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Type
HazMat fee for 500 gram (Estimated)
Excepted Quantity
USD 0.00
Limited Quantity
USD 15-60
Inaccessible (Haz class 6.1), Domestic
USD 80+
Inaccessible (Haz class 6.1), International
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Structure of 1079-66-9 * Storage: {[proInfo.prStorage]}
* 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.
Reference：
[1] Journal of the American Chemical Society, 1984, vol. 106, # 5, p. 1323 - 1332
[2] Phosphorus and Sulfur and the Related Elements, 1983, vol. 15, p. 165 - 176
[3] European Journal of Organic Chemistry, 2000, # 14, p. 2601 - 2604
2
[ 109-09-1 ]
[ 1079-66-9 ]
[ 37943-90-1 ]
Reference：
[1] Journal of Organometallic Chemistry, 1999, vol. 575, # 1, p. 63 - 66
[2] Russian Journal of General Chemistry, 2000, vol. 70, # 4, p. 524 - 528
3
[ 17624-36-1 ]
[ 1079-66-9 ]
[ 37943-90-1 ]
Reference：
[1] Zeitschrift fuer Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1980, vol. 35, # 11, p. 1329 - 1334
4
[ 21970-13-8 ]
[ 1079-66-9 ]
[ 37943-90-1 ]
Reference：
[1] Journal of Organic Chemistry, 1948, vol. 13, p. 502,529
5
[ 289-95-2 ]
[ 1079-66-9 ]
[ 2426-94-0 ]
Reference：
[1] Journal of Organic Chemistry, 2007, vol. 72, # 17, p. 6602 - 6605
6
[ 75-77-4 ]
[ 1079-66-9 ]
[ 17154-34-6 ]
Yield
Reaction Conditions
Operation in experiment
90 g
Stage #1: With sodium; potassium In tetrahydrofuran for 3 h; Reflux Stage #2: for 0.75 h; Reflux
1.13 parts of sodium (11.72 g, 0.51 mol) and 0.93 parts of potassium (16.42 g, 0.42 mol) into a 2 L flask,Heating to dissolve the two metals fully mixed into the alloy.Add magnetic stirring finger and 600mL of dry tetrahydrofuran solution, so that the alloy is covered. 1 part of diphenylphosphonium chloride (82.44 mL, 0.45 mol) was diluted into 150 mL of dry tetrahydrofuran solution and slowly dropped into the alloy mixture through a dropping funnel over half an hour. The mixed liquid was refluxed for 2.5 hours.After cooling, another 300 mL of dry tetrahydrofuran solution was added. 1.04 parts of trimethylsilyl chloride (60 mL, 0.468 mol) was diluted into 450 mL of dry tetrahydrofuran solution,Slowly drip into the mixed liquid through the dropping funnel for 45 minutes. The mixed liquid is heated to boiling with vigorous stirring.After cooling and filtering, the resulting filtrate was evaporated to dry tetrahydrofuran. The remaining oil was distilled to give 90 g of product.To 10 ml of pure acetic acid solution containing dichloromaleic anhydride (0.515 g, 0.003 mol) was added dropwise 20 ml of an acetic acid solution (1 g, 0.003 mol) dissolved in acetic acid and heated to boiling. After cooling, filtration,The precipitate was washed again with 10 ml of filtrate, 5 ml of water and 5 ml of ethanol solution respectively and dried to give 0.535 g of product 1.1 (0.46 g, 0.972 mmol) was dissolved in 15 ml of tetrahydrofuran, and a solution of diphenyl (trisMethylsilyl) phosphine (0.5 ml, 1.94 mmol) in tetrahydrofuran (10 ml) was added and the mixture was stirred at room temperature for 4 hours. After filtrationThe filtrate was taken and 0.069 g of product 2 was obtained by interfacial diffusion of 38 ml of ether.
Reference：
[1] Chemical Communications, 2005, # 14, p. 1848 - 1850
[2] Patent: CN107312037, 2017, A, . Location in patent: Paragraph 0012; 0026; 0030; 0034
Stage #1: With magnesium In tetrahydrofuran for 10 h; Inert atmosphere; Reflux Stage #2: With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 20℃; for 11 h; Reflux; Inert atmosphere
Under nitrogen protection,1L three bottles,From 50 g of 4-bromo-N, N-dimethylaniline,7 g of magnesium turnings and 400 ml of anhydrousTHF to produce Grignard reagent,Refluxed for 10 hours, reduced to room temperature,2.9 g of tetrakis (triphenylphosphine) palladium was added,Stirred for 3 hours,61 g of diphenylphosphonium chloride was added dropwise at room temperature,The reaction was refluxed for 8 hours.And the mixture was added dropwise to the reaction solution under ice-water bath200 mL of saturated aqueous ammonium chloride was quenched,Liquid separation, the organic phase solution,Add methanol crystallization,And filtered to obtain 74 g of white 4- (N, N-dimethylamino) diphenylphosphine benzene,Yield 96percent.
Reference：
[1] Patent: CN105859774, 2016, A, . Location in patent: Paragraph 0090; 0091; 0092; 0093
[2] Journal of Organometallic Chemistry, 1999, vol. 575, # 1, p. 63 - 66
[3] Russian Journal of General Chemistry, 2000, vol. 70, # 4, p. 524 - 528
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1974, p. 37 - 41
[5] Chemische Berichte, 1984, vol. 117, # 9, p. 2791 - 2802
[6] Phosphorus and Sulfur and the Related Elements, 1983, vol. 15, p. 165 - 176
[7] Australian Journal of Chemistry, 2003, vol. 56, # 11, p. 1135 - 1139
10
[ 121-69-7 ]
[ 1079-66-9 ]
[ 739-58-2 ]
Reference：
[1] Journal of the American Chemical Society, 1967, vol. 89, p. 5235 - 5246
11
[ 1079-66-9 ]
[ 1499-21-4 ]
Reference：
[1] Phosphorus and Sulfur and the Related Elements, 1987, vol. 29, p. 365 - 368
[2] Chemische Berichte, 1983, vol. 116, # 10, p. 3375 - 3405
[3] Patent: US4168287, 1979, A,
[4] Journal of Organic Chemistry, 1981, vol. 46, # 1, p. 43 - 46
[5] Phosphorus and Sulfur and the Related Elements, 1987, vol. 30, p. 125 - 128
[6] Canadian Journal of Chemistry, 1998, vol. 76, # 5, p. 518 - 521
[7] Doklady Chemistry, 2006, vol. 409, # 2, p. 129 - 132
[8] European Journal of Organic Chemistry, 2003, # 21, p. 4216 - 4226
[9] Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 107, # 1-4, p. 161 - 172
[10] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1980, p. 154 - 160
[11] Doklady Chemistry, 2008, vol. 419, # 2, p. 87 - 90
[12] Journal of Thermal Analysis and Calorimetry, 2010, vol. 102, # 2, p. 493 - 498
[13] Doklady Chemistry, 2011, vol. 438, # 2, p. 151 - 154
12
[ 56372-47-5 ]
[ 1079-66-9 ]
[ 1101-41-3 ]
[ 1499-21-4 ]
Reference：
[1] Phosphorus and Sulfur and the Related Elements, 1984, vol. 21, p. 161 - 170
13
[ 1079-66-9 ]
[ 67-64-1 ]
[ 1499-21-4 ]
Reference：
[1] J. Gen. Chem. USSR (Engl. Transl.), 1980, vol. 50, # 6, p. 1049 - 1052[2] Zhurnal Obshchei Khimii, 1980, vol. 50, # 6, p. 1297 - 1301
14
[ 1079-66-9 ]
[ 76-03-9 ]
[ 79-36-7 ]
[ 1499-21-4 ]
Reference：
[1] J. Gen. Chem. USSR (Engl. Transl.), 1984, vol. 54, # 1, p. 194 - 195[2] Zhurnal Obshchei Khimii, 1984, vol. 54, # 1, p. 219 - 220
15
[ 644-97-3 ]
[ 587-85-9 ]
[ 1079-66-9 ]
[ 1499-21-4 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1926, vol. 449, p. 228
[2] Justus Liebigs Annalen der Chemie, 1881, vol. 207, p. 210
[3] Justus Liebigs Annalen der Chemie, 1926, vol. 449, p. 228
[4] Chemische Berichte, 1885, vol. 18, p. 2109
[5] Justus Liebigs Annalen der Chemie, 1881, vol. 207, p. 210
16
[ 108-94-1 ]
[ 1079-66-9 ]
[ 1707-03-5 ]
[ 38868-16-5 ]
[ 20187-71-7 ]
[ 1499-21-4 ]
Reference：
[1] J. Gen. Chem. USSR (Engl. Transl.), 1980, vol. 50, # 6, p. 1049 - 1052[2] Zhurnal Obshchei Khimii, 1980, vol. 50, # 6, p. 1297 - 1301
17
[ 67-56-1 ]
[ 1079-66-9 ]
[ 4020-99-9 ]
Reference：
[1] Angewandte Chemie - International Edition, 2008, vol. 47, # 38, p. 7346 - 7349
[2] Phosphorus and Sulfur and the Related Elements, 1988, vol. 39, p. 141 - 152
[3] Zhurnal Obshchei Khimii, 1948, vol. 18, p. 2008,2013,2014[4] Chem.Abstr., 1949, p. 3801
[5] Journal of Organic Chemistry, 1978, vol. 43, p. 571 - 574
[6] Polish Journal of Chemistry, 2005, vol. 79, # 3, p. 541 - 545
[7] Russian Chemical Bulletin, 2015, vol. 64, # 1, p. 233 - 236[8] Izv. Akad. Nauk, Ser. Khim., 2015, # 1, p. 233 - 236,4
[9] Chemical Communications, 2015, vol. 51, # 92, p. 16561 - 16564
18
[ 1079-66-9 ]
[ 4020-99-9 ]
Yield
Reaction Conditions
Operation in experiment
73%
With ammonia In methanol; ethanol
Example 8 210 g (6.56 mol) of absolute ethanol are cooled to -15° C. under a nitrogen atmosphere. 200 g (0.907 mol) of chloro(diphenyl)phosphine are then added dropwise at this temperature with vigorous stirring. 18 g (1.06 mol) of ammonia gas are then introduced. The mixture is then stirred without cooling for 10 hours and filtered by suction. The filtrate is freed from methanol and excess ammonia in vacuo. The residue is filtered by suction through a glass frit. 143 g of crude methyl diphenylphosphinite are obtained. This corresponds to a yield of 73percent of theory.
Reference：
[1] Patent: US5705669, 1998, A,
19
[ 1079-66-9 ]
[ 719-80-2 ]
Yield
Reaction Conditions
Operation in experiment
83%
With ammonia In ethanol
Example 2 330 9 (7.17 mol) of absolute ethanol are cooled to -15° C. under a nitrogen atmosphere. 18 g (1.06 mol) of ammonia gas are then introduced at this temperature. 200 g (0.907 mol) of chloro(diphenyl)phosphine are then added dropwise at this temperature in one hour. The mixture is then allowed to come to room temperature with stirring and is stirred for a further 3.5 hours. The mixture is then cooled, filtered by suction and washed with ethanol. The filtrate is freed from ethanol and any ammonia present in vacuo. The remaining residue is freed from a slight precipitate by filtration through a glass frit. 172 g of ethyl diphenylphosphinite are then obtained by thin film distillation at a bath temperature of 140° C. and 0.3 mbar. This corresponds to a yield of 83percent of theory.
82%
With ammonia In ethanol
Example 1 330 g (7.17 mol) of absolute ethanol are cooled to -15° C. under a nitrogen atmosphere. 26.5 g (1.56 mol) of ammonia gas are introduced thereto at this temperature with constant stirring. 200 g (0.907 mol) of chloro(diphenyl)-phosphine are then added dropwise at this temperature. The mixture is then allowed to come to room temperature with stirring and is then kept under reflux for 11 hours until virtually no more ammonia gas escapes. The mixture is then cooled, filtered by suction, washed with ethanol and dried. 48 g of crude ammonium chloride are obtained. The filtrate is freed from ethanol and any ammonia present in vacuo. The remaining residue is freed from a slight salt precipitate by filtration through a glass frit. 170 g of ethyl diphenylphosphinite are then obtained by thin film distillation at a bath temperature of 160° to 175° C. and a pressure of 0.5 mbar. This corresponds to a yield of 82percent of theory.
88%
With pyridine In ethanol
EXAMPLE 2 Preparation of Ethyl Diphenylphosphinite A solution of diphenylphosphinous chloride (135 mmol) in dry ether (120 mL) was treated dropwise at 5° C. with a solution of ethanol (200 mmol) and pyridine (134 mmol) in ether (120 mL). After addition was complete, the mixture was warmed to room temperature, filtered under argon, and the solid hydrochloride washed with ether. Evaporation of the solvent gave an oil which was purified by Kugelrohr distillation at 95° C. (0.1 mmHg). Yield: 119 mmol (88percent); 1 H NMR (CDCl3) δ7.6-7.2 (m, 10H), 3.95 (doublet of quartets, JH-H =7 Hz, JP-H =10 Hz, 2H), 1.30 (t, J=7 Hz, 3H).
Reference：
[1] Patent: US5705669, 1998, A,
[2] Patent: US5705669, 1998, A,
[3] Patent: US5705669, 1998, A,
[4] Patent: US5705669, 1998, A,
[5] J. Gen. Chem. USSR (Engl. Transl.), 1961, vol. 31, p. 2214 - 2217[6] Zhurnal Obshchei Khimii, 1961, vol. 31, p. 2377 - 2380
[7] Patent: US4574060, 1986, A,
20
[ 64-17-5 ]
[ 1079-66-9 ]
[ 719-80-2 ]
Reference：
[1] Organic Letters, 2018, vol. 20, # 11, p. 3286 - 3290
[2] Inorganic Chemistry, 2018, vol. 57, # 18, p. 11530 - 11536
[3] Zhurnal Obshchei Khimii, 1950, vol. 20, p. 107,112;engl.Ausg.S.113,118
[4] Doklady Akademii Nauk SSSR, 1949, vol. 66, p. 389,391[5] Chem.Abstr., 1950, p. 127
[6] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1967, p. 568 - 572[7] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1967, p. 591 - 595
[8] Journal of Organic Chemistry, 1961, vol. 26, p. 4623 - 4626
[9] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1972, p. 304 - 311
[10] Phosphorus, Sulfur and Silicon and the Related Elements, 2008, vol. 183, # 2-3, p. 383 - 388
[11] Chemical Communications, 2015, vol. 51, # 92, p. 16561 - 16564
21
[ 141-52-6 ]
[ 1079-66-9 ]
[ 719-80-2 ]
Reference：
[1] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1910, vol. 42, p. 404,411[2] Chem. Zentralbl., 1910, vol. 81, # II, p. 454
[3] Chemische Berichte, 1968, vol. 101, # 4, p. 1414 - 1427
[4] Canadian Journal of Chemistry, 2001, vol. 79, # 5-6, p. 752 - 759
22
[ 78-39-7 ]
[ 1079-66-9 ]
[ 719-80-2 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1968, vol. 712, p. 21 - 27
23
[ 78-09-1 ]
[ 1079-66-9 ]
[ 719-80-2 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1968, vol. 712, p. 21 - 27
24
[ 60-29-7 ]
[ 141-52-6 ]
[ 1079-66-9 ]
[ 719-80-2 ]
[ 1707-03-5 ]
Reference：
[1] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1910, vol. 42, p. 404,411[2] Chem. Zentralbl., 1910, vol. 81, # II, p. 454
Reference：
[1] Organic and Biomolecular Chemistry, 2006, vol. 4, # 3, p. 544 - 550
[2] Synthetic Communications, 1992, vol. 22, # 10, p. 1453 - 1459
29
[ 1079-66-9 ]
[ 108-95-2 ]
[ 13360-92-4 ]
Reference：
[1] Journal of the Chemical Society. Dalton Transactions, 2003, # 21, p. 4164 - 4174
[2] Bulletin of the Chemical Society of Japan, 2009, vol. 82, # 3, p. 381 - 392
[3] Organometallics, 2011, vol. 30, # 22, p. 6225 - 6232
[4] Chemical Communications, 2001, # 1, p. 129 - 130
[5] Journal of Organic Chemistry, 1986, vol. 51, # 22, p. 4185 - 4189
[6] Chemische Berichte, 1885, vol. 18, p. 2109
[7] Chemische Berichte, 1885, vol. 18, p. 2109
[8] Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999), 1997, p. 1137 - 1148
[9] Bulletin of the Chemical Society of Japan, 2004, vol. 77, # 8, p. 1569 - 1579
[10] Chemical Communications, 2015, vol. 51, # 92, p. 16561 - 16564
30
[ 589-87-7 ]
[ 1079-66-9 ]
[ 5525-40-6 ]
Yield
Reaction Conditions
Operation in experiment
71.4%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: at -78℃; for 2 h;
20.0 g (70.6 mmol) of 1-bromo-4-iodobenzene was added to a three-necked 1.0 L flask, and a nitrogen atmosphereDissolve in 500 mL of THF under nitrogen. After cooling the reaction temperature to -78 ° C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solutionAnd the mixture was stirred at room temperature. After the dropwise addition was completed, the mixture was stirred at -78 ° C for one hour, and then chlorodiphenylphosphine13.9 mL (77.7 mmol) of chlorodiphenylphosphine was slowly added dropwise. After stirring for two hours, 10 mL of H2O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. To the concentrate was added methylene chloride 500ML and 500 mL of H2O, and the organic layer was separated and washed with water and brine. The reaction of the resulting intermediate mixtureAfter cooling the temperature to 0 ° C, 85.8 mL (0.988 mol) of hydrogen peroxide (H 2 O 2) was slowly added dropwise. The reaction temperature was raised to room temperatureAnd the mixture was stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filteredThe filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 18 g of a white solid compound (Intermediate (4)): 71.4percent).
