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Chemical Structure| 23783-42-8
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Product Details of [ 23783-42-8 ]

CAS No. :23783-42-8 MDL No. :MFCD00041756
Formula : C9H20O5 Boiling Point : -
Linear Structure Formula :- InChI Key :ZNYRFEPBTVGZDN-UHFFFAOYSA-N
M.W :208.25 Pubchem ID :90263
Synonyms :
Tetraethylene glycol monomethyl ether

Calculated chemistry of [ 23783-42-8 ]

Physicochemical Properties

Num. heavy atoms : 14
Num. arom. heavy atoms : 0
Fraction Csp3 : 1.0
Num. rotatable bonds : 11
Num. H-bond acceptors : 5.0
Num. H-bond donors : 1.0
Molar Refractivity : 50.88
TPSA : 57.15 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -8.32 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.84
Log Po/w (XLOGP3) : -1.05
Log Po/w (WLOGP) : -0.33
Log Po/w (MLOGP) : -0.95
Log Po/w (SILICOS-IT) : 1.05
Consensus Log Po/w : 0.31

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 1.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : 0.26
Solubility : 376.0 mg/ml ; 1.8 mol/l
Class : Highly soluble
Log S (Ali) : 0.34
Solubility : 454.0 mg/ml ; 2.18 mol/l
Class : Highly soluble
Log S (SILICOS-IT) : -1.9
Solubility : 2.63 mg/ml ; 0.0126 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 2.58

Safety of [ 23783-42-8 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P305+P351+P338 UN#:N/A
Hazard Statements:H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 23783-42-8 ]

* 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.

  • Upstream synthesis route of [ 23783-42-8 ]
  • Downstream synthetic route of [ 23783-42-8 ]

[ 23783-42-8 ] Synthesis Path-Upstream   1~18

  • 1
  • [ 727986-31-4 ]
  • [ 23783-42-8 ]
YieldReaction ConditionsOperation in experiment
90% With pyridinium p-toluenesulfonate In methanol at 0 - 20℃; for 16 h; To a solution of 2-(2,5,8,l l-tetraoxatridecan-13-yloxy)tetrahydro-2H-pyran 5-lA (280 mg, 0.96 mmol) in MeOH (5 mL) was added PPTS (24 mg, 0.096 mmol) and stirred at 0 °C to RT for 16 hr. The reaction mixture was concentrated under reduced pressure to get crude compound. Obtained crude was purified using silica gel column chromatography 5percent MeOH in DCM to afford 5-2A (180 mg, 0.87 mmol, 90percent yield) as a pale yellow liquid
Reference: [1] Patent: WO2016/154241, 2016, A1, . Location in patent: Paragraph 328; 331
[2] Macromolecules, 2004, vol. 37, # 14, p. 5133 - 5135
  • 2
  • [ 124-41-4 ]
  • [ 23783-42-8 ]
YieldReaction ConditionsOperation in experiment
75%
Stage #1: at 20℃; for 12 h; Inert atmosphere
Stage #2: With sulfuric acid; water In tetrahydrofuran for 1 h; Inert atmosphere; Reflux
Under an atmosphere of N2, to a stirring solution of NaOMe (3.0 g, 55.4 mmol) in DMF (100 mL) was slowly added a solution of macrocyclic sulfate 8 (9.5 g, 37.0 mmol, in 20 mL DMF), the mixture was stirred at rt for 12 h, DMF was removed under vacuum, and 100 mL THF was added to the mixture. Then, water (1.3 mL, 74.0 mmol) and H2SO4 (0.9 mL, 16.6 mmol) were added, and the resulting mixture was refluxed for 1 h. The reaction was neutralized with saturated NaHCO3 solution, and THF was removed under vacuum. The residue was concentrated under vacuum, and purified by column chromatography on silica gel (CH2Cl2/MeOH = 20/1) to give M-PEG 9 as a clear oil (5.8 g, 75percent yield). 1H NMR (400 MHz, CDCl3) δ 3.75-3.70 (m, 2H), 3.68-3.60 (m, 12H), 3.57-3.55 (m, 2H), 3.39 (s, 3H).
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 22, p. 3502 - 3505
  • 3
  • [ 87117-61-1 ]
  • [ 23783-42-8 ]
Reference: [1] Journal of the Chemical Society, Chemical Communications, 1990, # 13, p. 911 - 912
[2] Liebigs Annalen der Chemie, 1983, # 5, p. 770 - 801
[3] Helvetica Chimica Acta, 1984, vol. 67, p. 2128 - 2142
  • 4
  • [ 112-60-7 ]
  • [ 74-88-4 ]
  • [ 23783-42-8 ]
Reference: [1] Bioorganic and Medicinal Chemistry, 2008, vol. 16, # 24, p. 10295 - 10300
[2] Chemische Berichte, 1981, vol. 114, # 2, p. 477 - 487
[3] Journal of the American Chemical Society, 1981, vol. 103, # 25, p. 7484 - 7489
[4] Journal of Materials Chemistry, 1997, vol. 7, # 7, p. 1147 - 1154
  • 5
  • [ 112-60-7 ]
  • [ 23783-42-8 ]
Reference: [1] Helvetica Chimica Acta, 1984, vol. 67, p. 2128 - 2142
[2] Journal of the Chemical Society, Chemical Communications, 1990, # 13, p. 911 - 912
[3] Angewandte Chemie - International Edition, 2015, vol. 54, # 12, p. 3763 - 3767[4] Angew. Chem., 2015, vol. 127, # 12, p. 3834 - 3838,5
[5] Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 22, p. 3502 - 3505
  • 6
  • [ 112-60-7 ]
  • [ 77-78-1 ]
  • [ 23783-42-8 ]
Reference: [1] Molecular Crystals and Liquid Crystals, 2004, vol. 411, p. 421/[1463]-437/[1479]
[2] RSC Advances, 2014, vol. 4, # 22, p. 11064 - 11072
  • 7
  • [ 74654-05-0 ]
  • [ 107-21-1 ]
  • [ 23783-42-8 ]
Reference: [1] Synlett, 2005, # 15, p. 2342 - 2346
  • 8
  • [ 112-35-6 ]
  • [ 107-21-1 ]
  • [ 23783-42-8 ]
Reference: [1] Molecular Crystals and Liquid Crystals (1969-1991), 1988, vol. 160, p. 331 - 338
  • 9
  • [ 86259-87-2 ]
  • [ 23783-42-8 ]
Reference: [1] Helvetica Chimica Acta, 1984, vol. 67, p. 2128 - 2142
[2] Journal of the Chemical Society, Chemical Communications, 1990, # 13, p. 911 - 912
  • 10
  • [ 112-35-6 ]
  • [ 23783-42-8 ]
Reference: [1] Macromolecules, 2005, vol. 38, # 23, p. 9509 - 9517
[2] Synlett, 2005, # 15, p. 2342 - 2346
  • 11
  • [ 73159-12-3 ]
  • [ 23783-42-8 ]
Reference: [1] Analytical Chemistry, 2008, vol. 80, # 23, p. 9171 - 9180
  • 12
  • [ 62921-74-8 ]
  • [ 107-21-1 ]
  • [ 23783-42-8 ]
Reference: [1] Macromolecules, 2005, vol. 38, # 23, p. 9509 - 9517
  • 13
  • [ 52808-36-3 ]
  • [ 111-46-6 ]
  • [ 23783-42-8 ]
Reference: [1] Journal of Chemical Research - Part S, 2003, # 11, p. 698 - 699
  • 14
  • [ 128660-97-9 ]
  • [ 23783-42-8 ]
Reference: [1] Patent: WO2016/154241, 2016, A1,
  • 15
  • [ 111-77-3 ]
  • [ 23783-42-8 ]
Reference: [1] Journal of Chemical Research - Part S, 2003, # 11, p. 698 - 699
  • 16
  • [ 75-21-8 ]
  • [ 109-86-4 ]
  • [ 23783-42-8 ]
Reference: [1] Bulletin of the Chemical Society of Japan, 1973, vol. 46, p. 623 - 626
  • 17
  • [ 23783-42-8 ]
  • [ 98-59-9 ]
  • [ 62921-76-0 ]
YieldReaction ConditionsOperation in experiment
99% With sodium hydroxide In tetrahydrofuran; water at 0℃; for 5 h; Example 37; 1 -chloro-2,2,5,5-tetramethyl-3-(2,5,8, 1 1 -tetraoxatridecan-13-yl)imidazolidin-4-one(Compound 39-12)HN NHNaH2,5,8, 1 1 -tetraoxatridecan-13-yl 4-methylbenzenesulfonateTs0- -o- -o^[00285] To a solution of tetraethyleneglycol monomethyl ester (tech. grade, Aldrich, 10 g, 48 mmol) in 27 ml of tetrahydrofuran was added a solution of aqueous sodium hydroxide (5 M, 27 ml, 134 mmol). The solution was cooled to 0 °C and a solution of tosyl chloride (16.5 g, 86.4 mmol) in 27 mL THF was added dropwise to the cold stirring solution. The reaction mixture was stirred at 0 °C for 5 h, then diluted with 50 mL of water and extracted twice with dichloromethane. The organic fractions were washed twice with water and once with brine, then dried over magnesium sulfate andconcentrated under reduced pressure to give a clear liquid (17.1 g, 47.1 mmol, 99percent) the crude product was used directly without purification. LRMS (ESI/APCI) mlz 363 [M+H]+.
96% With sodium hydroxide In tetrahydrofuran; water at 0 - 20℃; for 21 h; Inert atmosphere A solution of para-toluenesulfonyl chloride (22.3 g, 105 mmol) in THF (35 mL) is added dropwise to a solution of tetraethyleneglycol methyl ether (20.0 g, 96 mmol) and NaOH (6.7 g, 166 mmol) in a mixture of THF/H20 (135 mL/45 mL) at 0°C. After 1 h stirring at 0°C, the reaction is allowed to warm at room temperature and is stirred 20 additional hours. The solution is then poured into 200 mL of brine and the volatiles are evaporated. The resulting mixture is extracted several times with dichloromethane and the combined organic layers are washed with brine, dried over MgS04 and filtered. The solvent is evaporated under reduced pressure and compound 19 is obtained as pale yellow oil in 96percent yield and is used without further purification.
96% With sodium hydroxide In tetrahydrofuran; water at 0 - 20℃; for 21 h; A solution of para-toluenesulfonyl chloride (22.3 g, 105 mmol) in THF (35 mL) was added dropwise to a solution of tetraethylene glycol methyl ether (20.0 g, 96 mmol) and NaOH (6.7 g, 166 mmol) in a THF/H2O mixture (135 mL/45 ml) at 0° C. After stirring for one hour at 0° C., the reaction mixture was left to return to room temperature and then it was stirred for a further 20 hours. The solution was then poured into 200 ml of brine and the volatile materials were evaporated. The resultant mixture was extracted several times with dichloromethane and the combined organic phases were washed with brine, dried over MgSO4, filtered and evaporated under reduced pressure. The oily residue was purified by silica gel chromatography with a dichloromethane/methanol mixture (98/2) as eluent. Compound 32 is obtained in the form of a pale yellow oil in 96percent yield (0310) 1H NMR (300 MHz, CDCl3) δ 2.39 (s, 3H, ArCH3), 3.31 (s, 3H, OCH3), 3.64 to 3.47 (m, 14H, OCH2CH2O), 4.11 to 4.08 (m, 2H, ArSO2OCH2), 7.28 (d, J=1.5 Hz, 2H, Ar-3,5-H), 7.73 (d, J=1.5 Hz, 2H, Ar-2,6-H); 13C NMR (75 MHz, CDCl3) δ 21.78, 59.14, 68.80, 69.45, 70.66, 70.73, 70.86, 72.07, 128.10, 129.99, 133.19, 144.96.
