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Chemical Structure| 126213-50-1 Chemical Structure| 126213-50-1

Structure of 126213-50-1

Chemical Structure| 126213-50-1

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Product Details of [ 126213-50-1 ]

CAS No. :126213-50-1
Formula : C6H6O2S
M.W : 142.18
SMILES Code : C12=CSC=C1OCCO2
MDL No. :MFCD02093622
InChI Key :GKWLILHTTGWKLQ-UHFFFAOYSA-N
Pubchem ID :4421864

Safety of [ 126213-50-1 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H311+H331-H302-H319-H412
Precautionary Statements:P261-P273-P264-P280-P302+P352+P312-P403+P233
Class:6.1
UN#:2810
Packing Group:

Computational Chemistry of [ 126213-50-1 ] Show Less

Physicochemical Properties

Num. heavy atoms 9
Num. arom. heavy atoms 5
Fraction Csp3 0.33
Num. rotatable bonds 0
Num. H-bond acceptors 2.0
Num. H-bond donors 0.0
Molar Refractivity 35.19
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

46.7 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

1.99
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

1.32
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

1.52
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

0.45
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

2.98
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

1.65

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-1.96
Solubility 1.54 mg/ml ; 0.0109 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Very soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-1.9
Solubility 1.78 mg/ml ; 0.0125 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Very soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-1.67
Solubility 3.02 mg/ml ; 0.0212 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

High
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-6.23 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

1.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

0.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

2.82

Application In Synthesis of [ 126213-50-1 ]

* 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 [ 126213-50-1 ]

[ 126213-50-1 ] Synthesis Path-Downstream   1~16

  • 1
  • [ 68-12-2 ]
  • [ 126213-50-1 ]
  • [ 211235-87-9 ]
  • [ 204905-77-1 ]
  • 2
  • [ 68-12-2 ]
  • [ 126213-50-1 ]
  • [ 204905-77-1 ]
YieldReaction ConditionsOperation in experiment
86.3% With bis(trichloromethyl) carbonate; In dichloromethane; at 0 - 35℃; for 1h; To a mixture of EDOT (15.0 g, 0.1 mol) and DMF (11.0 g, 0.15 mol), BTC (11.9 g, 0.04 mol) dissolved in dry CH2Cl2 (80 mL) was added dropwise at 0C. The mixture was heated to 35C and stirred for 1 h, then cooled and poured into ice water (250 mL). The pH of the aqueous phase was adjusted to 7-8 with 10% sodium hydroxide and the organic phase was separated. The aqueous phase was extracted with CH2Cl2 for three times. The organic phase was combined and dried with anhydrous magnesium sulfate. After removing the solvent under reduced pressure, the crude product was recrystallized in 95% ethanol to yield white needle crystals 1 (15.5 g, 86.3% yield). 1H NMR (400 MHz) delta/ppm: 9.90 (s, 1H), 6.79 (s, 1H), 4.38-4.25 (m, 4H).
83% With trichlorophosphate; at -10 - 20℃; for 4h;Cooling with ice; 3,4-Ethylenedioxythiophene (2 mL, 18 mmol) was dissolved in dry N N-Dimethylformamide(DMF) (10 mL, 126 mmol), the mixture was cooled to -10 C and POCl3 (1.76 mL, 18 mmol)was added slowly dropwise over min. The reaction mixture was then allowed to reach roomtemperature then stirred for an additional hour. The reaction was poured into an ice bath andneutralized using a basic aqueous solution. The product, in the form of white needles, wasfiltered and dried, yielding a quantitative yield (3.06 g). 1H NMR (300 MHz, CDCl3 , deltappm ):9.83 (s, 1H), 6.74 (s, 1H), 4.31 (d, 2H), 4.21 (d, 2H). 13C NMR (75 MHz, CDCl3 , deltappm ):180.0, 141.7, 110.8, 110.7, 65.2, 64.3.
67% With trichlorophosphate; at 0 - 20℃; for 8h;Inert atmosphere; 5g (35.21 mmol) of 3,4-ethylenedioxythiophene was dissolved in 70 mL of N,N-dimethylformamide (DMF) in a two-necked flask, magnetically stirred and argon gas was introduced, the reaction system was lowered to 0 C, and 10.8 g (70.42 mmol) of phosphorus oxychloride was added dropwise to the system, and the reaction system was slowly returned to room temperature for 8 h overnight. After the reaction is completed, a rotary evaporator was used to spin dried DMF, the system was reduced to 0 C, 50 mL of saturated sodium bicarbonate solution was added to quench the excess phosphorus oxychloride, extracted and separated with 3*50 mL of dichloromethane and organic phase was spin dried, the sample was mixed with silica gel, and 4g of product was obtained by column chromatography, yield was 67%. The structure of the intermediate is resolved as follows:
  • 3
  • [ 126213-50-1 ]
  • [ 174508-31-7 ]
YieldReaction ConditionsOperation in experiment
95% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0 - 20℃; for 2h; step 1),3,4-ethylenedioxythiophene (1.42 g, 10 mmol) was dissolved in 30 mL of DMF.And use an ice bath to drop to 0 C,N-bromosuccinimide (3.78 g, 21 mmol) was dissolved in 30 mL DMF.Slowly drip into the above solution with a constant pressure dropping funnel.After the addition is completed,The reaction was stirred at room temperature for 2 h.After the reaction is over,100 mL of ice water was slowly added to the reaction solution.Produces a large amount of light yellow solids,The product is filtered under reduced pressure,The filter residue was washed three times with 15 mL of deionized water.2.85 g of product, Compound 4, was obtained.Yield 95%;
83% With N-Bromosuccinimide; acetic acid; In tetrahydrofuran; at 20℃; for 2h; A THF (20 mL) solution of 3,4-ethoxylene dioxy thiophene(1.42 g,10.60 mmol), N-bromosuccinimide (3.74 g,12.80 mmol) andacetic acid (20 mL) were charged sequentially into a round-bottomflask. The mixturewas stirred for 2 h at room temperature. After thereaction, pouring the reaction mixture into distilled water andstirring with a glass rod, precipitate was filtered to afford A4 as awhite solid (2.50 g, 8.30 mmol, yield 83%). 1H NMR (400 MHz,CDCl3,ppm): delta = 4.27 (s, 4H).
74% With N-Bromosuccinimide; In tetrahydrofuran; at 10℃; for 80h;Inert atmosphere; General procedure: In a 150 mL 3-neckedflask, a solution of thienothiophene(TT) (11.2 g, 80 mmol) in dry THF (100 mL) was cooled to 10 C under a nitrogenatmosphere. NBS (35.6 g, 200 mmol) was addedslowly in portions and allowed to stir for 8 h at approximately 10 C. Thereaction mixture was then poured into dichloromethane (DCM).The organic layer was washed with water and dried over anhydrous MgSO4. After removing thesolvent, the crude product was recrystallized from petroleum ether (PE, boiling range: 60-90 C) to give a colorless solid(16.2 g, 68% yield).
72% With N-Bromosuccinimide; for 1h; A mixture of bromosuccinimide (NBS) (2.75 g, 15.45 mmol) and N,N-dimethylformamide (DMF) (15 ml) was added dropwise to the mixture of EDOT (1.0 g, 7.03 mmol) and DMF (15 ml) and the reaction temperature was kept between 18-23 C. After completion of the addition, the mixture was stirred for 1 h, and then poured into an equal of ice water. After vigorous shaking for 5 min, the mixture was extracted with CH2Cl2, and washed with saturated NaHCO3 solution once and with water for three times. The combined organic layer was dried over anhydrous MgSO4 and concentrated under reduced pressure to leave a crude residue. Purification by recrystallization with n-hexane afforded 1.5 g 2,5-dibromo-3,4-ethylenedioxythiophene as a white solid in 72% yield. 1H NMR (400 MHz, CDCl3): delta 4.27 (s, 4H); 13C NMR: delta 139.7, 85.5, 64.9.
33% With N-Bromosuccinimide; acetic acid; In tetrahydrofuran; at 20℃; for 3h; 5-Br was synthesized based onliterature.5 3,4-Ethylenedioxythiophene (1.0 g, 7.04 mmol) and a mixture of THF/CH3COOH(24 mL, 1:1 v/v) were added to a dry 100 mL 2-neck round-bottom flask. NBS (3.13 g, 17.6 mmol)was added and the solution was stirred at room temperature for 3 h. Then, distilled water (50 mL)was poured to the reaction mixture. A silver crystalline solid was precipitated, filtered, dried andused without further purification (0.7 g, 33%). 1H NMR (300 MHz, DMSO-d6), delta: 4.30 (s, 4H).13C NMR (75 MHz, DMSO-d6), delta: 140.1, 84.2, 64.7.
With N-Bromosuccinimide; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere; Compound 1 (0.3 g, 2.11 mmol) and N-bromosuccinimide (NBS)?(0.75 g, 4.22 mmol) were dissolved in 20 mL fleshly distilled THE and stirred at r.t. for 2 hr under N2. The reaction solution was transferred by syringe to a N2 protected 50 mL flask containing K2C03 (2 M, 5 ml), Pd(0)(PPh3)4 (0.129,0.1 mmol) and compound 4(1.47 g, 4.22 mmol). The reaction mixture was then stirred at reflux in the dark for 6 hr. The reaction mixture was cooled down to r.t. and poured into water, extracted with dichioromethane (DCM) and washed with water. The DCM layer was dried over MgSO4, concentrated and the residue mixture was purified by column chromatography on silica gel elutirig with DCM to obtain the product as a yellow solid (1.3 g, 82%). 1H NMR (CD2CI2) 6: 7.55 (br, 4H), 7.07 (d, J = 8.4 Hz, 8H), 6.90 (d, J = 7.6 Hz, 4H), 6.86 (d, J = 8.8 Hz, 12H), 4.34 (s, 4H), 3.81 (s, 12H). 13C NMR (CD2CI2) 6: 156.5, 147.7, 141.1, 138.3, 127.0, 125.8, 120.9, 115.1, 65.1, 55.9. HRMS (MALDI-TOF): calcd for C46H40N206S, 748.2607; found, 748.2656. Anal. calcd. for C46H40N206S: C, 73.78; H, 5.38; N, 3.74; S, 4.28 %. Found: C, 74.01; H, 5.29; N, 3.70; S, 4.21 %.

  • 4
  • [ 51792-34-8 ]
  • [ 107-21-1 ]
  • [ 126213-50-1 ]
YieldReaction ConditionsOperation in experiment
46.7% With toluene-4-sulfonic acid; In methanol; toluene; at 100℃; for 3h;Inert atmosphere; The following production was carried out using <strong>[51792-34-8]3,4-dimethoxythiophene</strong> prepared by the same production method as in Example 2 described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of <strong>[51792-34-8]3,4-dimethoxythiophene</strong>, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, <strong>[51792-34-8]3,4-dimethoxythiophene</strong> was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3,4-ethylenedioxythiophene,<strong>[51792-34-8]3,4-dimethoxythiophene</strong>,One in which one methoxy group of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> is substituted with ethylene glycol,And methoxy groups of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in the reaction solution to the amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3,4-ethylenedioxythiophene. The purity of its 3,4-ethylenedioxythiophene was 99.64percent by gas chromatography.
  • 5
  • [ 57381-43-8 ]
  • [ 126213-50-1 ]
  • 2,5-bis[(3,4-etylenedioxy)thien-2-yl]benzoic acid methyl ester [ No CAS ]
  • 6
  • [ 4805-22-5 ]
  • [ 126213-50-1 ]
  • 2,3-dihydro-5-(5-(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)thiophen-2-yl)thiophen-2-yl)thieno[3,4-b][1,4]dioxine [ No CAS ]
  • 7
  • [ 126213-50-1 ]
  • [ 174508-31-7 ]
  • poly(3,4-ethylenedioxythiophene); monomer(s): 3,4-ethylenedioxythiophene; 2,5-dibromo-3,4-ethylenedioxythiophene [ No CAS ]
  • 8
  • [ 126213-50-1 ]
  • [ 174508-31-7 ]
  • 2,3,2',3',2'',3''-hexahydro-[5,5':7',5'']ter(thieno[3,4-b]-[1,4]dioxine) [ No CAS ]
  • 9
  • [ 126213-50-1 ]
  • [ 204905-77-1 ]
  • 10
  • [ 126213-50-1 ]
  • [ 802919-90-0 ]
  • [ 1609470-37-2 ]
  • 11
  • [ 40318-15-8 ]
  • [ 126213-50-1 ]
  • methyl 5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4-methyl-1H-pyrrole-3-carboxylate [ No CAS ]
  • 12
  • [ 51792-34-8 ]
  • [ 107-21-1 ]
  • C7H10O3S [ No CAS ]
  • C8H12O4S [ No CAS ]
  • [ 126213-50-1 ]
YieldReaction ConditionsOperation in experiment
19.3%Chromat.; 12.84%Chromat.; 56.29%Chromat. With (+)-(1S)-camphor-10-sulphonic acid; In methanol; toluene; at 100℃; for 1h;Inert atmosphere; General procedure: The following production was carried out using <strong>[51792-34-8]3,4-dimethoxythiophene</strong> prepared by the same production method as in Example 2 described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of <strong>[51792-34-8]3,4-dimethoxythiophene</strong>, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, <strong>[51792-34-8]3,4-dimethoxythiophene</strong> was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3,4-ethylenedioxythiophene,<strong>[51792-34-8]3,4-dimethoxythiophene</strong>,One in which one methoxy group of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> is substituted with ethylene glycol,And methoxy groups of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in the reaction solution to the amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3,4-ethylenedioxythiophene. The purity of its 3,4-ethylenedioxythiophene was 99.64percent by gas chromatography. ((+) - 10-camphistsulfonic acid monohydrate of the same substance amount (mol number) was used in place of the cuedemen sulphonic acid monohydrate of Example 5, the compositional change in the reaction solution was evaluated by N, N-dimethylformamide was traced by gas chromatography as an internal standard. Table 7 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.
7.3%Chromat.; 11.78%Chromat.; 70.74%Chromat. With 2-aminonaphthalenesulfonic acid; In methanol; toluene; at 100℃; for 3h;Inert atmosphere; General procedure: The following production was carried out using <strong>[51792-34-8]3,4-dimethoxythiophene</strong> prepared by the same production method as in Example 2 described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of <strong>[51792-34-8]3,4-dimethoxythiophene</strong>, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, <strong>[51792-34-8]3,4-dimethoxythiophene</strong> was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3,4-ethylenedioxythiophene,<strong>[51792-34-8]3,4-dimethoxythiophene</strong>,One in which one methoxy group of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> is substituted with ethylene glycol,And methoxy groups of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in the reaction solution to the amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3,4-ethylenedioxythiophene. The purity of its 3,4-ethylenedioxythiophene was 99.64percent by gas chromatography. Except that 2-amino-1-naphthalenesulfonic acid monohydrate of the same substance (mol number) was used instead of the cuedemen sulphonic acid monohydrate of Example 5, and the compositional change in the reaction solution was evaluated by N, N-dimethylformamide was traced by gas chromatography as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 8.