71.4%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: for 2 h; Inert atmosphere Stage #3: With dihydrogen peroxide In dichloromethane; water at 25℃; for 18 h;
Into the 3-neck 1.0 L flask was charged with 1-bromo-4-iodo-benzene (1-bromo-4-iodobenzene ) 20.0 g (70.6 mmol)are dissolved in 500 mL THF under nitrogen atmosphere.After cooling the reaction temperature to -78 °C, a 2.5M n-BuLi solution, 31 mL (77.7mmol) was slowly added dropwise thereto and stirred. After the addition was terminated after han hour at -78°C , it was added dropwise the chloro-diphenylphosphine (chlorodiphenylphosphine) 13.9 mL (77.7mmol) slowly.After two hours stirring, H2O was added 10mL.Gave up after the temperature of the reaction slowly to room temperature, the reaction mixture was concentrated under reduced pressure. In 500 mL of methylene chloride and concentrate H2O after inserting the 500 mL, and the organic layer was separated and washed with water and brine (brine).After cooling the reaction temperature of the resulting intermediate mixture to 0°C , hydrogen peroxide (H2O2) was added dropwise 85.8 mL (0.988 mol) slowly. Raise the reaction temperature to room temperature, and stirred for 18 hours. After the reaction was completed when the separation of the organic phase was washed twice with water, MgSO4 dried, filtered, and concentrated under a reduced pressure.Solidifying the resultant purified concentrate with a solvent to obtain a compound (intermediate 1) 18g of a white solid (yield: 71.4percent) was obtained.
71.4%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: for 2 h; Inert atmosphere Stage #3: at 0 - 20℃; for 18 h; Inert atmosphere
In a three-necked 1.0 L flask20.0 g (70.6 mmol) of 1-bromo-4-iodobenzene was dissolved in 500 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 °C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred. After the dropwise addition was completed, the mixture was stirred at -78 ° C for 1 hour, 13.9 mL (77.7 mmol) of chlorodiphenylphosphine was slowly added dropwise.After stirring for two hours, 10 mL of H2O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. To the concentrate was added 500 mL of dichloromethane and 500 mL of H2O,The organic layer was separated and washed with water and brine.The reaction temperature of the obtained intermediate mixture was kept at 0 ° C, 85.8 mL (0.988 mol) of hydrogen peroxide (H2O2) was slowly added dropwise.The reaction temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure.The obtained concentrate was solidified and purified by using a solvent to obtain 18 g (yield: 71.4percent) of a white solid compound (intermediate (1)).
71.4%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1 h; Inert atmosphere Stage #2: at -78 - 20℃; for 2 h; Inert atmosphere Stage #3: With dihydrogen peroxide In tetrahydrofuran; water at 0 - 20℃; for 18 h; Inert atmosphere
A three-necked 1.0 L flask was charged with 1-bromo-4-iodobenzene20.0 g (70.6 mmol)And dissolved in 500 mL of THF under a nitrogen atmosphere.After cooling the reaction temperature to -78 ° C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solution was slowly added dropwiseAnd stirred. After the dropwise addition was completed, the mixture was stirred at -78 ° C for 1 hour,13.9 mL (77.7 mmol) of & lt; RTI ID = 0.0 & gt; chlorodiphenylphosphine &Was slowly added dropwise. After stirring for two hours, 10 mL of H2O was added.After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure.After adding 500 mL of dichloromethane and 500 mL of H2O to the concentrate, the organic layer was separated and washed with water and brine.After the reaction mixture was cooled to 0 , hydrogen peroxide (H 2 O 2) 85.8ML (0.988 mol) was slowly added dropwise. After the reaction temperature was raised to room temperature,And stirred for 18 hours.When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO4, filtered, and the filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 18 g (yield: 71.4percent) of a white solid compound (intermediate (1))
Reference：
[1] Patent: KR2016/64432, 2016, A, . Location in patent: Paragraph 0071-0073
[2] Patent: KR2016/50894, 2016, A, . Location in patent: Paragraph 0076-0078
[3] Patent: KR101652325, 2016, B1, . Location in patent: Paragraph 0076-0078
[4] Patent: KR101652323, 2016, B1, . Location in patent: Paragraph 0089-0091
31
[ 106-37-6 ]
[ 1079-66-9 ]
[ 5525-40-6 ]
Yield
Reaction Conditions
Operation in experiment
61%
Stage #1: With magnesium In diethyl ether at -10℃; for 1 h; Stage #2: With dihydrogen peroxide In methanol; dichloromethane
4-Bromophenyldiphenylphosphane oxide was synthesized without the isolation of the intermediate phosphane 1. Following the procedure described in [46], a solution of 4.42g (18.7mmol) of 1,4-dibromobenzene in 25mL of dry diethylether was added dropwise into a slurry of 450mg (18.5mmol) of Mg turnings in 5mL of ether. When all the Mg was consumed, the mixture was cooled to −10°C and, maintaining the temperature below 0°C, 3.97g (18mmol) of Ph2PCl in 5mL of ether were introduced. The cooling bath was removed and stirring was continued for an hour. The flask was cooled again to 0°C and 2.5g of NH4Cl in 7.5mL of water were added slowly. The organic phase was separated, the remainder was acidified with HCl and extracted with dichloromethane (3×15mL). The combined organic solution was dried over MgSO4 and evaporated to give 5.85g of a yellow sticky oil. ESI-MS analysis of the crude reaction mixture indicated the presence of the target compound 1 ((M+H)+=341, 343) that was accompanied with the diphosphane Ph2PC6H4PPh2 ((M+H)+=447) and the oxygenated derivatives of these constituents, namely 4-BrC6H4P(O)Ph2 ((M+H)+=357, 359)), Ph2PC6H4P(O)Ph2 ((M+H)+=463) and Ph2P(O)C6H4P(O)Ph2 ((M+H)+=479. In order to avoid an excessive high concentration of free phosphane in the Suzuki coupling reaction and also to promote the facile separation of the monophosphane from the diphosphane by-product, the crude mixture was oxidized with H2O2 in a 1:1 solution of CH2Cl2 and MeOH, then chromatographed on Kieselgel (60–200 mesh) using dichloromethane: ethylacetate eluents with an increasing proportion of the latter solvent from 1:0 to 1:2. 4-BrC6H4P(O)Ph2, 2, was isolated in high purity (3.9g, 61percent based on Ph2PCl). ESI-MS: (M+H)+=357, 359; 1H NMR (CDCl3) δ, ppm: 7.71–7.42 (overlapping multiplets); 31P NMR (CDCl3) δ, ppm: 29.6 (s).
45%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -80℃; for 1 h; Inert atmosphere Stage #2: at -80 - 20℃; Inert atmosphere Stage #3: With dihydrogen peroxide In dichloromethane; waterInert atmosphere
General procedure: The halogen compound was dissolved in THF. 2.5M n-BuLi solution inhexane was slowly dropped to this solution chilled to —80°C. (temperature measured directly in the solution). The stirring was continued for one hour. Diphenyl phosphine chloride or phenylphosphine dichloride, respectively, was added slowly at —80° C. The reaction mixture was allowed to warm to room temperature (RT) and stirred overnight. After methanol addition and reduction to dryness, the residue was dissolved in dichloromethane (DCM). The organic phase was washed with water, dried over Na2504 and reduced to dryness. The residue was dissolved in DCM again and oxidized with 30 wt. percent aqueous hydrogen peroxide solution. After stirring overnight, the organic solution was washed with water, dried over Na2504 and reduced to dryness. The crude product was purified by column chromatography. According to general procedure A) (0093) 1,4-dibromobenzene: 10.00 g (42.4 mmol, 1.0 eq) (0094) n-butyllithium, 2.5M in hexane: 17 mL (42.4 mmol, 1.0 eq) (0095) chlorodiphenylphosphine: 9.35 g (42.4 mmol, 1.0 eq) (0096) THF: 50 mL (0097) DCM: 50 mL (0098) H2O2, 30 wt. percent in water: 10 mL (0099) Column chromatography: SiO2, ethyl acetate (0100) Yield: 6.84 g white solid (45percent theoretical) (0101) mp: 166° C. (0102) GC-MS: m/z=356, 358
Reference：
[1] Polyhedron, 2015, vol. 92, p. 156 - 165
33
[ 1079-66-9 ]
[ 5525-40-6 ]
Reference：
[1] Journal of Materials Chemistry C, 2015, vol. 3, # 43, p. 11540 - 11547
[2] Patent: JP5808857, 2015, B2,
[3] Patent: KR2015/30616, 2015, A,
[4] Patent: KR2015/27720, 2015, A,
[5] Patent: KR101656560, 2016, B1,
[6] Journal of the American Chemical Society, 2018, vol. 140, # 3, p. 1131 - 1141
34
[ 2052-07-5 ]
[ 1079-66-9 ]
[ 13885-09-1 ]
Reference：
[1] Journal of the American Chemical Society, 2012, vol. 134, # 12, p. 5697 - 5705
[2] Organic Letters, 2013, vol. 15, # 20, p. 5302 - 5305
[3] Organic Letters, 2013, vol. 15, # 24, p. 6186 - 6189
[4] Chemical Communications, 2014, vol. 50, # 36, p. 4686 - 4689
[5] Organic Letters, 2017, vol. 19, # 7, p. 1842 - 1845
35
[ 2051-60-7 ]
[ 1079-66-9 ]
[ 13885-09-1 ]
Reference：
[1] European Journal of Organic Chemistry, 2012, # 11, p. 2127 - 2131
36
[ 1079-66-9 ]
[ 1707-03-5 ]
[ 2751-90-8 ]
[ 791-28-6 ]
Reference：
[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
37
[ 1079-66-9 ]
[ 2751-90-8 ]
Reference：
[1] Synthesis, 1980, # 7, p. 551 - 554
38
[ 108-86-1 ]
[ 1079-66-9 ]
[ 1707-03-5 ]
[ 2751-90-8 ]
[ 791-28-6 ]
Reference：
[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 2, p. 283 - 296
39
[ 64-17-5 ]
[ 1079-66-9 ]
[ 938-18-1 ]
[ 75980-60-8 ]
Yield
Reaction Conditions
Operation in experiment
92.2%
Stage #1: With sodium In toluene at 65 - 70℃; for 2 h; Stage #2: at 5 - 10℃; for 1 h; Stage #3: at 70 - 75℃; for 5 h;
In 100ml reaction flask was added toluene 32g, 3.45g of sodium metal particles (0.15mol), stirring, dropping 6.9g ethanol (0.15mol) dropwise, the process of maintaining the temperature at 65 ~ 70 ° C.Dropping end, stirring 2h, the reaction system was added dropwise phenylphosphine chloride 33. lg (0.15mol), the control temperature 5 ~ 10 ° C, the dropwise addition is complete,Stirring 1h, continue to the reaction system dropwise 2,4,6-trimethylbenzoyl chloride 30.1g (0.16mol), the dropping temperature was controlled at 70 ~ 75 ° C, and then stirred for 5h. The reaction was completed, the reaction material was added 15g of water, stirred lh, standing stratification, the resulting organic phase was adjusted to a saturated aqueous sodium bicarbonate solution pH 7 ~ 8, points to the aqueous phase, the organic phase was washed with water ,The resulting organic phase was dehydrated, cooled and crystallized, filtered,Dried to give a pale yellow powdery solid 48.2g, melting point 91 ~ 94 ° C, the liquid content of 99.3percent, a yield of 92.2percent
Reference：
[1] Patent: CN107304220, 2017, A, . Location in patent: Paragraph 0006; 0016-0023
40
[ 707-74-4 ]
[ 1079-66-9 ]
[ 75980-60-8 ]
Yield
Reaction Conditions
Operation in experiment
87 g
Stage #1: With magnesium In tetrahydrofuranReflux Stage #2: With hydrogenchloride; dihydrogen peroxide In water
Step 2: A mixture of 74 g of 1,3,5-trimethyl-2-trichloromethyl-benzene and 500 ml of dry THFmixing,Add 9 grams of acid activated magnesium shoulder,Maintain the reaction temperature at 20 degrees Celsius evenly until the magnesium shoulder almost disappeared,DripA solution of 68 grams of freshly distilled diphenylphosphonium chloride in 200 ml of dry THF,The reaction system was stirred at room temperature for 2 hours and then heated to reflux overnight.After the reaction system was cooled to room temperature,Remove most of the solvent,The residue was poured into 1 liter of water,The pH was adjusted between 3-4 with dilute hydrochloric acid and 90 g of a 30percent hydrogen peroxide solution was added with vigorous stirring. The aqueous phase was extracted three times with 400 ml of methylene chloride. The organic phases were combined, dried over magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The residue was crystallized from isopropyl ether87 grams of light yellow target compounds pure.