95%
Stage #1: With sodium hydroxide In tetrahydrofuran; water at 0℃; for 0.25 h;
Stage #2: at 0 - 20℃; for 6 h;
A solution of tetra (ethylene glycol) ethyl ether (1.96 g, 9.41 mmol, 1 eq.) Dissolved in THF (5 mL) was placed in a 30 mL flask and cooled to 0 ° C. in an ice bath.Then, a solution of sodium hydroxide (0.56 g, 14 mmol, 1.5 eq.) Dissolved in water (2 mL) was added and reacted with stirring for 15 minutes.Subsequently, p-toluenesulfonyl chloride (1.97 g, 10.35 mmol, 1.1 eq.) Was added dropwise over 10 minutes.The mixture was then reacted vigorously with stirring at 0 ° C. for 3 hours, then allowed to warm to room temperature and reacted with continuous stirring for a further 3 hours.The mixture was then diluted with ethyl acetate (30 mL), washed twice with water and brine, and the organic layer was dried over anhydrous sodium sulfate.Subsequently, the solvent was removed under reduced pressure to obtain compound (C-1) as a colorless oil (yield 3.231 g, 8.91 mmol, yield 95percent).
94% With pyridine In dichloromethane at -20℃; for 48 h; Inert atmosphere To a solution of tetraethyleneglycol monomethyl ether (2) (10.0 g, 48.0 mmol) and pyridine (84 mL) in CH2Cl2 (170 mL), solid p-toluenesulfonyl chloride (22.0 g, 115.4 mmol) was added portion-wise at -20 °C under nitrogen. The resulting reaction mixture was stirred for 2 days at -20 °C. Then, the reaction mixture was allowed to warm to room temperature and water (200 mL) was added. The aqueous layer was extracted with CH2Cl2 (150 mL .x. 3). The combined organic fractions were dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was purified by chromatography on silica (1:1 EtOAc:hexanes; Rf = 0.3) to yield 3 as a colorless oil, 16.4 g, 94percent.1H NMR (500 MHz, CDCl3): δ = 7.80 (d, Ar, 2H), 7.34 (d, Ar, 2H), 4.16 (t, 2H), 3.66 (t, 2H), 3.62-3.65 (m, 6H), 3.58 (s, 4H), 3.532-3.56 (m, 2H), 3.34 (s, 3H), 2.43 (s, 3H). 13C NMR (125 MHz, CDCl3): δ = 144.71 (s, CSO2O), 132.94 (s, CH3CCH), 129.74 (s, CHCHCSO2), 127.89 (s, CCHCH), 71.79, 70.57, 70.46, 70.44, 70.38, 70.36, 69.20, 68.52, 58.94 (CH3OCH2), 21.56 (CH3CHCH). Data was consistent with a previously reported compound [5].
94%
Stage #1: With pyridine; dmap In dichloromethane at 0℃; for 0.25 h;
Stage #2: at 20℃; for 6 h;
General procedure: Pyridine (1.09 mL, 13.5 mmol, 2.0 eq.) and DMAP (1.65 g, 13.5 mmol, 2.0 eq.) were added to a solution of methoxy-oligo(ethylene glycol) (6.75 mmol, 1.0 eq.) in DCM (10 mL), and the mixture was stirred at 0 °C for 15 min. A solution of tosyl chloride (1.93 g, 10.1 mmol, 1.5 eq.) in DCM (10 mL) was then added dropwise and the reaction mixture was stirred at room temperature for 6 h. The resulting mixture was diluted in DCM (150 mL) and washed with 0.5 N HCl (100 mL). The aqueous layer was washed with DCM (5 × 75 mL) and all the organic fractions were collected, dried over MgSO4 and filtered.The solvent was evaporated under reduced pressure and the residue was purified by flash chromatography.
94% With sodium hydroxide In tetrahydrofuran; water at 0 - 20℃; for 21 h; A solution of /?ara-toluenesulfonyl chloride (22.3 g, 105 mmol) in THF (35 mL) was added dropwise to a solution of tetraethyleneglycol methyl ether (20.0 g, 96 mmol) and NaOH (6.7 g, 166 mmol) in a mixture of THF/H20 (135 mL/45 mL) at 0°C. After 1 hour stirring at 0°C, the reaction was allowed to warm at room temperature and was stirred 20 additional hours. The solution was then poured into 200 mL of brine and the volatiles were evaporated. The resulting mixture was extracted several times with dichloromethane and the combined organic layers were washed with brine, dried over MgSC>4 and filtered. The solvent was evaporated under reduced pressure and the oil and was purified by column chromatography on silica gel eluting with dichloromethane/methanol (98/2). Compound 2 was obtained as a pale yellow oil in 94percent yield. FontWeight="Bold" FontSize="10" H NMR (300 MHz, CDC13) δ 7.73 (d, J = 1.5 Hz, 2H, Ar-2,6-H), 7.28 (d, J = 1.5 Hz, 2H, Ar-3,5-H), 4.11-4.08 (m, 2Η, ArS02OCH2), 3.64-3.47 (m, 14Η, OCH2CH20), 3.31 (s, 3H, OC), 2.39 (s, 3H, ArC); 1 C NMR (75 MHz, CDC13) δ 144.9, 133.2, 130.0, 72.1, 70.9, 70.7, 70.6, 69.5, 68.8, 59.1, 28.1 , 21.8.
94% With sodium hydroxide In tetrahydrofuran; water at 0 - 10℃; for 6 h; A method of synthesizing the silybin phenolic ether derivatives as shown in Formula I-d is as follows:1) Add 8.00 g (0.20 mol) NaOH, 80 ml water to a 250 ml three-necked flask.Stir to dissolve it evenly. 24.96 g (0.12 mol) of tetraethylene glycol monomethyl ether was added to 50 ml of THF to be uniformly dissolved, then added to the above-mentioned three-necked flask and uniformly mixed with the NaOH solution.The mixture was stirred in an ice bath at 0 55° C. and thoroughly deoxygenated with nitrogen. 22.88 g (0.12 mol) of p-toluenesulfonyl chloride and 40 ml of THF were mixed well, and then slowly added dropwise to the above three-necked flask. The dropping process kept the temperature of the reaction liquid. After exceeding 10°C, the reaction was continued for 6 hours after completion of the dropwise addition to stop the reaction.The reaction solution was extracted three times with diethyl ether, and the ether extract was washed with water until neutral and then dried over anhydrous magnesium sulfate. After filtration and rotary evaporation, the ether was removed.This gave 40.83 g (yield: 94percent) of the corresponding p-toluenesulfonate of formula III-b,
90% With dmap; triethylamine In dichloromethane at 20℃; for 20 h; (JACS, 2007, 129, 13364) To a solution of 2,5,8,11-tetraoxamidecan-13-ol (7 g, 33.6 mmol) and triethylamine (4.9 ml, 35.3 mmol) in dry CH2Cl2 (100 ml), 4-toluenesulfonyl chloride (6.7 g, 35.3 mmol) and DMAP (120 mg) were added.
The mixture was stirred at room temperature for 20 h.
The reaction mixture was washed with 80 mL of HCl (1M) and then water.
The extract was dried over anhydrous MgSO4, filtrated, and the filtrate was evaporated.
The residue was used in the next step without further purification. Yield: 11.0 g (90percent)
NMR: 1H NMR (400 MHz, CDCl3) δ 7.75-7.64 (m, 2H), 7.31-7.26 (m, 2H), 4.16-4.06 (m, 2H), 3.62 (m 2H), 3.59-3.40 (m, 10H), 3.30 (s, 3H), 2.38 (s, 3H).
13C{1H} NMR (101 MHz, CDCl3) δ 144.75 (s), 132.90 (s), 129.77 (s), 127.8 (s), 71.82 (s), 70.60 (s), 70.48 (s), 70.47 (s), 70.41 (s), 70.39 (s), 69.23 (s), 68.55 (s), 58.90 (s), 21.53 (s).
90% With dmap; triethylamine In dichloromethane at 20℃; for 20 h; Procedure: (JACS, 2007, 129, 13364) To a solution of 2,5,8,11-tetraoxatridecan- 13-ol (7 g, 33.6 mmol) and triethylamine (4.9 ml, 35.3 mmol) in dry CH2C12 (100 ml), 4-toluenesulfonyl chloride (6.7 g, 35.3 mmol) and DMAP (120 mg) were added. The mixture was stirred at room temperature for 20 h. The reaction mixture was washed with 80 mL of HCl (1M) and then water. The extract was dried over anhydrous MgS04, filtrated, and the filtrate was evaporated. The residue was used in the next step without further purification. Yield: 11.0 g (90percent) NMR: NMR (400 MHz, CDC13) δ 7.75 - 7.64 (m, 2H), 7.31 - 7.26 (m, 2H), 4.16 - 4.06 (m, 2H), 3.62 (m 2H), 3.59 - 3.40 (m, 10H), 3.30 (s, 3H), 2.38 (s, 3H). 13C{1H} NMR (101 MHz, CDC13) δ 144.75 (s), 132.90 (s), 129.77 (s), 127.8 (s), 71.82 (s), 70.60 (s), 70.48 (s), 70.47 (s), 70.41 (s), 70.39 (s), 69.23 (s), 68.55 (s), 58.90 (s), 21.53 (s).
90% With dmap; triethylamine In dichloromethane at 20℃; for 20 h; Procedure: (JACS, 2007, 129, 13364) To a solution of 2,5,8,11-tetraoxatridecan- 13-ol (7 g, 33.6 mmol) and triethylamine (4.9 ml, 35.3 mmol) in dry CH2C12 (100 ml), 4-toluenesulfonyl chloride (6.7 g, 35.3 mmol) and DMAP (120 mg) were added. The mixture was stirred at room temperature for 20 h. The reaction mixture was washed with 80 mL of HCl (1M) and then water. The extract was dried over anhydrous MgS04, filtrated, and the filtrate was evaporated. The residue was used in the next step without further purification. Yield: 11.0 g (90percent) NMR: NMR (400 MHz, CDC13) δ 7.75 - 7.64 (m, 2H), 7.31 - 7.26 (m, 2H), 4.16 - 4.06 (m, 2H), 3.62 (m 2H), 3.59 - 3.40 (m, 10H), 3.30 (s, 3H), 2.38 (s, 3H). 13C{1H} NMR (101 MHz, CDC13) δ 144.75 (s), 132.90 (s), 129.77 (s), 127.8 (s), 71.82 (s), 70.60 (s), 70.48 (s), 70.47 (s), 70.41 (s), 70.39 (s), 69.23 (s), 68.55 (s), 58.90 (s), 21.53 (s).
90% With dmap; triethylamine In dichloromethane at 20℃; for 20 h; Procedure: (JACS, 2007, 129, 13364) To a solution of 2,5,8,11-tetraoxatridecan- 13-ol (7 g, 33.6 mmol) and triethylamine (4.9 ml, 35.3 mmol) in dry CH2C12 (100 ml), 4-toluenesulfonyl chloride (6.7 g, 35.3 mmol) and DMAP (120 mg) were added. The mixture was stirred at room temperature for 20 h. The reaction mixture was washed with 80 mL of HCl (1M) and then water. The extract was dried over anhydrous MgS04, filtrated, and the filtrate was evaporated. The residue was used in the next step without further purification. Yield: 11.0 g (90percent) NMR: NMR (400 MHz, CDC13) δ 7.75 - 7.64 (m, 2H), 7.31 - 7.26 (m, 2H), 4.16 - 4.06 (m, 2H), 3.62 (m 2H), 3.59 - 3.40 (m, 10H), 3.30 (s, 3H), 2.38 (s, 3H). 13C{1H} NMR (101 MHz, CDC13) δ 144.75 (s), 132.90 (s), 129.77 (s), 127.8 (s), 71.82 (s), 70.60 (s), 70.48 (s), 70.47 (s), 70.41 (s), 70.39 (s), 69.23 (s), 68.55 (s), 58.90 (s), 21.53 (s).
90% With dmap; triethylamine In dichloromethane at 20℃; for 20 h; (JACS, 2007, 129, 13364) To a solution of 2,5,8,11-tetraoxatridecan-13-ol (7 g, 33.6 mmol) and triethylamine(4.9 ml, 35.3 mmol) in dry CH2C12 (100 ml), 4-toluenesulfo-nyl chloride (6.7 g, 35.3 mmol) and DMAP (120 mg) wereadded. The mixture was stirred at room temperature for 20 h.The reaction mixture was washed with 80 mE of HC1 (1M)and then water. The extract was dried over anhydrous Mg504,filtrated, and the filtrate was evaporated. The residue was usedin the next step without further purification.10137] Yield:10138] 11.0 g (90percent)10139] NMR:10140] ‘H NMR (400 MHz, CDC13) ö 7.75-7.64 (m, 2H),7.3 1-7.26 (m, 2H), 4.16-4.06 (m, 2H), 3.62 (m2H), 3.59-3.40(m, 1OH), 3.30 (s, 3H), 2.38 (s, 3H).10141] ‘3C{’H} NMR (101 MHz, CDC13) ö 144.75 (s),132.90 (s), 129.77 (s), 127.8 (s), 71.82(s), 70.60 (s), 70.48 (s),70.47 (s), 70.41 (s), 70.39 (s), 69.23 (s), 68.55 (s), 58.90 (s),
82% With sodium carbonate In tetrahydrofuran; water at 0℃; for 3 h; To a mixture of tetraethylene glycol monomethyl ether (3.00 g, 14.406 mmol) and soda (0.865 g, 21.6 mmol) diluted in THF (33 ml) and water (4 ml) cooled to 0° C., a solution of p-toluenesulfonic acid chloride (3.021 g, 15.8 mmol) in THF (4 ml) is slowly added. After 3 hours of stirring at 0° C., the mixture is poured into iced water (10 ml) and is diluted by dichloromethane. The aqueous phase is extracted with dichloromethane and the recombined organic phases are washed with water then with a NaCl-saturated solution, dried on MgSO4, filtered and concentrated under reduced pressure. The residue is purified by flash chromatography on a silica gel (petroleum ether/ethyl acetate 1/1 to 1/4) to yield 4.234 g (82percent) of a colorless oil. δH (300 MHz, CDCl3) identical to the literature.
70% With pyridine In dichloromethane; water O-Tosyltetraethyleneglycol methyl ether (109)
Tetraethyleneglycol monomethyl ether (2.0 g, 9.6 mmol) was combined with pyridine (0.93 mL, 11.5 mmol) in methylene chloride (20 mL) at 0° C. p-Toluenesulfonyl chloride (2.2 g, 11.5 mmol) dissolved in methylene chloride (10 mL) was added dropwise and the reaction was allowed to warm to room temperature as the ice bath thawed.
After stirring nine days, the product mixture was transferred to a separatory funnel with water (70 mL).
The layers were separated and the aqueous layer was extracted with methylene chloride (3*20 mL).
The extracts were combined and evaporated.
The residue (3.3 g) was chromatographed (silica gel, 4:1 to 3:1 gradient elution, methylene chloride/ethyl acetate) to afford 2.5 g (70percent) of compound 109 as an oil. 1H NMR (300 MHz, DMSO-d6) δ 1.56 (br s, 4H), 2.42 (br s, 2H), 3.34 (br s, 4H), 6.05 (s, 3H), 7.09 (s, 0.5H), 7.26 (s, 0.5H), 7.42 (br s, 2H), 7.70 (br s, 2H), 8.87 (br d, 2H), 9.07 (s, 2H), 9.22 (br s, 1H), 10.51 (s, 1H). CI MS m/z=363 [C16H26O7S+H]+.
47.3% With pyridine In tetrahydrofuran at 20℃; 2,5,8,1 1-Tetraoxatridecan-13-ol (5.0 g, 24.01 mmol) was dissolved in THF(20.01 ml). pyridine (5.83 ml, 72.0 mmol) was added to the mixture followed by 4-methylbenzene-1-sulfonyl chloride (5.49 g, 28.8 mmol). The mixture stirred at roomtemperature overnight. Mixture was concentrated by roto-vap. Residue was dissolved in dichloromethane. Material was washed twice with saturated aqueous sodium bicarbonate. Combined aqueous layers were back-extracted with dichloromethane. Combined organics were washed twice with iN hydrochloric acidand once with brine. Organics were dried MgSO4, filtered and then concentrated todryness to get 2,5,8,11-tetraoxatridecan-13-yl 4-methylbenzenesulfonate (4.12 g, 11.37 mmol, 47.3 percent yield) which was used as is in the next step.
39.6% With triethylamine In dichloromethane at 0 - 20℃; for 3 h; 150.41 g (0.79 mol) tosyl chloride was dissolved in 400 ml methylene chloride. 156.41 g (0.752 mol) tetraethylene glycol monomethyl ether was added and the mixture was cooled to 0°C. 79.74 g (0.79 mol) triethyl amine in 100 ml methylene chloride was added while the temperature was kept below 10 °C. The reaction was allowed to continue for three hours at room temperature. The reaction mixture was extracted twice with 300 ml 5N NaOH and twice with 300 ml water. The organic fraction was dried over Na2S04 and evaporated under reduced pressure. The crude product was purified using preparative column chromatography on a Prochrom LC80 column, using Kromasil Si60A 10 μτη as statoionary phase and methylene (0239) chloride/ethyl acetate 35/65 as eluent. 108 g of the tosylated tertaethylene glycol monomethyl ether was isolated as a slightly colored oil (y : 39.6 percent) (TLC analysis on TLC Silicagel 60F254 supplied by Merck, methylene chloride/ethyl acetate 35/65 as eluent : Rf = 0.45) .
70% With pyridine In dichloromethane; water O-Tosyltetraethyleneglycol Methyl Ether (109)
Tetraethyleneglycol monomethyl ether (2.0 g, 9.6 mmol) was combined with pyridine (0.93 mL, 11.5 mmol) in methylene chloride (20 mL) at 0° C. p-Toluenesulfonyl chloride (2.2 g, 11.5 mimol) dissolved in methylene chloride (10 mL) was added dropwise and the reaction was allowed to warm to room temperature as the ice bath thawed.
After stirring nine days, the product mixture was transferred to a separatory funnel with water (70 mL).
The layers were separated and the aqueous layer was extracted with methylene chloride (3*20 mL).
The extracts were combined and evaporated.
The residue (3.3 g) was chromatographed (silica gel, 4:1 to 3:1 gradient elution, methylene chloride/ethyl acetate) to afford 2.5 g (70percent) of compound 109 as an oil. 1H NMR (300 MHz, DMSO-d6) δ 1.56 (br s, 411), 2.42 (br s, 2H), 3.34 (br s, 4H), 6.05 (s, 3H), 7.09 (s, 0.5H), 7.26 (s, 0.5H), 7.42 (br s, 2H), 7.70 (br s, 2H), 8.87 (br d, 2H), 9.07 (s, 2H), 9.22 (br s, 1H), 10.51 (s, 1H). CI MS m/z=363 [C16H26O7S+H]+.

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  • 18
  • [ 23783-42-8 ]
  • [ 98-09-9 ]
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Reference: [1] Patent: CN107446379, 2017, A, . Location in patent: Paragraph 0015-0016; 0039-0041; 0049-0050; 0056-0057
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