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Chemical Structure| 127999-16-0 Chemical Structure| 127999-16-0

Structure of Tr-peg7
CAS No.: 127999-16-0

Chemical Structure| 127999-16-0

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Product Details of [ 127999-16-0 ]

CAS No. :127999-16-0
Formula : C31H40O7
M.W : 524.65
SMILES Code : OCCOCCOCCOCCOCCOCCOC(C1=CC=CC=C1)(C2=CC=CC=C2)C3=CC=CC=C3
English Name :Tr-peg7
MDL No. :MFCD22683315

Safety of [ 127999-16-0 ]

Application In Synthesis of [ 127999-16-0 ]

* 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.

  • Downstream synthetic route of [ 127999-16-0 ]

[ 127999-16-0 ] Synthesis Path-Downstream   1~10

  • 1
  • [ 2615-15-8 ]
  • [ 76-83-5 ]
  • [ 127999-16-0 ]
YieldReaction ConditionsOperation in experiment
88% With pyridine at 45℃;
74% With pyridine at 20℃;
70% With triethylamine In dichloromethane at 20℃; for 4h;
69% With potassium iodide; silver(I) oxide In dichloromethane for 14h; Heating;
45% With triethylamine In dichloromethane for 4h; Ambient temperature;
45% With triethylamine In dichloromethane at 20℃; for 16h; 27.1 Step (1) A mixture of 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol (5.0 g, 17.7 mmol) and N,N-diethylethanamine (3.58 g, 35.4 mmol) in DCM (100 mL) was added [chloro(diphenyl)methyl]benzene (4.94 g, 17.7 mmol). The mixture was stirred for 16 h at room temperature. The mixture was added DCM (100 mL) and washed with water, brine, dried over Na2SO4 and concentrated. The residue was purified by flash chromatography column on silica gel eluted with 0%~20% MeOH in DCM to afford 2-[2-[2-[2-[2-(2- trityloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol (4.2 g, 45%) as colourless oil. LCMS 542 (M+18), 99% UV:214 nm
With sodium hydroxide In tetrahydrofuran; water monomer; benzene for 24h; Heating;
With pyridine In acetonitrile at 0 - 20℃; 6.2 Step 2. Synthesis of 19,19,19-triphenyl-3,6,9,12,15,18-hexaoxanonadecanol 25 g of hexaethyleneglycol was dissolved in a mixture of 100 mL of acetonitrile and 30 mL of pyridine, to which 12.5 g of trityl chloride was added at 0 °C, and then the solution was stirred overnight at room temperature. The reaction solution was mixed with iced water and subjected to extraction with ethyl acetate, and then the organic layer was washed with water and concentrated under reduced pressure after drying. The residue was purified with silica gel column chromatography to obtain 15.7 g of the objective compound.

  • 2
  • [ 127999-16-0 ]
  • [ 124-63-0 ]
  • [ 745048-16-2 ]
YieldReaction ConditionsOperation in experiment
100% With triethylamine In dichloromethane at 0℃; for 1h;
97% With triethylamine In dichloromethane at 0 - 20℃;
95.3% With triethylamine In dichloromethane at 0 - 20℃; 27.2 Step (2) To a mixture of 2-[2-[2-[2-[2-(2-trityloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol (4.2 g, 8.01 mmol) and N,N-diethylethanamine (1.62 g, 16 mmol) in DCM (60 mL) cooled to 0oC was added methanesulfonyl chloride (1.38 g, 12 mmol). The reaction mixture was stirred for 3 h at room temperature. The mixture wa diluted with DCM (100 mL) and washed with water, brine, dired over Na2SO4 and concentrated to give 2-[2-[2-[2-[2-(2-trityloxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethyl methanesulfonate (4.6 g, 95.3%) as yellow oil. LCMS 620 (M+18), 97% UV:214 nm
91% With triethylamine In dichloromethane at 20℃; for 24h; 1 Triethylamine (1.7 mL, 12.14 mmol) was added to a solution of T1O-PEG6-OH 8 (n = 6) (4.2159 g, 8.04 mmol) in dichloromethane (30 mL), cooled to 00C. Methanesulfonyl chloride (0.75 mL, 9.6 mmol) was added dropwise. After the addition, the resulting solution was stirred at room temperature for one day. Water was added to quench the reaction. The organic phase was separated and washed with brine (3 x 100 mL), dried over Na2SO4 and concentrated to afford the product as oil (4.399 g) in 91% yield. 1H-NMR (CDCl3) 7.46-7.18 (m, 15 H, Ar-H), 4.36-4.33 (m, 2 H, CH2), 3.74-3.72 (m, 2 H, CH2), 3.68-3.60 (m, 18 H, 9 CH2), 3.21 (t, J= 5.1-5.4 Hz, 2 H, CH2), 3.04 (s, 3 H, CH3). Other TrO-PEGn-OMs of different sizes can be synthesized following the same procedures from the corresponding TrO-PEGn-OH.

  • 3
  • [ 127999-16-0 ]
  • [ 98-59-9 ]
  • [ 1191065-70-9 ]
YieldReaction ConditionsOperation in experiment
82% With pyridine; dmap In dichloromethane at 20℃; for 20h;
82 % Stage #1: hexaethylene glycol mono(triphenylmethyl ether) With sodium hydroxide In tetrahydrofuran; water at 0℃; Stage #2: p-toluenesulfonyl chloride In tetrahydrofuran; water at 0 - 20℃;
  • 4
  • [ 127999-16-0 ]
  • [ 1274892-60-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1.1: 97 percent / Et3N / CH2Cl2 / 0 - 20 °C 2.1: t-BuOK / 2-methyl-propan-2-ol / 0.5 h / Heating 2.2: 94 percent / 2-methyl-propan-2-ol / 4 h / Heating 3.1: 81 percent / Et3N / CH2Cl2 / 0 - 20 °C 4.1: 80 percent / NaN3 / acetonitrile / Heating 5.1: TsOH; methanol / 2 h / Heating
  • 5
  • [ 2615-15-8 ]
  • [ 76-83-5 ]
  • [ 127999-16-0 ]
  • [ 144270-96-2 ]
YieldReaction ConditionsOperation in experiment
With dmap In N,N-dimethyl-formamide; toluene at 85℃; for 22h; 1 PEG6-di-OH 7 (n = 6) (17.3238 g,59.52 mmol) was dissolved in toluene (100 mL), concentrated to remove some of toluene (-80 mL). Anhydrous DMF (125 mL) was added, followed by an addition of DMAP (7.4825 g, 60.02 mmol) and TrCl (13.7833 g, 48.45 mmol). The resulting mixture was heated at 85 0C for 22 hours. The reaction was concentrated to remove the solvents (high vacuum, 50 0C). The residue was mixed with EtOAc (400 mL), washed with 10 % K2CO3 solution (100 mL), water (100 mL) and brine (300 mL), dried over Na2CO3, concentrated. The residue was purified with flash column chromatography on silica gel to result in 14.1 g of product in 55 % yield with some side product (TrO-PEG6-OTr). 1H- NMR (CDCl3) 7.46-7.18 (m, 15 H, Ar-H), 3.72-3.56 (m, 22 H, 11 CH2), 3.21 (t, J= 5.1- 5.4 Hz, 2 H, CH2), 2.66 (t, 2 H, J= 6.0-6.3 Hz, OH). Other TrO-PEGn-OH of different sizes can be synthesized following the same procedures from the corresponding PEGn-di- OH.
  • 6
  • [ 127999-16-0 ]
  • [ 134179-43-4 ]
  • [ 877239-08-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 19-(triphenylmethyl)-1,4,7,10,13,16,19-heptaoxanonadecanol With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 1h; Stage #2: 11-azide-1-{(methylsulfonyl)oxy}-3,6,9-trioxaundecane In N,N-dimethyl-formamide at 0 - 110℃; for 2h; 6.3 Step 3. Synthesis of 1-azide-31,31,31-triphenyl-3,6,9,12, 15,18,21,24,27,30-decaoxahentriacontanol 15 g of 19,19,19-triphenyl-3,6,9,12,15,18-hexaoxanonadecanol obtained in the above step 2 was dissolved in 100 mL of dimethylformamide. The solution was added dropwise to a suspension containing 1.3 g of sodium hydride in 50 mL of dimethylformamide at 0 °C. After stirring at room temperature for 1 hour, the solution was again cooled at 0 °C, and then a solution of 7 g of 11-azide-1-(methylsulfonyl)oxy-3,6,9-trioxaundecane obtained in the above step 1 in 50 mL of dimethylformamide was added dropwise. Subsequently, the solution was stirred at 110 °C for 2 hours. The reaction solution was mixed with iced water and subjected to extraction with ethyl acetate, and then the organic layer was washed with water and concentrated under reduced pressure after drying. The residue was purified with silica gel column chromatography to obtain 10.5 g of the objective compound.