Stage #1: With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tert-butyl methyl ether; cyclohexane at 6 - 10℃; Stage #2: at 20℃; for 14 h; Stage #3: at 10 - 20℃; for 5.16667 h;
Example 2A Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 5L round bottom flask (RBF) are added MTBE (2.5 L), 9,9-dimethylxanthene (131.4 g, 0.60 mole) and TMEDA (155 g, 1.32 mole). After degassing the solution, s-BuLi (1.11 L, 1.3 M in cyclohexane, 1.44 mole) is cannulated into a dropping funnel and then slowly added over 60 min while maintaining the batch temperature at 6-10° C. The mixture is then aged for 14 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20° C. ~60percent of the Ph2PCl (175 mL, 0.93 mole) is added in 0.5 hour. The mixture is aged for 10 minutes before addition of the remaining Ph2PCl (120 mL, 0.63 mole). After aged for 5 h at room temperature, the reaction is quenched with MeOH (9.9 mL, 0.24 mole). The product is filtered and the slightly yellow solid is washed consecutively with MTBE (250 mL), MeOH (2*250 mL), water (2*300 mL), MeOH (2*250 mL) and MTBE (250 mL) and dried to give an off-white solid as product (304.2 g, 88percent yield).
77%
Stage #1: With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In tert-butyl methyl ether; cyclohexane at 10 - 20℃; for 16 h; Stage #2: at 20℃; for 5.75 h;
Example 2 Preparation of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, Xantphos To a 1L round bottom flask (RBF) are added MTBE (500 mL), 9,9-dimethylxanthene (26.65 g) and TMEDA (30.6 g). After degassing the solution, s-BuLi (155 g, 1.3 M in cyclohexane) is cannulated into a dropping funnel and then slowly added over 30 min while maintaining the batch temperature at 10-20° C. The mixture is then aged for 16 h at room temperature. Ph2PCl is added slowly via a dropping funnel while maintain the mildly exothermic reaction at 10-20° C. ~60percent of the Ph2PCl (30 mL) is added in 0.5 hour. The mixture is aged for 15 minutes before addition of the remaining Ph2PCl. After aged for 5.5 h at room temperature, the reaction is quenched with MeOH (2.0 mL). The product is filtered and the slightly yellow solid is washed consecutively with MeOH (200 mL), water (200 mL), MeOH (200 mL) and MTBE (200 mL) and dried to give an off-white solid as product (54.8 g, 77percent yield).
Reference：
[1] Russian Journal of Organic Chemistry, 2001, vol. 37, # 11, p. 1583 - 1586
[2] Phosphorus, Sulfur and Silicon and Related Elements, 1996, vol. 109, # 1-4, p. 545 - 548
[3] Patent: US2011/124904, 2011, A1, . Location in patent: Page/Page column 3
46
[ 101-84-8 ]
[ 1079-66-9 ]
[ 183383-68-8 ]
[ 166330-10-5 ]
Reference：
[1] Chemistry - A European Journal, 2013, vol. 19, # 1, p. 141 - 154
47
[ 251320-87-3 ]
[ 1079-66-9 ]
[ 402822-72-4 ]
Reference：
[1] Chemical Communications, 2014, vol. 50, # 36, p. 4686 - 4689
48
[ 102-54-5 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference：
[1] Chemistry - A European Journal, 2012, vol. 18, # 39, p. 12267 - 12277
49
[ 591-51-5 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference：
[1] Journal of Organometallic Chemistry, 1980, vol. 185, # 1, p. C1 - C5
[2] Organometallics, 1982, vol. 1, p. 1275 - 1282
50
[ 12098-17-8 ]
[ 1079-66-9 ]
[ 12150-46-8 ]
Reference：
[1] Organometallics, 1986, vol. 5, p. 2537 - 2542
51
[ 1079-66-9 ]
[ 147118-36-3 ]
[ 289042-10-0 ]
Yield
Reaction Conditions
Operation in experiment
25.1 %
With sodium iodide; sodium hydrogensulfite In trans-Decalin; ethyl acetate; mineral oil
EXAMPLE 1 N-[5-(Diphenylphosphinoylmethyl)-4-(4-fluorophenyl)-6-isopropylpyrimidin-2-yl]-N-methylmethanesulfonamide 1.00 g (2.83 mmol) of [4-(4-fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino)pyrimidin-5-yl]methanol was initially charged in 5 ml of cis/trans-decalin and admixed with 204 mg (4.68 mmol) of sodium hydride (55 percent dispersion in mineral oil). After 30 min at room temperature, 680 mg (2.93 mmol) of chlorodiphenylphosphine was added with vigorous stirring over a period of 6 min. The mixture was admixed with 52.2 mg (0.35 mmol) of sodium iodide and heated at 184° to 186° C. for 2 h, 15 min. After cooling to room temperature, 50 ml of 38 to 40 percent strength sodium bisulfite solution and 50 ml of ethyl acetate were added. The organic phase was separated off and the aqueous phase was extracted with 50 ml of ethyl acetate. The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. This gave 1.74 g of crude product which was purified by silica gel chromatography (mobile phase: n-hexane/ethyl acetate 1:2). This gave 382.4 mg (25.1 percent) of N-[5-(diphenylphosphinoylmethyl)-4-(4-fluorophenyl)-6-isopropylpyrimidin-2-yl]-N-methylmethanesulfonamide in the form of a colorless solid. The melting point was 180° to 185° C. Other data concerning the product was:
Reference：
[1] Patent: US6160115, 2000, A,
[2] Patent: US6160115, 2000, A,
[3] Patent: US6160115, 2000, A,
[4] Patent: US6160115, 2000, A,
[5] Patent: US6160115, 2000, A,
[6] Patent: US6160115, 2000, A,
[7] Patent: US6160115, 2000, A,
[8] Patent: US6160115, 2000, A,
[9] Patent: US6160115, 2000, A,
Under nitrogen protection,1L three bottles,From 50 g of 4-bromo-N, N-dimethylaniline,7 g of magnesium turnings and 400 ml of anhydrousTHF to produce Grignard reagent,Refluxed for 10 hours, reduced to room temperature,2.9 g of tetrakis (triphenylphosphine) palladium was added,Stirred for 3 hours,61 g of diphenylphosphonium chloride was added dropwise at room temperature,The reaction was refluxed for 8 hours.And the mixture was added dropwise to the reaction solution under ice-water bath200 mL of saturated aqueous ammonium chloride was quenched,Liquid separation, the organic phase solution,Add methanol crystallization,And filtered to obtain 74 g of white 4- (N, N-dimethylamino) diphenylphosphine benzene,Yield 96percent.
3-[(diphenylphosphino)(methyl)amino]propyldiphenylphosphinite[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With triethylamine; In toluene; at -78 - 20℃; for 24h;Schlenk technique; Inert atmosphere;
Triethylamine (0.860mL; 0.630g; 6.20mmol) in toluene (5.0mL) was slowly added to a suspension of 3-(methylamino)propan-1-ol (0.300mL; 0.280g; 3.10mmol) in toluene (10.0mL). Then the mixture was cooled to ?78°C. A solution of PPh2Cl (1.03mL; 1.37g; 6.20mmol) in toluene (5.0mL) was slowly added dropwise. After addition, the mixture was stirred at room temperature for 24h. Et3N·HCl was separated with canula. Toluene was evaporated under vacuum and a light yellow oil was formed. 1H NMR (400MHz, CDCl3, 25°C): delta=1.78?1.83 (m, 2H, ?CH2?), 2.24?2.48 (m, 3H, N?CH3), 3.06?3.12 (m, 2H, N?CH2?), 3.77?3.72 (m, 2H, O?CH2?), 7.06?7.70 (m, 20H, ArH). 13C{1H} NMR (100MHz, CDCl3) ppm: delta=35.8 (d, N?CH3), 32.7 (t, ?CH2?), 49.3?49.8 (dd, ?CH2?N), 66.8?67.9 (dd, ?CH?O), 126?140 (m, Ar?C), 31P{1H} NMR (162MHz, CDCl3): delta=113ppm (P?O) and delta=65.3ppm (P?N).
30 mL of tetrahydrofuran was added to 2 g of <strong>[57103-20-5]3,6-dibromo-9-phenylcarbazole</strong>, and temperature was adjusted to -78 degree C. Subsequently, 0.84 mL of butyllithium was slowly added dropwise. While maintaining the temperature, the mixture was stirred for 2 hours, and 2.42 g of chlorodiphenylphosphine was slowly added dropwise, after which the temperature of the mixture was raised to room temperature. After completion of the reaction, methanol was added and the reaction mixture was stirred and extracted, followed by drying the solvent. To the resulting solid was added dichloromethane, and while the mixture was being stirred, a small amount of hydrogen peroxide was added, yielding 3,6-bis(diphenyl phosphonyl)-9-phenylcarbazole (PPO2) having the structure of the compound 2 as white phosphine oxide.
General procedure: To a stirred mixture of Ph2PCl (6.0 mmol), NaI (6.0 mmol) and anhydrous CH3CN (5.0 mL) was added alcohol 2(1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, 30 % H2O2 aqueous (0.5 mL) was slowly added, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine oxide.
(2,4-dimethylbenzyl)diphenylphosphine sulfide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
53%
General procedure: To a stirred mixture of Ph2PCl (6.0mmol), NaI (6.0 mmol) and anhydrous CH3CN (5 mL) was added alcohol 2 (1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, aqueous Na2S2O3 (2.0 mL) was added to the reaction mixture, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine sulfoxide.
General procedure: To a stirred mixture of Ph2PCl (6.0 mmol), NaI (6.0 mmol) and anhydrous CH3CN (5.0 mL) was added alcohol 2(1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, 30 % H2O2 aqueous (0.5 mL) was slowly added, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine oxide.
(2,4,6-trimethylbenzyl)diphenylphosphine sulfide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
38%
General procedure: To a stirred mixture of Ph2PCl (6.0mmol), NaI (6.0 mmol) and anhydrous CH3CN (5 mL) was added alcohol 2 (1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, aqueous Na2S2O3 (2.0 mL) was added to the reaction mixture, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine sulfoxide.
2-(trifluoromethyl)benzyl diphenylphosphine oxide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
General procedure: To a stirred mixture of Ph2PCl (6.0 mmol), NaI (6.0 mmol) and anhydrous CH3CN (5.0 mL) was added alcohol 2(1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 °C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, 30 percent H2O2 aqueous (0.5 mL) was slowly added, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine oxide.
diphenyl(2-(trifluoromethyl)benzyl)phosphine sulfide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49%
General procedure: To a stirred mixture of Ph2PCl (6.0mmol), NaI (6.0 mmol) and anhydrous CH3CN (5 mL) was added alcohol 2 (1.0 mmol) at room temperature under argon atmosphere. The reaction mixture was stirred at 80 °C in oil bath for 12 h. When the reaction temperature was cooled to room temperature, aqueous Na2S2O3 (2.0 mL) was added to the reaction mixture, and stirred for another 10 minutes. The organic layer was extracted with dichloromethane, washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by chromatography on silica gel to obtain the corresponding phosphine sulfoxide.
