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To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL)was added N,N,N’,N’-tetramethylethylenediamine(0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux withstirring for 2 h, during which time a pale-yellow solid was observed. To thewarm reaction mixture was added cold acetone (~9 mL), and the reaction mixturewas cooled to 0 °C, which led to a white precipitate. Filtration through aBuchner funnel furnished a white powder, which was washed with cold acetone (~4mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 94percent) as a whitepowder: mp= 189.0-194.0 °C; 1H NMR (300 MHz, CDCl3) δ4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J = 6.3 Hz, 6H); 13CNMR (75 MHz, CDCl3) δ 65.87, 56.75, 51.28, 31.99, 29.78, 29.75,29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum(ESI) m/z 227.5 [M2+; calcd for C30H66N2:227.26].
92%
for 2 h; Reflux
Comparative compound (12,2,12) bromide To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL) was added N,N,N',N'-tetramethylethylenediamine (0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux with stirring for 2 h, during which time a pale-yellow solid was observed. To the warm reaction mixture was added cold acetone (~9 mL), and the reaction mixture was cooled to 0 °C, which led to a white precipitate. Filtration through a Buchner funnel furnished a white powder, which was washed with cold acetone (~4 mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 92percent) as a white powder: mp 189.0-194.0 °C; 1H NMR (300 MHz, CDC13) δ 4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J= 6.3 Hz, 6H); 13C NMR (75 MHz, CDC13) δ 65.87, 56.75, 51.28, 31.99, 29.78, 29.75, 29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum (ESI) m/z 227.5 M2+; calcd for C30H66N2: 227.26].
82%
for 12 h; Reflux
General procedure: A magnetically stirred solution of N,N,N0,N0-tetramethylethylenediamine(4.64 g, 40 mmol) and 1-bromodecane(17.68 g, 80 mmol) in 200 mL of acetone was refluxed for 12 h. Then the mixture was cooled and was left for 12 h in cold conditions. The crude product was precipitated in the form of white crystals. It was recrystallized two times from acetone then filtered and dried in air, yielding 10.4 g of white crystals (47 percent).
Reference：
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[2] Patent: WO2015/69760, 2015, A1, . Location in patent: Paragraph 0098; 0099
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[22] Patent: US2113606, 1935, ,
[23] Patent: FR790279, 1936, ,
To a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL)was added N,N,N?,N?-tetramethylethylenediamine(0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux withstirring for 2 h, during which time a pale-yellow solid was observed. To thewarm reaction mixture was added cold acetone (~9 mL), and the reaction mixturewas cooled to 0 C, which led to a white precipitate. Filtration through aBuchner funnel furnished a white powder, which was washed with cold acetone (~4mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 94%) as a whitepowder: mp= 189.0-194.0 C; 1H NMR (300 MHz, CDCl3) delta4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J = 6.3 Hz, 6H); 13CNMR (75 MHz, CDCl3) delta 65.87, 56.75, 51.28, 31.99, 29.78, 29.75,29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum(ESI) m/z 227.5 [M2+; calcd for C30H66N2:227.26].
92%
In acetonitrile; for 2h;Reflux;
Comparative compound (12,2,12) bromideTo a solution of 1-bromododecane (0.39 mL, 1.6 mmol) in CH3CN (0.12 mL) was added N,N,N',N'-tetramethylethylenediamine (0.080 mL, 0.53 mmol). The resulting clear solution was warmed to reflux with stirring for 2 h, during which time a pale-yellow solid was observed. To the warm reaction mixture was added cold acetone (~9 mL), and the reaction mixture was cooled to 0 C, which led to a white precipitate. Filtration through a Buchner funnel furnished a white powder, which was washed with cold acetone (~4 mL) and then hexanes (~4 mL), affording (12,2,12) (306 mg, 92%) as a white powder: mp 189.0-194.0 C; 1H NMR (300 MHz, CDC13) delta 4.79 (s, 4H), 3.74-3.69 (m, 4H), 3.50 (s, 12H), 1.79 (br s, 4H), 1.38-1.25 (m,36H), 0.88 (t, J= 6.3 Hz, 6H); 13C NMR (75 MHz, CDC13) delta 65.87, 56.75, 51.28, 31.99, 29.78, 29.75, 29.69, 29.65, 29.46, 26.36, 23.16, 22.76, 14.21; low resolution mass spectrum (ESI) m/z 227.5 M2+; calcd for C30H66N2: 227.26].
82%
In acetone; for 12h;Reflux;
General procedure: A magnetically stirred solution of N,N,N0,N0-tetramethylethylenediamine(4.64 g, 40 mmol) and 1-bromodecane(17.68 g, 80 mmol) in 200 mL of acetone was refluxed for 12 h. Then the mixture was cooled and was left for 12 h in cold conditions. The crude product was precipitated in the form of white crystals. It was recrystallized two times from acetone then filtered and dried in air, yielding 10.4 g of white crystals (47 %).
In ethanol; acetone; at 74.99℃; for 48h;
Gemini surfactant i.e. ethanediyl-1,2-bis(dimethyldodecylammonium bromide) was prepared by followingthe well established procedure (Scheme 1) reported in literature [23,24]. Mixture of N, N, N, N-tetramethyl ethylene diamine (TEMED) and1-bromododecane (molar ratio of 1:2) in 10 ml of ethyl alcohol wastaken in round bottom flask then 5 ml of acetone was added to removeturbidity and get clear solution. This solution was then refluxed at348.15 K for approximately 48 h until the entire volume of TEMEDwas consumed. After removal of the solvent by evaporation, the preparedwaxy compound was allowed to cool at room temperature and washed with mixture of ethyl acetate and acetone in 1:1 ratio. Thewashing was repeated 6-7 times to eliminate excess of alkyl bromide.The resulting white product was crystallized twice in dry acetone anddried in vacuum oven at 323.15 K.
bis(N,N-dimethyl-n-dodecyl)ethylene-1,2-diammonium dipicrate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In water; for 2191.5h;
General procedure: Yellow crystals of the 1:2, 1:3, and 1:4 oligomeric surfactant-picrate compounds 1-3 were made from equimolar heated aqueous solution of picric acid and surfactant ammonium bromide, after three months of aging, as described by us previously [1]. Novel picrate (P) compounds are presented in Scheme 1 and marked as follows: bis(N,N-dimethyl-n-dodecyl)ethylene-1,2-diammonium dipicrate, abbreviated (12-2-12), 2P- (compound 1); N-bis[2-(N?,N?-dimethyl-n-dodecylammonio)ethylene]-n-dodecyl-N-methyl-1,2-diammonium tripicrate, abbreviated (12-2-12-2-12), 3P- or [12-(2-12)2], 3P- (2); and N,N?-bis[2?-(N?,N?-dimethyl-n-dodecylammonio)ethylene]-di-n-dodecyl-N,N?-dimethyl-ethylene-1,2 diammonium tetrapicrate, abbreviated (12-2-12-2-12-2-12), 4P- or [12-(2-12)3], 4P- (3). The purity of compounds was checked by elemental analysis. Anal. for (1) (C30H66N2)2+.2(C6H2N3 O7)-, i.e. C42H70N8O14, found: C, 55.35; H, 7.76; N, 12.27%; requires C, 55.37; H, 7.74; N, 12.30%; for (2) (C45H98N3)3+. 3(C6H2N3O7)-, i.e. C63H104N12O21, found: C, 55.40; H, 7.66; N, 12.28%; requires C, 55.41; H, 7.68; N, 12.31%; and for (3) (C60H130N4)4+.4(C6H2N3O7)-, i.e. C84H138N16O28, found: C, 55.40; H, 7.66; N, 12.28%; requires C, 55.43; H, 7.64; N, 12.31%.
General procedure: General procedure for the synthesis of Gemini (L)-N-acetylmethioninate 3a-d Gemini bromide [Gemini(Br)2] [19] (1 equiv.) and silver (L)-N-acetylmethioninate [Ag(L-acmet)] 2 (2.2 equiv.) were dissolved in water or a mixture of water and methanol. The mixture was stirred for 1 to 12 h at room temperature or 40 C, depending of the length of the alkyl chain of surfactant. The solvent was removed under vacuum and the residue was extracted with methanol, filtered off and evaporated under vacuum. [Gemini(L-acmet)2] 3a-d were obtained as white solids in 80 to 97% yields.
Materials
SGS was synthesized in our laboratory according to (Lai et al., 2014), while BQAS was synthesized from 1,2-dibromoethane and N,N-dimethyldodecylamine (Liet al., 2018). Specifically, 1.88 g of 1,2-dibromoethane, and 6.40 g of N,N-dimethyldodecylamine were dissolved in 50 ml of isopropyl alcohol. The reaction was conducted at 80°C for 48 h. Then the solvent was removed using a rotary evaporator and purified by recrystallization using the mixed solvent hexane-ethanol (vol/vol = 1/1).
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