2-METHYLDIPHENYLAMINE

General procedure: In a typical example, phenylboronic acid 1 (1.22 g, 1 mmol) was charged in the flask containing KGeneral procedure: To a stirred solution of phenylboronic acid (1.0 mmol), aniline (1.0 mmol), and KGeneral procedure: The 25 mL RB flask was charged with arylboronic acid (1 mmol), N-nucleophile (2 mmol), Ni(OAc)General procedure: Typically, [Pd(cinnamyl)Cl]2 (0.0031 g, 0.006 mmol), ligand 1 (0.0107 mg, 0.012 mmol), and KO(t-Bu) (0.081 g, 0.72 mmol) were loaded into a Schlenk tube. If a solid aryl bromide or amine was used, it was also added at this time. To the mixture of solids, the aryl bromide (0.6 mmol) and amine (0.72 mmol) were added via syringe (if liquid), followed by toluene (2 mL). The resulting mixture was stirred at room temperature for 1 min., then placed in a pre-heated, 80 °C oil bath and allowed to react for 12 h. After this time, the mixture was removed from the bath and cooled to room temperature, diluted with EtOAc (5 mL), and filtered through silica (1 × 4 cm column, ~10 mL), eluting with EtOAc (20 mL) or until the filtrate ran clear. The volatiles were removed from the filtrate via rotary evaporation and the resulting residue was subjected to flash chromatography on silica gel (8 × 2 cm column, ~25 mL silica). Specific details related to the synthesis, yield and characterization of each coupled product are described below in Section 4.8.General procedure: In a Schlenk tube with a magnetic bar, base (3.0mmol), PdClUnder a nitrogen atmosphere, 25 g of 2-bromotoluene and 40 g of aniline were dissolved in 200 ml of dehydrated toluene, 0.5 g of palladium acetate, 27 g of sodium t-butoxide and 1.4 g of tri-t-butylphosphine were added and the mixture was heated at 120 ° C. for 8 hours. After the reaction, water was added, the organic layer and the aqueous layer were separated with a separating funnel, and the organic layer was concentrated. The crude product was purified on a silica gel short column (solvent: toluene)19 g (yield 49percent) of the following target compound was obtained.General procedure: A Schlenk ask was charged with the required aryl chloride (0.25 mmol), amine (0.30 mmol), N-heterocyclic carbene–palladium(II) complex (2 molpercent), KOtBu (1.3 equiv), and toluene (0.5 mL). The mixture was stirred at 110 C for 15 h under N2. After cooling, the mixture was evaporated and the product was isolated by preparative TLC on silica gel plates. The puried products were identied by 1H NMR spectra, and their analytical data are given in the Supporting Information.The general reaction conditions: 1, 4 - dioxane (0.5 ml) in, will aryl chloride (0.7mmol), level aromatic amine (1.2equiv. , Relative to the aryl chloride) butyl potassium (1.3equiv. , Relative to the aryl chloride) complex (41), reaction 1 - 24 hours. Yield rate of the product after separation and purification. The following product 53a - 53r in, the right half part of the aryl group is derived from the aromatic amine compound.General procedure: Under a N2 atmosphere, KOtBu (102.1 mg, 1.3 equiv) and a so-lution of complex 3a (10e50 mL, 0.01e0.05 molpercent, prepared from4.6 mg of complex 3a in 1.0 mL dichloromethane) were added into aSchlenk reaction tube. The tube was sealed and the solvent wasremoved under reduced pressure. Then toluene (0.5 mL), amines(0.84 mmol) and aryl chlorides (0.70 mmol) were successivelyadded. The mixture was stirred vigorously at the specied tem-perature for 3e24 h. Then the solvent was removed under reducedpressure and the residue was puried by ash column chroma-tography (SiO2) to give the corresponding products.Example 9General Procedure for Pd-Catalysed Amination Reactions[0045] The phosphine ligand compounds of the present invention can be used in conjunction with transition metal catalysts employed in the animation of aryl chlorides. Pd- catalyzed amination of aryl halides has become a powerful method for the synthesis of aniline derivatives. Employing readily available aryl chlorides in this transformation has also become a focus and met with moderate success in recent years. EPO General procedure: Under NExample 48 Reaction flask was added 2-methylaniline 0.107 g (1 mmol), phenylhydrazine 0.216 g(2 mmol), CuPc 0.116 Ke (0.2 mmol), Cu (SO 4) 20.052 g (0.2 mmol) and 10 ml of aceticacid, 25 °C reaction; TLC until complete reaction was followed over; After the reaction, the crude product obtained was purified by column chromatography (petroleum ether: ethylacetate = 100: 1) to give the desired product (88percent yield)General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)General procedure: In a typical run, an oven-dried 10 mL round bottom flask was charged with a known mole percent of catalyst, NaOtBu (1.3 mmol), aryl amine (1.2 mmol) and aryl halide (1 mmol) with the appropriate solvent(s) (4 mL). The flask was placed in a preheated oil bath at required temp. After the specified time the flask was removed from the oil bath, water (20 mL) was added, and extraction with ether (4 × 10 mL) was done. The combined organic layers were washed with water (3 × 10 mL), dried over anhydrous Na2SO4, and filtered. Solvent was removed under vacuum. The residue was dissolved in hexane and analyzed by GC–MS.#10;To a mixture of 0.05 g catalyst and aryl iodide (1.0 mmol) in9.0 cm3 DMSO, amine (1.2 mmol) and KOH (1.5 mmol)was added and the mixture was vigorously stirred at 120 Cfor appropriate time under a dry nitrogen atmosphere. Afterthe completion of the reaction, the catalyst was filtered offand washed with water followed by acetone and dried inoven. The filtrate was extracted with ethyl acetate(3 9 20 cm3) and the combined organic layers were driedwith anhydrous Na2SO4 by vacuum. The filtrate was concentratedby vacuum and the resulting residue was purifiedby column chromatography on silica gel to provide thedesired product. All the products are known and the spectroscopicdata (FT-IR and NMR) and melting points wereconsistent with those reported in the literature [26].General procedure: In an oven dried 100 mL RB flask, polymer supported Cu(II)catalyst (50 mg, 0.0098 mmol), aryl halide (1 mmol), aromatic amines (1.2 mmol), KOH (1 mmol), and 10 ml DMSO were stirred under nitrogen atmosphere, at 140 °C. 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 NaGeneral procedure: In an oven dried 100 mL round bottom flask, Cu-grafted cat-alyst (0.05 g), aryl halide (1 mmol), aromatic amines (1.2 mmol), KOH (1 mmol), and 10 mL DMSO were stirred under nitrogen atmo-sphere, at 140C. The reaction mixtures were collected at differenttime intervals and identified by GC–MS and quantified by GC.After the completion of the reaction, the catalyst was filtered offand washed with water followed by acetone and dried in oven.The filtrate was extracted with ethyl acetate (3 × 20 mL) and thecombined 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.General procedure: In a 50 mL round bottom flask, the mixture of iodobenzene (2 mmol), amine (2.4 mmol), t-BuONa (3 mmol), and 1 as catalyst (0.05 mol percent) was taken in toluene (10 mL). The reaction mixture was then heated to 110°C and continued for 12–18 h. The progress of the reaction was monitored by TLC. Upon completion of the reaction the aqueous reaction mixture was extracted with ethyl acetate, washed with brine, dried over MgSOAniline reaction flask was added 0.093 g (1 mmol), 2- methyl-phenylhydrazine 0.244g (2 mmol), CoPc 0.057 Ke (0.1 mmol), Cu (SO 4) 20.026 g (0.1 mmol) and 10 ml of methylene chloride, 20 °C reaction; TLC until the reaction was followed completelyfinished; the crude product after the reaction was subjected to column chromatography(petroleum ether: ethyl acetate = 100: 1) to give the target product (64percent yield).General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)General procedure: A Schlenk reaction tube was charged with Amine or amide 1 (1.2 mmol), aryltrimethylgermane 2 (1.0 mmol), Pd(OAc)2 (5 mol percent), PPh3 (5 mol percent), toluene (2.0 mL), under argon atmosphere at 100 °C for 12 h. After completion of the reaction, asindicated by TLC, the reaction mixture was extracted with diethyl ether (3×10 mL). The combined organic layer was washedby water and dried by Na2SO4. The solvent was removed in vacuo and the residue, further purification was carried out byshort column chromatography (silica gel 300400 mesh, petroleum ether / ethyl acetate as the eluent) to give the targetmolecules.The reaction was conducted at 130°C in DMSO (3mL) with substituted amine (3 mmol), substituted benzoic acid (1.3mmol), KOH (7 mmol), and 200 mL of the solution containing CuNP- or NiNP-PNF. The progress of the reaction was monitored by TLC. After reaction completion, the mixture was cooled to room temperature and was extracted with ethyl acetate (220mL). The organic extract was washed twice with water and dried with anhydrous NaGeneral procedure: A Schlenk reaction tube was charged with Amine or amide 1 (1.2 mmol), aryltrimethylgermane 2 (1.0 mmol), Pd(OAc)2 (5 mol percent), PPh3 (5 mol percent), toluene (2.0 mL), under argon atmosphere at 100 °C for 12 h. After completion of the reaction, asindicated by TLC, the reaction mixture was extracted with diethyl ether (3×10 mL). The combined organic layer was washedby water and dried by Na2SO4. The solvent was removed in vacuo and the residue, further purification was carried out byshort column chromatography (silica gel 300400 mesh, petroleum ether / ethyl acetate as the eluent) to give the targetmolecules.

Molecular Weight:183.25
XLogP3:3.7
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:183.104799419
Monoisotopic Mass:183.104799419
Topological Polar Surface Area:12
Heavy Atom Count:14
Complexity:161
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes