110-70-3 | Page 6 of 27 | Chiral nitrogen ligands

Extracurricular laboratory: Synthetic route of 110-70-3

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of N1,N2-Dimethylethane-1,2-diamine, 110-70-3

The major producers of chemicals have been the Europe, Japan and China. Due to the growing call for a cleaner, greener environment, people will have to find innovative ways to maintain their relevance. N1,N2-Dimethylethane-1,2-diamine, cas is 110-70-3,the chiral-nitrogen-ligands compound. Here is a downstream synthesis route of the compound., 110-70-3

The ligand L1 was synthesized via previously reported procedure[23]. A solution of potassium carbonate (2.55 g, 18.45 mmol)in 10 mL water was dropwise added to the aqueous solution of 2-(chloromethyl)-pyridine hydrochloride (1.5 g, 9.15 mmol in10 mL). After about 30 min. of stirring at room temperature, thereaction mixture was extracted with dichloromethane(3 20 mL). The combined organic extracts were dried over anhydroussodium sulfate. The solution was filtered and the solvent wasremoved under vacuum. The resulted residue was then dissolvedin dichloromethane (10 mL). The dichloromethane solution of 2-chloromethyl-pyridine was added dropwise to a solution of N,N0-dimethylethylenediamine (0.471 mL, 5.34 mmol) in dichloromethane(15 mL). After this addition, 10 mL of aqueous sodiumhydroxide (1 M) was added slowly and the reaction mixture wasstirred for next 60 h at room temperature. After stirring was finished,another fraction of sodium hydroxide (10 mL, 1 M) wasadded rapidly. The reaction mixture was extracted with dichloromethane(3 25 mL) and combined organic portion was dried overanhydrous sodium sulfate. Evaporation of solvent led to isolationof the ligand L1 as a dark orange oil. (1.13 g, Yield 79%) 1H NMR(500 MHz, Methanol-d4) d 7.27 (m, 2H, pyridine ring), 7.50 (d,2H, pyridine ring), 7.76 (m, 2H, pyridine ring), 8.45 (d, 2H, pyridinering), 3.68 (s, 4H, -N-CH2-Py), 2.63 (s, 4H, -CH2-CH2-), 2.26 (s, 6H,N-CH3). IR (cm1): 2945, 2789, 1589, 1569, 1472, 1432, 1360,1304, 1146, 1090, 1031, 994, 635, 614, 418.

Reference£º
Article; Singh, Nirupama; Niklas, Jens; Poluektov, Oleg; Van Heuvelen, Katherine M.; Mukherjee, Anusree; Inorganica Chimica Acta; vol. 455; (2017); p. 221 – 230;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Extracurricular laboratory: Synthetic route of 110-70-3

110-70-3, In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles.,110-70-3 ,N1,N2-Dimethylethane-1,2-diamine, other downstream synthetic routes, hurry up and to see

A solution of di-tert-butyl dicarbonate (4.95 g, 22.69 mmol) in CH2Cl2 (240 mL) was added dropwise to a stirred solution of N,N?-dimethylethane-1,2-diamine (4 g, 45.38 mmol) in CH2Cl2 (80 mL) over a period of 20h. The resulting mixture was stirred at r.t. for 3h. The mixture was then washed sequentially with sat. Na2CO3 (2 x 100 mL), water (50 mL), and sat. brine (50 mL). The organic solution was dried (MgSO4) and concentrated in vacuo. Purification by FCC, eluting with 0-10% CH3OH in CH2Cl2 gave the title compound (2.177 g, 51%) as a pale yellow oil; 1H NMR: 1.40 (9H, s), 2.28 (3H, s), 2.57 (2H, t), 2.79 (3H, s), 3.20 (2H, t).

Reference£º
Patent; ASTRAZENECA AB; ASTRAZENECA UK LIMITED; BUTTERWORTH, Sam; FINLAY, Maurice, Raymond, Verschoyle; WARD, Richard, Andrew; KADAMBAR, Vasantha, Krishna; CHANDRASHEKAR, Reddy, C.; MURUGAN, Andiappan; REDFEARN, Heather, Marie; WO2013/14448; (2013); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

The origin of a common compound about 110-70-3

The chemical industry reduces the impact on the environment during synthesis,110-70-3,N1,N2-Dimethylethane-1,2-diamine,I believe this compound will play a more active role in future production and life.

A solution of N,N?-dimethylethylenediamine (1.72g, 20mmol) in dry tetrahydrofuran (60mL) was treated with 2-chloromethylpyridine hydrochloride (6.604g, 40mmol) and triethylamine (8.093g, 80mmol) and the mixture was stirred under reflux for 18h. The resulting mixture was cooled to in ice and the triethylamine hydrobromide was removed by filtration. The filtrate was then treated with 10mL 15% NaOH solution and extracted with CH2Cl2 (3¡Á40mL). The combined extracts were dried over anhydrous MgSO4. Removal of the solvent with rotary evaporator yielded dark brown oil which was chromatographed on alumina and eluted with 95/5 (v/v) mixture of ethyl acetate/MeOH (Rf=0.81). The purified ligand was obtained as yellow viscous oil (yield: 4.2g, 79%). Selected IR bands (cm-1): nu(C-H) 3064 (w), 2949 (m), 2802 (m); pyridyl groups: 1592 (s), 1577 (m), 1474 (m), 1435 (s). 1H NMR: 8.43 (m, 2H), 7.70 (m, 2H), 7.37 (m, 2H), 7.72 (m, 2H), 3.58 (s, 4H), 2.51 (s, 4H), 2.14 (s, 6H); 13C NMR: 159.74 (2-py), 149.06 (6-py), 136.78 (4-py), 123.01 (3-py), 122.42 (5-py), 63.95 (N-CH2-py), 35.40 (-CH2-CH2-N), 42.94 (CH3-N), 40.60 (CH3-N).

Reference£º
Article; Mautner, Franz A.; Koikawa, Masayuki; Mikuriya, Masahiro; Harrelson, Emily V.; Massoud, Salah S.; Polyhedron; vol. 59; (2013); p. 17 – 22;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Introduction of a new synthetic route about 110-70-3

As a common heterocyclic compound, it belongs to chiral-nitrogen-ligands compound, name is N1,N2-Dimethylethane-1,2-diamine, and cas is 110-70-3, its synthesis route is as follows.

Example 71Synthesis of tert-butyl methyl [2-(methylamino)ethyl]carbamate (VI-I) A solution of di-tert-butyl dicarbonate (2.18 g, 0.01 mol) in CH2Cl2 (120 mL) was added dropwise to a solution of N,N’-Dimethyl-ethane-1,2-diamine (1.76 g, 0.02 mol) in CH2Cl2 (40 mL) over 6 h with vigorous stirring. The reaction mixture was continued to stir for a further 18 h at room temperature. Then the solvent was concentrated in vacuo to give an oily residue, which was dissolved in 60 mL of 2M Na2CO3 aqueous solution, and extracted with CH2Cl2 (30 mL x 2). The combined organic layers were washed with 2M Na2CO3 (30 mL x 2), and dried over anhydrous MgSO4. The solvent was evaporated in vacuo to yield the product, which was purified by column chromatography (silica gel, CH2Cl2 : MeOH, 9: 1) to afford colorless oil (VI-I, 1.15 g, 61%)

Reference£º
Patent; NORTHWESTERN UNIVERSITY; SILVERMAN, Richard, B.; JI, Haitao; LAWTON, Graham, R.; WO2008/42353; (2008); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

New downstream synthetic route of 110-70-3

This compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route,110-70-3,N1,N2-Dimethylethane-1,2-diamine,its application will become more common.

General procedure: To a cooled to 0 C suspension consisting of N,N’-dimethyl-1,2-ethylenediamine (4.4 g, 0.05 mol), sodium bicarbonate (33.6 g, 0.40 mol), and CH2Cl2 (50 mL), a solution of 2-bromopropionyl chloride (1a) (25.7 g, 0.15 mol) in CH2Cl2 (40 mL) was added. The reaction temperature was maintained within 0-5 C and the addition time was 40 min. The mixture was stirred for 4 h at the same temperature. Water (130 mL) and CH2Cl2 (60 mL) were added and the organic layer was separated. The combined organic fractions were dried over sodium sulfate. The solvent was removed under reduced pressure. The residue was treated with hexane (30 mL) and a solid product was filtered off and recrystallized from diethyl ether to give pure compound 2a (13.25 g, 74%), m.p. 77.0-77.4 C (from diethyl ether).