  • 7
  • [ 127999-16-0 ]
  • [ 1444123-36-7 ]
YieldReaction ConditionsOperation in experiment
84% Stage #1: 19-(triphenylmethyl)-1,4,7,10,13,16,19-heptaoxanonadecanol With methanesulfonyl chloride; triethylamine In dichloromethane at 20℃; for 1h; Stage #2: With sodium azide In dichloromethane at 50℃; Intermediate VII.1 Intermediate VII.1 A mixture of the alcohol I.2 (5.00 g; 9.53 mmol), methanesulphonyl chloride (1.11 ml; 14.3 mmol) and triethylamine (3.35 ml; 23.8 mmol) in DCM (50 ml) is stirred at ambient temperature for 1 h. Sodium azide (1.86 g; 28.6 mmol) is added and the mixture is stirred overnight, then for 2 h at 50° C. Further DCM is added and the mixture is extracted with sodium carbonate solution. The organic layer is separated, dried with magnesium sulphate, filtered and evaporated. The residue is purified by silica gel column chromatography (gradient: DCM/methanol 100:0→70:30 to yield the title compound. Yield: 4.39 g (84% of theory) C31H39N3O6 ESI Mass spectrum: m/z=567 [M+H]+; m/z=594 [M+HCOO]-
84% Stage #1: 19-(triphenylmethyl)-1,4,7,10,13,16,19-heptaoxanonadecanol With methanesulfonyl chloride; triethylamine In dichloromethane at 20℃; for 1h; Stage #2: With sodium azide In dichloromethane at 50℃; for 2h; VII.1 Intermediate VII.1 A mixture of the alcohol 1.2 (5.00 g; 9.53 mmol), methanesulphonyl chloride (1.11 ml; 14.3 mmol) and triethylamine (3.35 ml; 23.8 mmol) in DCM (50 ml) is stirred at ambient temperature for 1 h. Sodium azide (1.86 g; 28.6 mmol) is added and the mixture is stirred overnight, then for 2 h at 50 °C. Further DCM is added and the mixture is extracted with sodium carbonate solution. The organic layer is separated, dried with magnesium sulphate, filtered and evaporated. The residue is purified by silica gel column chromatography (gradient: DCM / methanol 100:0→70:30 to yield the title compound. Yield: 4.39 g (84% of theory) C31H39N3O6 ESI Mass spectrum: m/z = 567 [M+H]+; m/z = 594 [M+HCOO]-.
Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 1 h / 0 °C 2: sodium azide / N,N-dimethyl-formamide / 16 h / 50 °C
  • 8
  • [ 105589-77-3 ]
  • [ 127999-16-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: sodium hydride / mineral oil; tetrahydrofuran / 0.25 h / 0 °C / Inert atmosphere 1.2: 12 h / 0 - 20 °C / Inert atmosphere 2.1: sulfuric acid; water / mineral oil; tetrahydrofuran / 3 h / 20 °C / Inert atmosphere
  • 9
  • [ 112-60-7 ]
  • [ 146462-58-0 ]
  • [ 127999-16-0 ]
YieldReaction ConditionsOperation in experiment
64% Stage #1: Tetraethylene glycol With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol for 0.5h; Reflux; Stage #2: 2-<2-(triphenylmethoxy)ethoxy>ethyl methanesulfonate In <i>tert</i>-butyl alcohol for 2h; Reflux;
  • 10
  • [ 127999-16-0 ]
  • [ 877239-08-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1.1: triethylamine / dichloromethane / 1 h / 0 °C 2.1: potassium <i>tert</i>-butylate / <i>tert</i>-butyl alcohol / 0.5 h / Reflux 2.2: 4 h / Reflux 3.1: triethylamine / dichloromethane / 2 h / 0 °C 4.1: sodium azide / N,N-dimethyl-formamide / 16 h / 50 °C
 

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