H, dt), 6.85 (2H, d), 6.77 (2H, t). In the compound represented by Formula ii, phosphonium and salicylamide corresponding to an anionic part were found to be present in a ratio of 1:2 through integration of the ?H NMR spectrum. When salicylamide was used in an amount exceeding 2 equivalent weights, phosphonium and salicylamide were found to maintain a ratio of 1:2 through integration of the ?H NMR spectrum. Therefore, it was determined that the structure represented by Formula ii was a stable form.
50.8g
50gMeOH added to 27.4g of salicylamide, followed by adding a solution of sodium methoxide 21.6g25wt%, while it was completely dissolved without following the reaction at room temperature for 30 minutes.Was slowly added previously dissolved in 50g methanol solution 41.9g <strong>[2751-90-8]tetraphenyl phosphonium bromide</strong> to the solution.The mixture was further reacted for 1 hour.The resulting white solid was filtered to give 50.8g compound.The identification of compounds by NMR data represented by a compound of formula 1i:[Formula 1i]
Preparative Example 5 Preparation of Phosphonium Compound Represented by Formula 1e 33.0 g of pyrocatechol was added to 50 g of ethanol (EtOH), followed by adding 21.6 g of 25% sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 41 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (previously dissolved in 50 g of EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 60 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1e (yield: 84%). 1H NMR (300 MHz, DMSO) delta 8.02-7.91 (m, 4H), 7.89-7.67 (m, 16H), 6.17 (s, 12H).
Preparative Example 6 Preparation of Phosphonium Compound Represented by Formula 1f 33.0 g of pyrocatechol was added to 50 g of ethanol (EtOH), followed by adding 28.1 g of 25% potassium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 41 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> previously dissolved in 50 g of ethanol (EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 57 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1e (yield: 80%). 1H NMR (300 MHz, DMSO) delta 8.12-7.99 (m, 4H), 7.88-7.63 (m, 16H), 6.23 (s, 12H).
Preparative Example 7 Preparation of Phosphonium Compound Represented by Formula 1 g 37.2 g of 4-methylcatechol was added to 50 g of ethanol (EtOH), followed by adding 21.6 g of 25% sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 41 g of tetraphenylphosphonium bromide (previously dissolved in 50 g of EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 59 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1 g (yield: 78%). 1H NMR (300 MHz, DMSO) delta 8.03-7.91 (m, 4H), 7.86-7.70 (m, 16H), 6.06-5.91 (m, 3H), 2.04 (s, 3H).
Preparative Example 8 Preparation of Phosphonium Compound Represented by Formula 1h 37.2 g of 4-methylcatechol was added to 50 g of ethanol (EtOH), followed by adding 28.1 g of 25% potassium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 41 g of tetraphenylphosphonium bromide (previously dissolved in 50 g of EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 56 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1g (yield: 74%). 1H NMR (300 MHz, DMSO) delta 8.11-7.98 (m, 4H), 7.96-7.81 (m, 16H), 6.03-5.94 (m, 3H), 2.14 (s, 3H).
Preparative Example 1 Preparation of Phosphonium Compound Represented by Formula 1a 48.1 g of 2,3-dihydroxynaphthalene was added to 50 g of ethanol (EtOH), followed by adding 21.6 g of 25% sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 41 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (previously dissolved in 50 g of EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 78 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1a (yield: 95%). 1H NMR (300 MHz, DMSO) delta 8.01-7.91 (m, 4H), 7.84-7.69 (m, 16H), 7.33 (dd, J=6.0, 3.3 Hz, 6H), 6.92 (dd, J=6.0, 3.3 Hz, 6H), 6.48 (s, 6H).
Preparative Example 2 Preparation of Phosphonium Compound Represented by Formula 1b 48.1 g of 2,3-dihydroxynaphthalene was added to 50 g of ethanol (EtOH), followed by adding 28.1 g of 25% potassium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. Then, 20.8 g of tetraethyl orthosilicate was added, followed by reaction at ambient temperature for 10 minutes. To the solution, a solution of 43 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (previously dissolved in 50 g of EtOH) was slowly added and the mixture was allowed to further react for 30 minutes. The resulting grey solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 79 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1b (yield: 89%). 1H NMR (300 MHz, DMSO) delta 8.04-7.96 (m, 4H), 7.82-7.73 (m, 16H), 7.39 (dd, J=6.1, 3.3 Hz, 6H), 6.99 (dd, J=6.1, 3.3 Hz, 6H), 6.53 (s, 6H).
34.8 g of 1,2-phenylenebis(2-hydroxybenzamide) was added to 50 g of methanol (MeOH), followed by adding 21.6 g of 25% sodium methoxide solution, which in turn was completely dissolved while reacting at ambient temperature for 30 minutes. To the solution, a solution of 41 g of <strong>[2751-90-8]tetraphenylphosphonium bromide</strong> (previously dissolved in 50 g of methanol (MeOH)) was slowly added and the mixture was allowed to further react for 1 hour. The resulting white solid was filtered to remove a solvent component of the solution at low pressure, thereby obtaining 65 g of a compound. The compound was identified based on NMR data as a compound represented by Formula 1a (yield: 95%). ?H NMR (400 MHz, DMSO) 8.5 (br, 2H), 8.05-7.88 (m, 4H), 7.85-7.69 (m, 18H), 7.62 (m, 2), 7.34 (t, J=12.1Hz, 2H), 7.01-6.98 (m, 4H), 6.91 (d, J=7.2 Hz, 2H), 4.9 (s,1H)ppm; ?3C NMR (100 MHz, DMSO) 164.8, 159.4,137.4,137.3, 133.6, 129.0, 128.9, 128.8, 128.2, 124.6 121.5, 119.9,116.0 ppm; 3?P NMR (166 MHz, DMSO) 24.20 ppm;LC-MS mlz=686 (M); Anal. Calcd for CH35N2O4P: C,76.95; H, 5.14; N, 4.08. Found: C, 76.49; H, 5.43; N, 4.38.
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