  • 13
  • [ 51792-34-8 ]
  • [ 107-21-1 ]
  • C7H10O3S [ No CAS ]
  • [ 126213-50-1 ]
YieldReaction ConditionsOperation in experiment
13.67%Chromat.; 79.08%Chromat. With para-dodecylbenzenesulfonic acid; In methanol; toluene; at 100℃; for 1h;Inert atmosphere; The following production was carried out using <strong>[51792-34-8]3,4-dimethoxythiophene</strong> prepared by the same production method as in Example 2 described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of <strong>[51792-34-8]3,4-dimethoxythiophene</strong>, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, <strong>[51792-34-8]3,4-dimethoxythiophene</strong> was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3,4-ethylenedioxythiophene,<strong>[51792-34-8]3,4-dimethoxythiophene</strong>,One in which one methoxy group of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> is substituted with ethylene glycol,And methoxy groups of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in the reaction solution to the amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3,4-ethylenedioxythiophene. The purity of its 3,4-ethylenedioxythiophene was 99.64percent by gas chromatography. The same procedure as in Example 5 was repeated except that dodecylbenzene sulfonic acid monohydrate (moles) was used in place of the cuedemen sulphonic acid monohydrate in Example 5 to change the composition in the reaction solution to N, N-dimethylform The amide was traced by gas chromatography as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 5
  • 14
  • [ 51792-34-8 ]
  • [ 107-21-1 ]
  • C8H12O4S [ No CAS ]
  • [ 126213-50-1 ]
YieldReaction ConditionsOperation in experiment
14.42%Chromat.; 78.58%Chromat. With naphthalene-2-sulfonate; In methanol; toluene; at 100℃; for 3h;Inert atmosphere; The following production was carried out using <strong>[51792-34-8]3,4-dimethoxythiophene</strong> prepared by the same production method as in Example 2 described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of <strong>[51792-34-8]3,4-dimethoxythiophene</strong>, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, <strong>[51792-34-8]3,4-dimethoxythiophene</strong> was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3,4-ethylenedioxythiophene,<strong>[51792-34-8]3,4-dimethoxythiophene</strong>,One in which one methoxy group of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> is substituted with ethylene glycol,And methoxy groups of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in the reaction solution to the amount of <strong>[51792-34-8]3,4-dimethoxythiophene</strong> in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3,4-ethylenedioxythiophene. The purity of its 3,4-ethylenedioxythiophene was 99.64percent by gas chromatography. (Number of moles) of cadmium sulfonic acid monohydrate of Example 52-naphthalene sulfonic acidMonohydrate was used, and the compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 5
  • 15
  • [ 1000623-95-9 ]
  • [ 126213-50-1 ]
  • 3,6-bis(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione [ No CAS ]
  • 16
  • [ 75-27-4 ]
  • [ 126213-50-1 ]
  • [ 211235-87-9 ]
  • [ 204905-77-1 ]
YieldReaction ConditionsOperation in experiment
43%; 22% General procedure: To a 50 mL of Schlenk tube were added 1 or 3 (0.2 mmol, 1.0 equiv), Pd(OAc)2 (10 mol%), dppf (10 mol%) under air, followed by K3PO4·3H2O (0.3 mmol, 1.5 equiv) and Ag2CO3 (0.3 mmol, 1.5 equiv) . The mixture was then evacuated and back filled with N2 (3 times). Bromodichoromethane (0.4 mmol, 2.0 equiv), Ac2O (2 mmol, 190 uL) and CH3CN (1 mL) were added subsequently. The Schlenk tube was screw capped and put into a preheated oil bath (60 C). After stirring for 24 hours, the reaction mixture was cooled to room temperature, diluted with CH2Cl2 and Ethyl Acetate, then filtered with a pad of silica gel. The isolated yield was given by a hydrolysis pathway, in which the concentrated reaction mixture was diluted with 5 mL CH2Cl2 and 10 mL 3 N HCl and stirred over night. The reaction mixture was extracted with dichloromethane (3 times) and the solvent was removed under rotary evaporation. The residue was then purified by a preparative TLC to give product 2 or 4.
 

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