3,6-Dibromo-9-phenylcarbazole (5.2 g) was dissolved in 52.5 mL of dehydrated tetrahydrofuran for dissolution,It was cooled to -80 ° C. there, n-Butyllithium (17 mL) was added dropwise, and the mixture was stirred at -80 ° C. for 2 hours. Further, diphenylphosphinochloride (5 mL) was added dropwise,The temperature was gradually raised. Tetrahydrofuran was removed under reduced pressure, ethyl acetate and water were added, and the organic layer was extracted to obtain a white precipitate.The white powder (4.3 g) obtained above was dissolved in methylene chloride (47 mL)It was cooled to 0 ° C.Thereafter, 30 mass percent hydrogen peroxide water (9.3 ml) was added dropwise, and the mixture was stirred at 0 ° C. for 2 hours.Water was added to the reaction solution, and the organic layer was extracted to obtain an active ligand c (white, yield 1.88 g (yield 42percent)).
With triethylamine; In dichloromethane;Inert atmosphere;
Under argon 1-Isopropyl-4-piperidinylamine (10 mmol) and triethylamine (3-10 equiv. To amine) Dichloromethane (80 ml).With the flask immersed in a water bath,Chlorodiphenylphosphine (20 mmol) Slowly added and stirred overnight.After removing the solvent under vacuum, tetrahydrofuran was added and stirred sufficiently to remove triethylammonium chloride salt with an air-free glass filter. The solvent was removed from the filtrate to obtain the above compound.
7.6 g (50 mmol) of o-nitrobenzaldehyde was added to a round bottom flask and 170 mL of absolute ethanol was added. After stirring, 20 g (357 mmol) of iron powder was added,Acetic acid 170mL and distilled water 85mL, and finally add a drop of concentrated hydrochloric acid,Reflux 15min (TLC monitoring reaction is complete) to stop the reaction, filter, washed with water 100mL filter, the filtrate was extracted with CH2Cl2,The combined organic layers were washed with aqueous NaHCO3 and distilled water, dried over anhydrous MgSO4,Concentrated to a yellow oil o-aminobenzaldehyde. 7.8 mmol of o-aminobenzaldehyde and 7.8 mmol of p-bromoacetophenone were added to 30 mL of absolute ethanol,Add saturated NaOH to ethanol solution. The reaction mixture was heated and refluxed overnight, cooled and filtered, and the resulting crude product was recrystallized from ethanol to give white needle-like crystals to p-bromoquinoline.All the glass instruments were dried at 180 C for 5 hours and then cooled in a vacuum state.A solution of p-bromoquinoline (0.50 g, 1.76 mmol) and 18 mL of THF was added to a 50 ml reaction flask. The reaction system was cooled to -78 C with a liquid nitrogen-acetone cold bath,1.6M n-butyllithium in n-hexane was added to the syringe using a syringe. Stirring at -78 & lt; 0 & gt; C for about 1 hour,Under nitrogen, 2.11 mmol of diphenylphosphonium chloride was rapidly injected into the reaction flask with a syringe. The mixture was naturally warmed to room temperature with stirring and the reaction was continued for 18 hours. The above reaction is carried out under dry nitrogen protection.After completion of the reaction, the mixture was carefully poured into 50 mL of distilled water, hydrolyzed three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated and purified by column chromatography to give a white solid.The resulting white solid (0.26 mg, 0.69 mmol) and 20 mL of CH2Cl2 solution were added to a 100 mL reaction flask and 9 mL of H2O2 solution was added,And stirred at room temperature for 24 h. After completion of the reaction, the target compound was isolated by column chromatography. White solid in 20% yield.
With isopropylmagnesium chloride; In tetrahydrofuran;
3,6-dibromo-2-methyl pyridine was dissolved in THF, isopropyl magnesium chloride (iPrMgCl) was added dropwise thereto, and the mixture was stirred to obtain a Grignard reagent. Diphenyl chlorophosphine (PPhCl2) was added to the Grignard reagent, and then the mixture was stirred to obtain Intermediate 20-1. Intermediate 20-1 was identified by LC-MS. C18H15BrNP: M+1 356.1.
A single-mouth flask was taken, 3.26 g of 3,6-dibromodibenzothiophene was added, sealed and vacuum-dried with nitrogen three times, and 100 mL of anhydrous tetrahydrofuran (THF) was dissolved and dissolved under a nitrogen atmosphere.The device was then placed in a dry ice/acetone bath at -78 C for 15 min.13.75 mL of a n-hexane solution of n-butyllithium was weighed using a syringe.The mixture was added dropwise to a reaction flask, and reacted at -78 C for 1.5 h under a nitrogen atmosphere to obtain a reaction system.3.74 mL of diphenylphosphonium chloride was added to the reaction system, and the mixture was allowed to react at room temperature for 12 hours.The reaction solution was quenched with 50 mL of water and extracted with 3×50 mL of dichloromethane.The organic phase was collected and dried over anhydrous sodium sulfate. The dichloromethane solution was spun off using a rotary evaporator.The crude product was then dissolved in 50 mL of dichloromethane, silica gel powder was added and the solvent was dried.Purification by chromatography gave an arylphosphine derivative. The obtained arylphosphine derivative and 0.6 gThe sulfur powder was dissolved in a dichloromethane solution and allowed to react at room temperature overnight.The dichloromethane solution was spun off using a rotary evaporator. Then the crude product was dissolved to 50 mLAdd silica gel to the dichloromethane and spin dry the solvent.Purification by chromatography gave 1.91 g of a white solid.The yield was 37.1%.
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