Reference£º
Article; Goncharova; Yakushchenko; Raevskaya; Yakushchenko; Konovalova; Russian Chemical Bulletin; vol. 68; 1; (2019); p. 181 – 185; Izv. Akad. Nauk, Ser. Khim.; 1; (2019); p. 181 – 185,5;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Discovery of N1,N2-Dimethylethane-1,2-diamine

110-70-3, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact.110-70-3, N1,N2-Dimethylethane-1,2-diamine it is a common compound, a new synthetic route is introduced below.

a 1,3-Dimethyl-2-(2-thienyl)-imidazolidine 23.5 g (267 mmol) of N,N’-dimethylethylenediamine were dissolved in 300 ml of toluene and treated with 29.8 g (266 mmol) of thiophene-2-carbaldehyde. The clear mixture was refluxed for 4 hours using a Dean-Stark trap. After that time 4.9 ml of water had separated in the trap. After cooling, the solution was filtered and evaporated. The oily residue was destined in vacuo. Yield: 45 g. Boiling point: 65 C. (0.1 mm Hg).

Reference£º
Patent; Aventis Pharma Deutschland GmbH; Genentech, Inc.; US6566366; (2003); B1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

The origin of a common compound about 110-70-3

The above mentioned protocol was adapted for preparation ofligand L2. In a solution of 2-(chloromethyl)-3,4-dimethoxypyridinehydrochloride (2.09 g, 9.34 mmol) in 10 mL of water, a solution ofpotassium bicarbonate(2.73 g, 19.74 mmol) in water (10 mL) wasadded dropwise. The reaction mixture was stirred at room temperaturefor next 30 min. After stirring is done, solution was extractedwith dichloromethane (3 20 mL). The combined dichloromethanelayer was treated with anhydrous sodium sulfate. Thesolution was filtered and solvent was removed by rotatory evaporation.The collected light yellow oil was dissolved in dichloromethane(10 mL). The 2-(chloromethyl)-3,4-dimethoxypyridinesolution in dichloromethane was added dropwise to a solution of N,N0-dimethylethylenediamine (0.503 mL, 4.67 mmol) in dichloromethane(15 mL). In the next step aqueous 1 M sodium hydroxide(10 mL) was slowly added and solution was stirred for additional60 h at room temperature. After 60 h of stirring followed by therapid addition of a second fraction of aqueous 1 M sodium hydroxide(10 mL, 10 mmol), the product was extracted with dichloromethane(3 25 mL). The combined organic layers were driedover anhydrous sodium sulfate and filtered. Subsequently, theexcess solvent was evaporated by vacuum to afford yellow colorviscous oil (1.86 g, Yield 89%). 1H NMR (500 MHz, Methanol-d4) d8.14 (d, 2H, pyridine ring), 7.05 (d, 2H, pyridine ring), 3.95 (s,6H,-O-CH3-Py), 3.85 (s, 6H,-O-CH3-Py), 3.66 (s, 4H,-N-CH2-Py),2.67 (s, 4H, -CH2-CH2-), 2.26 (s, 6H, -N-CH3). 13C NMR (126 MHz,Methanol-d4) d 160.77, 152.19, 147.28, 146.07 (d, J = 10.3 Hz),108.87, 61.40, 58.17, 56.43, 56.07, 43.10. ESI-MS (in CH3OH).observed m/z 391.3 [(L2 + H)+] (z = 1); theoretical-391.23[(L2 + H)+] (z = 1). IR (cm1): 3375, 2945, 1626, 1584, 1447, 1425,1261, 1228, 1173, 1073, 994, 828, 651, 603.

Application of 110-70-3

In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact.110-70-3, N1,N2-Dimethylethane-1,2-diamine it is a common compound, a new synthetic route is introduced below.110-70-3

