* 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.
With potassium hydroxide; silver(l) oxide In dimethyl sulfoxide at 100℃; for 24 h;
General procedure: To a test tube containing a magnetic rod was added 4-iodotoluene, 1.0 mmol, Cu2O (14.3 mg, 0.1 mmol), KOH (169 mg, 3.0 mmol), 2-dimethylaminoethanol , 0.3 mL, 3.0 mmol) and DMSO / H2O (1.5 mL / 0.5 mL). After flushing with argon, the mixture was stirred at 100 & lt; 0 & gt; C for 24 hours in a preheated oil bath. After cooling to ambient temperature, the reaction mixture was distributed in aqueous HCl (5percent) and ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgSO4 and concentrated in vacuo. The crude product was purified by column chromatography (EtOAc / n-Hexane) to give phenol.
Reference：
[1] Patent: KR2017/91976, 2017, A, . Location in patent: Paragraph 0046; 0047
[2] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 12, p. 2833 - 2840
[3] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 12, p. 2833 - 2840
2
[ 624-31-7 ]
[ 51628-12-7 ]
Yield
Reaction Conditions
Operation in experiment
68.9%
With N-Bromosuccinimide In tetrachloromethane; water; dimethyl sulfoxide
Referential Example 3 Synthesis of 4-iodophenylacetonitrile A mixture of 4.36 g (20.0 mmol) of p-iodotoluene (purchased from Tokyo Kasei), 3.92 g (22.0 mmol) of N-bromosuccinimide (purchased from Tokyo Kasei) and 60 ml of carbon tetrachloride (purchased from Wako Junyaku Kogyo) was refluxed under irradiation by an incandescent lamp for 4 hours to give 2.67 g (yield: 45.0percent) of 4-iodobenzyl bromide (as a white crystalline). Subsequently, to a solution of 0.49 g (10.0 mmol) of sodium cyanide (purchased from Kokusan Kagaku) in 10 ml of dimethyl sulfoxide (purchased from Aldrich) heated at 50° C. was added 1.48 g (5.0 mmol) of the above 4-iodobenzyl bromide, the mixture was stirred at ambient temperature for 3 hours, the resultant reaction mass was dissolved in water and extracted with hexane, and hexane was removed to give 0.84 g (yield: 68.9percent) of 4-iodophenylacetonitrile as a white crystalline.
68.9%
With N-Bromosuccinimide In tetrachloromethane; water; dimethyl sulfoxide
Referential Example 9 Synthesis of 4-iodophenylacetonitrile A mixture of 4.36 g (20.0 mmol) of p-iodotoluene (purchased from Tokyo Kasei), 3.9 g (22 mmol) of N-bromosuccinimide (purchased from Tokyo Kasei) and 60 ml of carbon tetrachloride (purchased from Wako Junyaku Kogyo) was refluxed under the irradiation by means of an incandescent lamp for 4 hours to give 2.67 g (yield: 45.0percent) of 4-iodobenzyl bromide (as a white crystalline). Subsequently, to 0.49 g (10 mmol) of sodium cyanide (purchased from Kokusan Kagaku) in 10 ml of dimethyl sulfoxide (purchased from Aldrich) solution heated at 50° C. was added 1.48 g (5.00 mmol) of the above 4-iodobenzyl bromide, the mixture was stirred at ambient temperature for 3 hours, the resultant reaction mass was dissolved in water and extracted with hexane, and hexane was removed to give 0.84 g (yield: 68.9percent) of 4-iodophenylacetonitrile as a white crystalline.
Reference：
[1] Patent: US5574062, 1996, A,
[2] Patent: US5574062, 1996, A,
[3] Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1114 - 1126
3
[ 624-31-7 ]
[ 16004-15-2 ]
[ 51628-12-7 ]
Yield
Reaction Conditions
Operation in experiment
45%
With N-Bromosuccinimide In tetrachloromethane; water; dimethyl sulfoxide
Referential Example 4 [Preparation of 4-Iodophenylacetonitrile] A mixture of p-iodotoluene (4.36 g, 20 mmol, purchased from Tokyo Kasei) and N-bromosuccinimide (3.92 g, 22 mmol, purchased from Tokyo Kasei) in 60 ml of carbontetrachloride (purchased from Wako Junyaku Kogyo) was refluxed for 4 hours under irradiation by means of an incandescent lamp to give 2.67 g (yield: 45.0percent) of 4-iodobenzyl bromide as a white crystalline. To a hot solution (50° C.) of sodium cyanide 0.49 g, 10.0 mmom, purchased from Kokusan Kagaku) in 10 ml of dimethyl sulfoxide (purchased from Aldrich) was added the above 4-iodobenzyl bromide (1.48 g, 5.0 mmol) and the mixture was stirred for three hours at ambient temperature. To the resultant reaction mass was added water and extracted with hexane. The solvent was removed to give 0.84 g (yield: 69percent) of 4-iodophenylacetonitrile as a white crystalline.
Reference：
[1] Patent: US5589506, 1996, A,
[2] Patent: US5589506, 1996, A,
4
[ 624-31-7 ]
[ 107-21-1 ]
[ 106-44-5 ]
[ 15149-10-7 ]
Reference：
[1] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 12, p. 2833 - 2840
[2] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 12, p. 2833 - 2840
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 7 h; Heating / reflux; Photolysis
Synthesis of Compound 1D [0026] p-Iodotoluene (Compound 1C, 25 g), N-bromosuccinimide (23.5 g) and benzoyl peroxide (375 mg) were added to carbon tetrachloride (375 ml) and refluxed with heating for 7 hours under photoirradiation. Further, the reaction mixture was stirred overnight at room temperature, then insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrated residue was recrystallized from ethyl acetate and hexane to obtain Compound 1D (yield: 60.3percent). [0027] NMR chemical shift, CDCl3, TMS as standard [0028] d 7.72 (d, 2H), 7.14 (d, 2H), 4.39 (s, 2H)
Reference：
[1] Macromolecules, 2013, vol. 46, # 12, p. 4754 - 4763
[2] Acta Crystallographica Section C: Crystal Structure Communications, 2003, vol. 59, # 4, p. o216-o218
[3] Journal of Materials Chemistry C, 2015, vol. 3, # 4, p. 734 - 741
[4] Chemistry - An Asian Journal, 2017, vol. 12, # 6, p. 690 - 697
[5] Journal of Organic Chemistry, 2014, vol. 79, # 1, p. 223 - 229
[6] Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1114 - 1126
[7] Tetrahedron, 2003, vol. 59, # 7, p. 1021 - 1032
[8] Angewandte Chemie - International Edition, 2018, vol. 57, # 3, p. 800 - 804[9] Angew. Chem., 2018, vol. 57, # 3, p. 800 - 804,5
[10] Patent: US2004/228793, 2004, A1, . Location in patent: Page/Page column 4
[11] Journal of Medicinal Chemistry, 1989, vol. 32, # 5, p. 1057 - 1062
[12] Chemistry - A European Journal, 2012, vol. 18, # 23, p. 7229 - 7242
[13] Journal of the Chemical Society, 1949, p. 1089,1096
[14] Chem. Penicillin, <Princeton 1949>, S. 94,
[15] Journal of the American Chemical Society, 1948, vol. 70, p. 2310,2313
[16] American Chemical Journal, 1880, vol. 2, p. 250
[17] American Chemical Journal, 1879, vol. 1, p. 103
[18] Chemische Berichte, 1878, vol. 11, p. 55
[19] American Chemical Journal, 1908, vol. 40, p. 466
[20] Recueil des Travaux Chimiques des Pays-Bas, 1923, vol. 42, p. 522
[21] Journal of the American Chemical Society, 1949, vol. 71, p. 3360
[22] Journal of Organic Chemistry, 1949, vol. 14, p. 228,232
[23] Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 53, # 1-4, p. 43 - 67
[24] Tetrahedron Letters, 1994, vol. 35, # 3, p. 481 - 484
[25] Journal of the American Chemical Society, 2001, vol. 123, # 5, p. 946 - 953
[26] Advanced Synthesis and Catalysis, 2004, vol. 346, # 7, p. 767 - 776
[27] Patent: EP1647546, 2006, A1, . Location in patent: Page/Page column 54
[28] Organic Letters, 2013, vol. 15, # 16, p. 4194 - 4197
[29] European Journal of Organic Chemistry, 2014, vol. 2014, # 16, p. 3402 - 3410
10
[ 624-31-7 ]
[ 34241-39-9 ]
[ 16004-15-2 ]
Yield
Reaction Conditions
Operation in experiment
45%
With N-Bromosuccinimide In tetrachloromethane
Step 1 4-Iodobenzyl bromide A mixture of 4-iodotoluene (21.8 g, 100 mmol), N-bromosuccinimide (18.69 g, 105 mmol) and αα-azobisisobutyronitrile (100 mg) in carbon tetrachloride (100 ml) was refluxed for 20 hours. The reaction was cooled, the precipitate filtered, washed with carbon tetrachloride (50 ml), and the filtrate evaporated. The residue was chromatographed on silica, eluding with petrol (60°-80° C.) to give the product as a white solid (13 g, 45percent); δH (CDCl3) 4.42 (2H, ArCH2 Br), 7.11 (2H, d, J 15.3 Hz, 2-H, 6-H), 7.67 (2H, d, J 15.3 Hz, 3'-H, 5'-H).
Reference：
[1] Patent: US5861407, 1999, A,
11
[ 624-31-7 ]
[ 34241-39-9 ]
[ 16004-15-2 ]
Reference：
[1] Patent: US5965738, 1999, A,
12
[ 624-31-7 ]
[ 99-99-0 ]
[ 5326-39-6 ]
[ 41252-97-5 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1281 - 1286
13
[ 624-31-7 ]
[ 99-99-0 ]
[ 1608-47-5 ]
[ 32704-08-8 ]
[ 32704-10-2 ]
[ 5326-39-6 ]
[ 41252-97-5 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1988, vol. 24, # 11, p. 2029 - 2035[2] Zhurnal Organicheskoi Khimii, 1988, vol. 24, # 11, p. 2251 - 2258
14
[ 869373-61-5 ]
[ 624-31-7 ]
[ 5458-84-4 ]
Reference：
[1] Bulletin of the Chemical Society of Japan, 2005, vol. 78, # 9, p. 1654 - 1658
15
[ 624-31-7 ]
[ 26670-89-3 ]
Reference：
[1] Chemische Berichte, 1896, vol. 29, p. 1410
16
[ 624-31-7 ]
[ 99-99-0 ]
[ 5326-39-6 ]
[ 41252-97-5 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1281 - 1286
17
[ 624-31-7 ]
[ 41252-97-5 ]
Reference：
[1] Chemische Berichte, 1897, vol. 30, p. 3001
18
[ 624-31-7 ]
[ 99-99-0 ]
[ 1608-47-5 ]
[ 32704-08-8 ]
[ 32704-10-2 ]
[ 5326-39-6 ]
[ 41252-97-5 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1988, vol. 24, # 11, p. 2029 - 2035[2] Zhurnal Organicheskoi Khimii, 1988, vol. 24, # 11, p. 2251 - 2258
19
[ 624-31-7 ]
[ 42906-19-4 ]
Reference：
[1] Dyes and Pigments, 2011, vol. 88, # 3, p. 333 - 343
[2] Dyes and Pigments, 2017, vol. 140, p. 431 - 440
20
[ 624-31-7 ]
[ 62-53-3 ]
[ 20440-95-3 ]
Reference：
[1] Tetrahedron Letters, 2006, vol. 47, # 52, p. 9275 - 9278
[2] Journal of Organic Chemistry, 1999, vol. 64, # 2, p. 670 - 674
[3] Inorganic Chemistry Communications, 2011, vol. 14, # 9, p. 1352 - 1357
[4] Dyes and Pigments, 2011, vol. 88, # 3, p. 333 - 343
[5] Dyes and Pigments, 2017, vol. 140, p. 431 - 440
21
[ 66-71-7 ]
[ 624-31-7 ]
[ 20440-95-3 ]
Reference：
[1] Patent: US5648542, 1997, A,
22
[ 624-31-7 ]
[ 620-84-8 ]
[ 20440-95-3 ]
Reference：
[1] Russian Journal of Organic Chemistry, 1997, vol. 33, # 8, p. 1100 - 1102
23
[ 624-31-7 ]
[ 620-84-8 ]
[ 4316-53-4 ]
[ 20440-95-3 ]
Reference：
[1] Chemistry - A European Journal, 2011, vol. 17, # 9, p. 2716 - 2723
24
[ 624-31-7 ]
[ 620-84-8 ]
[ 122-39-4 ]
[ 4316-53-4 ]
[ 20440-95-3 ]
Reference：
[1] Chemistry - A European Journal, 2011, vol. 17, # 9, p. 2716 - 2723
25
[ 624-31-7 ]
[ 106-40-1 ]
[ 58047-42-0 ]
Reference：
[1] New Journal of Chemistry, 2015, vol. 39, # 3, p. 1840 - 1851
[2] RSC Advances, 2015, vol. 5, # 37, p. 28879 - 28884
[3] Journal of Organic Chemistry, 1999, vol. 64, # 2, p. 670 - 674
[4] RSC Advances, 2014, vol. 4, # 32, p. 16385 - 16390
[5] Journal of Materials Chemistry A, 2013, vol. 1, # 23, p. 6949 - 6960
[6] Patent: CN103601757, 2016, B, . Location in patent: Page/Page column 13
26
[ 624-31-7 ]
[ 3366-72-1 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1973, p. 25 - 33
27
[ 624-31-7 ]
[ 637-60-5 ]
Reference：
[1] Chinese Journal of Chemistry, 2018, vol. 36, # 11, p. 1003 - 1006
[2] RSC Advances, 2014, vol. 4, # 7, p. 3364 - 3367
28
[ 201230-82-2 ]
[ 624-31-7 ]
[ 6638-79-5 ]
[ 122334-36-5 ]
Reference：
[1] RSC Advances, 2014, vol. 4, # 57, p. 30019 - 30027
[2] Chemistry - A European Journal, 2014, vol. 20, # 20, p. 5885 - 5889
Reference：
[1] Angewandte Chemie - International Edition, 2017, vol. 56, # 6, p. 1506 - 1509[2] Angew. Chem., 2017, vol. 129, # 6, p. 1528 - 1531,4
31
[ 52670-38-9 ]
[ 624-31-7 ]
[ 124643-45-4 ]
Reference：
[1] Dalton Transactions, 2012, vol. 41, # 39, p. 12259 - 12269
[2] Organic and Biomolecular Chemistry, 2015, vol. 13, # 16, p. 4652 - 4656
32
[ 624-31-7 ]
[ 23432-40-8 ]
Reference：
[1] Australian Journal of Chemistry, 2011, vol. 64, # 4, p. 454 - 470
33
[ 624-31-7 ]
[ 38846-64-9 ]
[ 189008-33-1 ]
Yield
Reaction Conditions
Operation in experiment
71%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 80℃; for 1 h; Inert atmosphere
General procedure: A mixture of 2-ethynylbenzaldehyde (12a) (1.00 g, 7.68 mmol), 1-bromo-2-iodo-benzene (13a) (1.18 mL, 9.22 mmol), CuI (146 mg, 0.77 mmol), PdCl2(PPh3)2 (107 mg, 0.15 mmol), and Et3N (15 mL) in THF (15 mL) was stirred at 80 °C for 2 h under argon, and filtrated through a pad of Celite. The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography over silica gel with hexane-EtOAc (15:1).
Reference：
[1] Chemistry - A European Journal, 1997, vol. 3, # 5, p. 807 - 816
[2] Chemical Communications, 2012, vol. 48, # 61, p. 7634 - 7636
[3] Angewandte Chemie - International Edition, 2017, vol. 56, # 36, p. 10928 - 10932[4] Angew. Chem., 2017, vol. 129, # 36, p. 11068 - 11072,5
[5] Tetrahedron, 2011, vol. 67, # 29, p. 5168 - 5175
With copper(l) iodide; potassium carbonate; dimethylbiguanide; In acetonitrile; at 20 - 60℃; for 10.1667h;
General procedure: To a 25 mL flask containing a mixture of CuI (19.2 mg,0.1 mmol), metformin (0.1 mmol), phenol (1.0 mmol), and K2CO3(2 mmol, 276 mg) in CH3CN (5 mL) was added an aryl halide(1.1 mmol). The mixture was stirred for 10 min at room temperature, and then heated to 60?C for the appropriate amount of time(see Table 4). The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was extracted with EtOAc (5 1 mL) and the organic phase separated and evaporated. Further purification by column chromatography gave the desired coupled product.
92%
With copper(I) oxide; caesium carbonate; imidazole-4-carboxylic acid; In acetonitrile; at 80℃; for 24h;
General procedure: To a screw-capped vial (4-mL) were added Cs2CO3 (1.0 mmol, 325 mg), Cu2O (0.005 mmol, 0.7 mg), 1H-imidazole-4-carboxylic acid (0.01 mmol, 1.1 mg) and acetonitrile (0.25 mL). The vial was sealed with septum and allowed to stir for a while; the iodoarene (0.5 mmol) and phenol (0.6 mmol) were then injected into the reaction mixture via a syringe. The septum was removed, and the vial was sealed with a screw cap. The reaction mixture was stirred at 80 oC for 24 h. The crude reaction mixture was diluted with CH2Cl2, filtered through a thin Celite pad, and concentrated in vacuo. The residue was isolated through a column chromatography by using hexane and ethyl acetate as eluent to give the pure product. Products 3a-v were obtained according to this procedure. The known structures were characterized by the 1H NMR and 13C NMR of reported literatures.1-3 Spectral data, 1H NMR and 13C NMR spectra for all the new compounds are listed below.
90%
With tetrabutylammomium bromide; caesium carbonate; In dimethyl sulfoxide; at 120℃; for 14h;
General procedure: Polymer supported Cu(II) catalyst (0.05 g, 0.0098 mmol) in DMSO (5 mL) was taken in a 100 ml R.B flask and stirred at room temperature for 10 min. Then aryl halide (1 mmol), phenol(1 mmol), tetrabutylammonium bromide (tBu4NBr) (0.1 mmol),Cs2CO3 (1 mmol) and DMSO (5 mL) were added to it. The final reaction mixture was refluxed at 120 C under an open air condition.The reaction mixtures were collected at different time intervals and identified by GCMS and quantified by GC. After the completion of the reaction, the catalyst was filtered off and washed with water followed by acetone and dried in oven. The filtrate was extracted with ethyl acetate (3 x 20 ml) and the combined organic layers were dried with anhydrous Na2SO4 by vacuum. The filtrate was concentrated by vacuum and the resulting residue was purified by column chromatography on silica gel to provide the desired product.
90%
With potassium phosphate; 2-((o-toluidino)methyl)phenol; copper(l) chloride; In acetonitrile; at 81℃; for 24h;Schlenk technique; Inert atmosphere;Catalytic behavior;
General procedure: Aminophenol (5 mol %), CuCl (5 mol %), phenol (1.5 mmol), aryl halide (if solid, 1 mmol), and K3PO4 (425 mg, 2.0 mmol) were added to a screwcapped Schlenk tube under argon. The tube was then evacuated and backfilled with argon (three cycles). Aryl halide (if liquid, 1.0 mmol) and dry CH3CN (0.5 mL) were added by syringe at room temperature. The reaction mixture was stirred at needed temperature (110 oC) for 24 h. The reaction mixture was allowed to reach room temperature and then diluted with dichloromethane (10 mL). The slurry was filtered, and filter cake was washed with 10 mL of dichloromethane. The solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel to afford the desired product.
87%
With caesium carbonate; In tetrahydrofuran; at 150℃; for 3h;Inert atmosphere;Catalytic behavior;
General procedure: The catalytic O-arylation reactions were conducted in asealed stainless-steel reactor. A phenol (14 mmol), aryl halide(14 mmol), Cs2CO3 (14 mmol), tetrahydrofuran (THF, 10 mL),and the Cu2O/SiC catalyst (10 mg) were placed in the reactor.The reaction was performed under Ar at 150 C for 3 h. Afterthe reaction, the suspension was collected and centrifuged. Thesupernatant was analyzed using gas chromatography-massspectrometry (Bruker SCION SQ 456GC-MS, Germany). Theyields and TOFs were calculated based on the aryl halide usingthe following equations:Yield = Conversion (%) selectivity (%)= (1 - na/nb) x ntp/(ntp + nbp) x 100%TOF = Amount of aryl halides (mol) x conversion (%)x selectivity (%)/(mass of Cu2O/SiC (g) x Cu2O loading (%) xreaction time (h)/M[Cu2O] (g/mol))where na is the moles of aryl halide after reaction, nb is themoles of aryl halide before reaction, ntp is the moles of targetproduct after reaction, and nbp is the moles of byproduct afterreaction.
85%
With tetrabutylammomium bromide; caesium carbonate; In dimethyl sulfoxide; at 120℃; for 12h;
General procedure: Cu- catalyst (0.05 g) in DMSO (5 mL) was taken in a 100 mLround bottom flask and stirred at room temperature for 10 min.Then aryl halide (1 mmol), phenol (1 mmol), tetrabutylammoniumbromide (tBu4NBr) (0.1 mmol), Cs2CO3(1 mmol) and DMSO (5 mL)were added to it. The final reaction mixture was heated at 120Cunder an open air condition. The reaction mixtures were collectedat different time intervals and identified by GC-MS and quantifiedby GC. After the completion of the reaction, the catalyst was fil-tered off and washed with water followed by acetone and dried inoven. The filtrate was extracted with ethyl acetate (3 × 20 mL) andthe combined organic layers were dried with anhydrous Na2SO4byvacuum. The filtrate was concentrated by vacuum and the result-ing residue was purified by column chromatography on silica gelto provide the desired product.
76%
With N-phenylpicolinamide; copper; caesium carbonate; In acetonitrile; at 82℃; for 24h;Inert atmosphere;
General procedure: To a 50mL multi-necked round bottom flask, 1 mmol of aryl halide, 1.2 mmol of phenol, 20 mol% ligand, 20 mol% copper powder, 2.0 mmol of base, and 20 mL of acetonitrile were added. The mixture was stirred at 82 C for 24 h. The reaction mixture was diluted with ethyl acetate and filtered through Celite in a fritted filter funnel to remove any inorganic salts. The solvent was then removed with the help of a rotary evaporator. The residue was purified by flash chromatography using hexane and ethyl acetate as an eluent to yield the product.
With dodecane; sodium methylate; acetylacetone; In N,N-dimethyl-formamide; at 120℃; for 2h;Green chemistry;
The MOF-199 was used as a solid catalyst for the coppercatalyzed Ullmann-type coupling reaction of aryl iodides with phenols. In a typical experiment, a pre-determined amount of MOF-199 was added to the flask containing a solution of 4 - iodoacetophenone (0.246 g, 1.0 mmol), phenol (0.188 g, 2.0 mmol), K3PO4 as a base (0.424 g, 2.0 mmol), acetylacetone (0.02 ml, 0.2 mmol) as ligand, and n-dodecane (0.15 ml) as internal standard in DMF (10 ml). The catalyst concentration was calculated based on the molar ratio of copper/4 -iodoacetophenone. The reaction mixture was magnetically stirred at 120 ?C for 2 h. The reaction conversion was monitored by withdrawing aliquots from the reaction mixture at different time intervals, quenching with an aqueous KOH solution (1%, 0.1 ml), drying over anhydrous Na2SO4, analyzing by GC with reference to n-dodecane, and further confirming product identity by GC-MS. To investigate the recyclability of MOF-199, the catalyst was filtered from the reaction mixture after the experiment, washed with copious amounts of DMF and methanol, dried under vacuum at 120 ?C for 4 h, and reused if necessary. For the leaching test, a catalytic reaction was stopped after 20 min, analyzed by GC, and filtered to remove the solid catalyst. The reaction solution was then stirred for a further 100 min. Reaction progress, if any, was monitored by GC as previously described.
With potassium tert-butylate; In dimethyl sulfoxide; at 120℃; for 2h;Inert atmosphere;
General procedure: A 25-mL Schlenk tube was flame-dried under vacuum and filled with argon after cooling to room temperature. To thistube were added 1.0 mmol phenols, 2.0 mmol t-BuOK (312 mg, 2.0 mmol TEMPO for eq 6) . The tube was then evacuated and backfilled with argon (3 cycles). A dry 1.0 mL DMSO solution of 2.0 mmol aryl bromides or aryl aryl iodide was loaded into a plastic syringe. After the tube was purged with argon, this solution was injected intothe tube by syringe. The mixture was stirred under Ar atmosphere in sealed Schlenk tubes at the 120 ?. After the reaction was cooled down to room temperature, the mixture was filtered through a short plug of silica gel and washed withcopious amounts of dichloromethane and water. The combined organic phase was concentrated under vacuum. The product was purified through flash column chromatography on 200-300 mesh silica gel with petroleum ether/ethyl acetate as eluent with a suitable ratio according to the TLC experiments (the eq 3, eq 4 and eq 6 was determined by GC analysis using standard curve method). The identity and purity of the product were ascertained by GC-MS, 1H and 13C NMR spectroscopy.
With Pd(tris[2-(diphenylphosphino)ethyl]phosphine tetrasulfide)(dibenzylideneacetone); caesium carbonate; In isopropyl alcohol; at 80℃; for 2h;
General procedure: Iodobenzene (1.2 mmol) and [Pd(pp3S4)(dba)] (1 mol %) were stirred in isopropanol (2.5 ml). Alcohol (1 mmol) followed by Cs2CO3 (5 mol %) were added to the above solution in the atmosphere of air. The mixture was heated to 80 C and the progress of the reaction was monitored by TLC. Rest of the procedure is same as described above.
With [(1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)Cu(O-tBu)]; In benzene; at 50℃;Sealed tube;
General procedure: A vial was charged with 270 mg(1.20 mmol) of 2-iodotoluene or 4-iodotoluene, 106 mg(0.24 mmol) of [(SIMes)Cu(O-t-Bu)] and 0.053 mL(0.36 mmol) of (Me)3SiCF3 in 5.4 mL of DMI/benzene(1.5:7.5) with 90.0 muL (0.95 mmol) of fluorobenzene, asinternal standard. After the solution was allowed to stir for fiveminutes, 0.60 mL aliquots were taken and transferred into 5 mL air-tight ampules. The ampules were sealed and placed in an oilbath at 50 °C. The reactions were removed from the oil bath atvarious time intervals and quenched with 0.6 mL of methanol inair. Each aliquot was monitored by 19F NMR spectroscopy forformation of the respective 2-trifluoromethyltoluene or 4-trifluoromethyltoluene product.
General procedure: For the generation of (phen)CuCF3 insitu, a vial was charged with 28.4 mg (0.28 mmol) of CuCl,32.3 mg (0.28 mmol) of KO-t-Bu, and 51.5 mg (0.28 mmol) of1,10-phenanthroline. To the vial, 5.4 mL of DMF was added.The solution was stirred for 0.5 h before the addition of0.042 mL (0.28 mmol) of Me3SiCF3. The solution was stirredfor an additional hour before the introduction of 52.1 mg(0.23 mmol) of 2-iodotoluene or 4-iodotoluene and 90.0 muL(0.95 mmol) of fluorobenzene, as internal standard. After thesolution was allowed to stir for five minutes, 0.60 mL aliquotswere taken and transferred into 5 mL air-tight ampules. Theampules were sealed and placed in an oil bath at 50 °C. Thereactions were removed from the oil bath at various time intervals and quenched with 0.6 mL of methanol in air. Each aliquotwas monitored by 19F NMR spectroscopy for formation of therespective 2-trifluoromethyltoluene or 4-trifluoromethyltolueneproduct
With potassium phosphate; nickel dichloride; Trimethylacetic acid; at 80℃; under 760.051 Torr; for 20h;Green chemistry;
General procedure: Into a 25 ml reaction flask was successively added nickel chloride (0.01 mmol), R2 substituted aryl iodide (table 2) (0.5 mmol), R3 substituted arylboronic acid (0.75 mmol), potassium phosphate (1.0 mmol), pivalic acid (0.25 mmol) and polyethylene glycol 400 (2.0 g), and introduce one atmospheric pressure carbon monoxide. The reaction mixture at 80 °C react until starting material reaction complete and cool to room temperature, pressure reducing evaporate the solvent column chromatography separation to obtain the product. The experimental results are set out in table 2.
91%
With palladium diacetate; sodium carbonate; In water; at 100℃; under 760.051 Torr; for 6h;Sealed tube; Autoclave; Green chemistry;
General procedure: A 75 mL autoclave equipped with a Teflon liner and a magnetic stirrer bar was charged with Pd(OAc)2 (4.48 mg, 2.0 × 10?2 mmol), L (46.7 mg, 4.0 × 10?2 mmol) and H2O (6 mL) and the mixture was stirred at room temperatures for 0.5 h under N2. Then iodobenzene (113 muL, 1 mmol), phenylboronic acid (134 mg, 1.1 mmol), Na2CO3(106 mg, 1 mmol), and n-decane (0.1 mL, GC internal standard) were added. Once sealed, the autoclave was purged three times with CO, and pressurized to 1 atm of CO. The reaction mixture was stirred at 100 °C for 2 h. After reaction, the mixture was extracted with diethyl ether (3 × 5 mL). The combined organic layer was concentrated in vacuo and the product was purified by column chromatography. In the recycling experiment, the aqueous phase containing the catalyst was subjected to a second run by charging it with the same substrates as mentioned above, and the reaction performed under the same conditions.
[(5-methoxy-4'-methyl-biphenyl-2-carbonyl)amino]acetic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With sodium acetate; palladium diacetate; In dimethyl sulfoxide; at 120℃; for 24h;Schlenk technique;
General procedure: A mixture of benzoyl aminoacetic acid 1a (90 mg, 0.5 mmol), 4-iodo-toluene 2a (218 mg, 1.0 mmol), Pd(OAc)2(11 mg, 0.05 mmol), anhydrous NaOAc (82 mg, 1.0 mmol), and DMSO (2 mL) wasplaced in a 25 mL Schlenk tube with a rubber plug in air. The tube was heatedat 120 for 24 h. The reaction mixture was cooled, diluted with alcohol, filtered through Celite, and concentrated in vacuo. Theresidue was purified by silica gel column chromatographywith ethyl acetate/ acetic acid (v:v = 80:1) to afford the desired product 3a (120 mg, 89percent).
1,10-phenanthroline trifluoroacetic acid cuprous (I)[ No CAS ]
[ 6140-17-6 ]
Yield
Reaction Conditions
Operation in experiment
83%Spectr.
With sodium fluoride; In N,N-dimethyl-formamide; at 140℃; for 8h;
In a nitrogen atmosphere, A polytetrafluoroethylene magnet was placed in a reactor, Followed by addition of 0.20 mmol of Example 1. 1,10-phenanthroline trifluoroacetic acid cuprous (I) complex (phen-CuO2CCF3),0.20 mmol to 4-iodotoluene and 0.60 mmol of NaF, Finally add 5 mL of N, N-dimethylformamide solvent, After stirring for 8 h at 140 ° C in a closed system, Cooled to room temperature, Extracted with ether three times, Each time 10 mL, The extract was concentrated on silica gel column chromatography, Eluting with n-pentane as the eluent, To give 4-trifluoromethyltoluene (83percent nuclear magnetic yield).
ethyl 5-methyl-1-(p-tolyl)-1H-indole-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46.74%
With potassium phosphate; copper(l) iodide; cis-N,N'-dimethyl-1,2-diaminocyclohexane; In toluene; for 22h;Reflux;
A mixture of <strong>[16382-15-3]ethyl 5-methyl-1H-indole-2-carboxylate</strong> (2.032 g, 10.00 mmol), 1-iodo-4-methyl-benzene (2.180 g, 10.00 mmol), iodocopper (95.22 mg, 0.5000 mmol), N1,N2-dimethylcyclohexane-1,2-diamine (284.5 mg, 315.4 muL, 2.000 mmol), and potassium phosphate (4.458 g, 21.00 mmol) in toluene (50.00 mL) was heated to reflux for 22 hours. The cooled reaction was filtered and evaporated. The green residue was purified by silica gel chromatography with 0-15percent ethyl acetate in hexanes to give ethyl 5-methyl-1-(p-tolyl)-1H-indole-2-carboxylate (1.43 g, 4.875 mmol, 48.74percent) as a colorless oil. ESI-MS m/z calc. 293.14. found 294.2 (M+1)+. Retention time: 0.83 minutes (1 minute run).
N-methyl-2-phenyl-2-trifluoromethylbenzimidazoline[ No CAS ]
[ 6140-17-6 ]
Yield
Reaction Conditions
Operation in experiment
42%
With potassium carbonate; copper(l) chloride; at 60℃; for 48h;Inert atmosphere;
General procedure: Under a nitrogen atmosphere, a mixture of iodoarene 1a (0.10 mmol), 5a (0.20 mmol, 2.0 equiv), copper(I) chloride (0.30 mmol, 3.0 equiv), and potassium carbonate (0.40 mmol, 4.0 equiv) in propionitrile (1.0 mL) was stirred at 60 C for 2 d, and the reaction was monitored by TLC. After completion of the reaction, supernatant of the reaction mixture was purified by preparative TLC to give trifluorotoluene 2a (88%).
With copper(l) iodide; (R,R)-N,N'-dimethyl-1,2-diaminocyclohexane; caesium carbonate; In N,N-dimethyl-d6-formamide; at 100℃; for 2h;Inert atmosphere;
Cyanimidazole (2.50 g, 26.86 mmol), dry N,N-dimethylformamide (40 mL), 1-iodo-4-methylbenzene (8.78 g, 40.29 mmol), (1R,2R)-N1,N2-dimethylcyclohexane-1,2-diamine (0.38 g, 2.69 mmol), cuprous iodide (0.51 g, 2.69mmol) and cesium carbonate (17.50 grams, 53.72 mmol) were sequentially added to a dry 250 mL one-neck flask at room temperature. Nitrogen was pumped and ventilated for 3 times. The reaction system was heated to 100°C for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, poured into 200 ml of water and extracted with ethyl acetate (150 ml 3 2). The organic phase was collected, washed with saturated brine (150 ml31), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The crude product was purified using a chromatography column (petroleum ether: ethyl acetate = 2:1) to afford a product 1-(ptolyl)-<strong>[57090-88-7]1H-<strong>[57090-88-7]imidazole-4-carbonitrile</strong></strong> (2.20 g, almost white solid), yield 44.7percent. 1H-NMR(CDCl3, 400 MHz): 8.71 (s, 1H), 8.47 (s, 1H), 7.59-7.58 (d, J =6.8Hz, 2H), 7.44 (d, J =6.4Hz, 2H).
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In dimethyl sulfoxide; at 20 - 120℃;
General procedure: Isoindolin-1-one (200 mg, 1.50mmol) was dissolved in super-dry DMSO (4 mL), and Cs2CO3 (1215 mg, 3.75 mmol), CuI (58 mg, 0.30mmol) and N1,N2-dimethylethane-1,2-diamine (27 mg, 33 muL, 0.30 mmol) were added to the solution.The resulting mixture was stirred at room temperature for 10 min, after which iodobenzene (2.25mmol) was added. Then the mixture was heated to 120 C. When TLC showed that isoindolin-1-onehad been fully converted, the reaction was stopped. The mixture was extracted with ethyl acetate (20mL) and H2O (10 mL). The water phase was re-extracted with ethyl acetate (20 mL). The organic layerwas combined and washed with brine (10 mL). Then the solution was dried over anhydrous MgSO4,filtered and concentrated, and the crude residue was purified by flash chromatography over silica gelusing CH2Cl2/CH3OH as the gradient elution to afford the title compounds.
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