The ligand L1Q was synthesized via similar procedure mentionedabove [23]. To an aqueous solution of 2-(chloromethyl)-quinoline hydrochloride (2 g, 9.34 mmol), a solution of potassiumcarbonate (2.73 g, 18.66 mmol) in 10 mL water was added in dropwisemanner. The reaction mixture was stirred for 30 min at ambienttemperature. After stirring, the resulting solution wasextracted with dichloromethane (3 20 mL). The combinedorganic extracts were dried over anhydrous sodium sulfate andsolvent was evaporates under vacuum. The product 2-(chloromethyl)-quinoline was then dissolved in dichloromethane(10 mL) and was added dropwise to a solution of N,N0-dimethylethylenediamine (0.503 mL, 5.34 mmol) in 15 mL dichloromethane.After this addition, aqueous sodium hydroxide (10 mL,1 M) was added slowly. The reaction mixture was stirred for next60 h at room temperature, followed by rapid addition of anotherfraction of sodium hydroxide (10 mL, 10 mmol). The reaction mixturewas then extracted with dichloromethane (3 25 mL) andorganic portions were combined and dried over anhydrous sodiumsulfate. Volatile solvents were removed under vacuum to obtaincrude ligand L1Q as dark brown oil (1.68 g, Yield 85%). 1H NMR(500 MHz, Methanol-d4) d 7.57 (m, 2H, quinoline ring),7.63 (d,2H, quinoline ring), 7.73 (m, 2H, quinoline ring), 7.88 (d, 2H, quinolinering),7.98 (d, 2H, quinoline ring), 8.21 (d, 2H, quinoline ring),3.84 (s, 4H, -N-CH2-Quinoline), 2.71 (s, 4H, -CH2-CH2-), 2.32 (s,6H, -N-CH3). IR (cm1): 3384, 3056, 2946, 2800, 1617, 1598,1564, 1504, 1456, 1426, 1361, 1309, 1223, 1141, 1119, 1032,985, 951, 828, 784, 756, 619.

New downstream synthetic route of N1,N2-Dimethylethane-1,2-diamine

110-70-3, The major producers of chemicals have been the Europe, Japan and China. Due to the growing call for a cleaner, greener environment, people will have to find innovative ways to maintain their relevance. N1,N2-Dimethylethane-1,2-diamine, cas is 110-70-3,the chiral-nitrogen-ligands compound. Here is a downstream synthesis route of the compound.

The mixture of N, N’-Dimethylene diamine 21-1 (5 mL, 46.5 mmol) and tert-butyl acrylate 13 mL (116 mmol) was heated at 85 C for 1 hour. Another 13 mL (116 mmol) of tert- butyl acrylate was added. The reaction mixture was continuely heated at 85C for 1 hour and stirred at room temperature overnight. The reaction mixture was concentrated in vacuo. The residue wasdiluted with hexanes and purified by flash column chromatography using SiliaSep Cartridges (120g), eluting with 0-5% methanol/DCM to give 10.1 g (62%) of compound 21-2. MS (ESI) m/z 345 [M+H].

Reference£º
Patent; AMBRX, INC.; MIAO, Zhenwei; ATKINSON, Kyle, C.; BIROC, Sandra; BUSS, Timothy; COOK, Melissa; KRAYNOV, Vadim; MARSDEN, Robin; PINKSTAFF, Jason; SKIDMORE, Lillian; SUN, Ying; SZYDLIK, Angieszka; VALENTA, Ianina; WO2012/166560; (2012); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Application of N1,N2-Dimethylethane-1,2-diamine

110-70-3, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. N1,N2-Dimethylethane-1,2-diamine, cas is 110-70-3,the chiral-nitrogen-ligands compound, it is a common compound, a new synthetic route is introduced below.

To a solution of N,N’-dimethylethane-l,2-diamine (40.4 g) in DCM (300 mL) was added a solution of Boc20 (10 g, 10.6 mL, 45.8 mmol) in DCM (100 mL) dropwise at 0 C over 1 hr. The reaction mixture was stirred at room temperature for 18 hrs. The organic layer was washed with saturated aqueous NaHC03 (50 mL), brine (50 mL), dried over Na2S04 and concentrated in vacuo. The residue was purified by column chromatography to afford ie/t-butyl N-methyl-N-[2- (methylamino)ethyl]carbamate (6.8 g, Compound BC-1) as a yellow oil. 1H NMR (400MHz, CDC13) delta ppm: 3.34 (br. s., 2H), 2.89 (s, 3H), 2.74 (t, / = 6.7 Hz, 2H), 2.46 (s, 3H), 1.47 (s, 9H).

Reference£º
Patent; F. HOFFMANN-LA ROCHE AG; HOFFMANN-LA ROCHE INC.; GAO, Lu; LIANG, Chungen; YUN, Hongying; ZHENG, Xiufang; WANG, Jianping; MIAO, Kun; ZHANG, Bo; (157 pag.)WO2018/41763; (2018); A1;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis